Hydrolysis, Oxidation and Reduction

CATALYSTS FOR
FINE CHEMICAL
SYNTHESIS
Catalysis by
Polyoxometalates
Catalysts for Fine Chemical Synthesis
Catalysts for Fine
Series Editors
Chemical Synthesis
Stan M Roberts, Ivan V Kozhevnikov and Eric Derouane
University o f Liverpool, UK
Volume 2
Previously Published Volumes
Catalysts for Fine Chemical Synthesis Volume 1

Hydrolysis, Oxidation and Reduction
Edited by Stan M. Roberts and Geraldine Poignant
Catalysis by
ISBN 0 471 98123 0

Polyoxometalates
Forthcoming Volumes Ivan Kozhevnikov
Catalysts for Fine Chemical Synthesis Volume 3
Edited by Eric Derouane
ISBN 0 471 49054 7
JO H N W I L E Y & S O N S , L T D
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Library o f Congress Cataloging-in-Publication Data
Catalysis by polyoxometalates / edited by Ivan Kozhevnikov,

p. cm.— (Catalysts for fine chemical synthesis; v. 2)
Includes bibliographical references and index.
ISBN 0-471-62381^1 (acid-free paper)
1. Polyoxometalates. 2. Catalysis. 3. Organic compounds— Synthesis. I. Kozhevnikov,
Ivan. II. Series.
QD474.C375 2002
547'.0304595—dc21
2002072641
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ISBN 0 471 62381 4
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C o n te n ts
Series Preface........................................................................................................ xi
Preface to Volume 2 ............................................................................................ xiii
1 I n tr o d u c tio n .......................................................................................... 1
1.1 Scope and d e fin itio n s ................................................................. 1
1.2 N o m en c la tu re............................................................................... 2
1.3 Historical b ack g ro u n d ................................................................. 2
1.4 Introduction to catalysis by polyoxom etalates....................... 4
R e fe r e n c e s ............................................................................................. 5
2 Properties of Polyoxometalates............................................................ 9
2.1 Structures of polyoxometalates................................................... 10
2.1.1 General p rinciples............................................................ 10
2.1.2 The Keggin stru ctu re....................................................... 10
2.1.3 The W ells-Dawson s tr u c tu re ........................................ 12
2.1.4 The Anderson-Evans s t r u c t u r e ................................... 13
2.1.5 The Dexter-Silverton s t r u c t u r e ................................... 13
2.2 Crystal structure of heteropoly co m p o u n d s............................ 14
2.3 Thermal sta b ility ........................................................................... 15
2.4 Solubility......................................................................................... 19
2.5 Form ation and state in s o lu t io n ............................................... 19
2.5.1 Stability of polyoxometalates in so lu tio n ..................... 19
2.5.2 Polyoxometalates as l i g a n d s ........................................ 22
2.5.3 Isotope e x c h a n g e ............................................................ 23
2.5.4 Kinetics and mechanism of substitution in
polyoxmetalates................................................................. 24
2.6 Acid properties................................................................................ 25
2.6.1 Proton s t r u c t u r e ............................................................ 25
2.6.2 Heteropoly acids in so lu tio n s........................................ 29
2.6.3 Acidity of solid heteropoly a c id s................................... 32
2.7 Redox p ro p erties........................................................................... 37
R e fe r e n c e s .............................................................................................. 42
CONTENTS
CONTENTS IX
3 Synthesis of Polyoxom etalates............................................................. 47

4.5 Deactivation and regeneration of solid heteropoly acid
3.1 General methods of s y n th e sis ................................................. 48 c a ta ly s ts .......................................................................................... 107
3.2 Keggin polyoxometalates.............................................................. 50 R e fe r e n c e s ............................................................................................... 109
3.2.1 12-Molybdosilicicacid, a-H 4[SiMoi204o ]............ 50
3.2.2 12-Tungstosilicic acid, a-H 4[SiWi204o].......... 51 5 Polyoxometalates as Catalysts for Selective Oxidation.................... 117
3.2.3 12-Tungstophosphoric acid, a-H 3[PW |204o]- • • • 51
3.2.4 12-Molybdophosphoric acid, a-H 3[PM oi204o] • • . 51 5.1 Liquid-phase o x i d a t i o n .............................................................. 118
5.1.1 Oxidation with d i o x y g e n .............................................. 118
3.2.5 12-Tungstogermanic acid, a-H 4[GeWi204o] • • • 52
3.2.6 11-Molybdo-1 -vanadophosphoric acid, 5.1.2 Oxidation with hydrogen p e r o x id e ............................... 136
5.1.3 Oxidation with organic p e r o x i d e s ............................... 148
H 4[PM o 11V 0 4o].......................................................... 53
3.2.7 10-Molybdo-2-vanadophosphoric acid, 5.1.4 Miscellaneous o x i d a t i o n s .............................................. 149
5.2 Gas-phase oxidation....................................................................... 149
H 5[PM o10V 2 0 4 o ] ..................................................... 53
5.2.1 General o v e rv ie w ............................................................. 149
3.2.8 9-M olybdo-3-vanadophosphoric acid,
5.2.2 Oxidation c a t a l y s t s ........................................................ 150
H 6[PMo9V304o]...................................................... 53
3.2.9 Transition-metal-substituted tungstophosphates, 5.2.3 R e ac tio n s............................................................................ 151
R e f e r e n c e s ............................................................................................... 159
{PW uM 039} ...................................................... 54
3.3 Wells-Dawson polyoxometalates............................................. 54
6 Miscellaneous Catalytic Applications of Polyoxometalates . . . 167
3.3.1 18-Tungstodiphosphoric acid, H 6[P2Wi8062]. . . 54
3.4 Sandwich-type polyoxom etalates................................................ 55 6.1 Hydrogenation, carbonylation and related reactions. . . . 167
3.4.1 Na,2[WZn3(H20)2(ZnW9034)2] .......................... 55 6.2 Polyanion-stabilised clusters......................................................... 169
3.4.2 N a12[WCo34*I1(H20 )2(CoIIW9034)2] ...................... 55 6.3 Polyoxometalates as catalyst p r e c u r s o r s ................................. 170
R e f e r e n c e s ............................................................................................... 172
3.4.3 Kii[WZnRu 2in(0 H)(H 20 )(ZnW 9034)2] ........... 56
3.4.4 Kio[WZnRhni2(H20)(ZnW 9034)2]..................... 56
3.5 Peroxo polyoxometalates.............................................................. 56 7 Catalysis by Polyoxometalates in Industry......................................... 175
3.5.1 Venturello complex, {P04[W0 (02)2]4}3 - ........... 56 7.1 Acid c a ta ly s is ................................................................................. 176
3.6 Polyoxometalate c a ta ly s ts ..................................................... 57 7.1.1 Hydration o f o le f in s ........................................................ 176
3.6.1 Solid acid c a t a l y s t s .................................................... 57 7.1.2 Synthesis of ethyl acetate from ethylene and
3.6.2 Homogeneous catalysts........................................ 58 acetic ac id ............................................................................ 178
R eferen ces........................................................................................ 59 7.2 Selective o x id a tio n ....................................................................... 179
7.2.1 Oxidation o f methacrolein in methacrylic acid . . . 179
4 Acid Catalysis by Heteropoly Compounds......................................... 61 7.2.2 Oxidation of ethylene to acetic ac id ............................... 180
R e f e r e n c e s ............................................................................................... 182
4.1 General overview...................................................................... 62
4.1.1 The scope of ap p lic a tio n s................................... 62
8 Other Applications of Polyoxometalates.............................................. 183
4.1.2 Mechanistic p rin c ip le s ................................................ 63
4.2 Homogeneous acid catalysis..................................................... 67 8.1 Analytical chemistry........................................................................ 184
4.2.1 Introduction........................................................... 67 8.1.1 Elemental analysis............................................................. 184
8.1.2 Analysis o f biom aterials................................................... 186
4.2.2 Acid-catalysed reactions........................................ 68
8.2 S e p a r a tio n ..................................................................................... 186
4.3 Acid-catalysed reactions in biphasic liquid-liquid systems . 76
8.2.1 Processing o f radioactive w a s t e .................................... 186
4.3.1 Introduction................................................................... 76
8.2.2 Sorption o f g a s e s ............................................................. 187
4.3.2 Biphasic reactions................................................. 77
8.3 Corrosion-resistant coatings......................................................... 187
4.4 Heterogeneous acid c a ta ly s ts ................................................. 80
8.4 Polyoxometalates as additives to inorganic and
4.4.1 Heteropoly acid c a ta ly s ts ................................... 80
organic m a tr ic e s ............................................................................ 188
4.4.2 Heterogeneous catalysis in liquid-solid systems . . 89
8.4.1 Additives in sol-gel m a tr ic e s ......................................... 188
4.4.3 Heterogeneous catalysis in gas-solid systems. . . 99
8.4.2 Additives in polymer m atrices......................................... 189
X CONTENTS
8.5 M em branes................................................................................... 190

8.5.1 Fuel c e lls .......................................................................... 190
8.5.2 Selective e l e c tr o d e s ....................................................... 192
8.5.3 Gas s e n s o rs ...................................................................... 192 C a ta ly s ts fo r F in e C h e m ic a l
8.6 Polyoxometalates in medicine: antiviral and
antitumoral activity............................................................ 192 S y n th e sis
R e fe ren ce s........................................................................................ 193
S eries P re fa c e
I n f c x ............................................................................................................. 195
During the early-to-mid 1990s we published a wide range of protocols, detailing

the use of biotransformations in synthetic organic chemistry. The procedures
were first published in the form of a loose-leaf laboratory manual and, recently,
all the protocols have been collected together and published in book form
{Preparative Biotransformations, Wiley-VCH, 1999).
Over the past few years the employment of enzymes and whole cells to carry
out selected organic reactions has become much more commonplace. Very few
research groups would now have any reservations about using commercially
available biocatalysts such as lipases. Biotransformations have become
accepted as powerful methodologies in synthetic organic chemistry.
Perhaps less clear to a newcomer to a particular area o f chemistry is when to
use biocatalysis as a key step in a synthesis, and when it is better to use one of
the alternative non-natural catalysts that may be available. Therefore we set out
to extend the objective of Preparative Biotransformations, so as to cover the
whole panoply of catalytic methods available to the synthetic chemist, incorp
orating biocatalytic procedures where appropriate.
In keeping with the earlier format we aim to provide the readership with
sufficient practical details for the preparation and successful use of the relevant
catalyst. Coupled with these specific examples, a review of the products that
may be obtained by a particular technology will be reviewed.
In the different volumes of this new series we will feature catalysts for
oxidation and reduction reactions, hydrolysis protocols and catalytic systems
for carbon-carbon bond formation inter alia. Many of the catalysts featured
will be chiral, given the present day interest in the preparation o f single
enantiomer fine chemicals. When appropriate, a catalyst type that is capable
of a wide range of transformations will be featured. In these volumes the
amount of practical data that is described will be proportionately less, and
attention will be focused on the past uses of the system and its future potential.
Newcomers to a particular area of catalysis may use these volumes to
validate their techniques, and, when a choice of methods is available, use the
xii SERIES PREFACE
background information better to delineate the optimum strategy to try to

accomplish a previously unknown conversion.
P re fa c e fo r V o lu m e 2: C a ta ly s is b y
S.M. ROBERTS
I. KOZHEVNIKOV P o ly o x o m e ta la te s
E. DEROUANE
LIVERPOOL, 2002
The chemistry of polyoxometalates (heteropoly acids and heteropoly salts),

started by Berzelius back in 1826, has now reached maturity. But it is still a
rapidly developing field interconnected with many disciplines. Among numer
ous applications of polyoxometalates (Chapter 8), catalysis is by far the most
important. Arguably, catalysis by polyoxometalates has been one of the most
successful areas in fundamental and applied catalysis in the last few decades.
Industry has now used polyoxometalates as catalysts for several large-scale
chemical processes (Chapter 7). On the other hand, the enormous versatility of
polyoxometalates offers significant opportunities for clean synthesis of fine and
specialty chemicals. Consequently, much current research is focussed on vari
ous aspects of catalysis by polyoxometalates. Specific topics relevant to the
field have been reviewed extensively (see references to Chapter 1).
This book presents a survey of recent developments in catalysis by polyox
ometalates, both homogeneous and heterogeneous, focusing on its two major
directions - acid catalysis and selective oxidation. The book is mainly addressed
to academic and industrial chemists engaged with organic synthesis and cataly
sis who are concerned with research and development. The primary target is to
facilitate a better understanding and promote a greater utilisation of catalysis
by polyoxometalates in organic synthesis.
This book is written in the following sequence. Chapter 1 is an introduction,
providing a brief historical overview of the field together with the scope,
definitions and nomenclature of polyoxometalates. Chapter 2 gives a general
review of the key physiochemical properties of polyoxometalates that underlie
the catalysis by polyoxometalates. Knowledge of these properties is essential
for understanding and practicing within the field. Chapter 3 briefly describes
general methods of synthesis of polyoxometalates and provides the reader with
a collection of laboratory procedures for the preparation of polyoxometalates
that are most frequently used as catalysts for organic synthesis. The practical
preparation of some specific acid and oxidation catalysts is also given. Most of
information on catalysis by polyoxometalates is given in the following two
chapters. Chapter 4 describes in detail the homogeneous and heterogeneous
acid catalysis by heteropoly acids and salts. Likewise, Chapter 5 deals with the
catalysis for selective oxidation. Miscellaneous catalytic applications as well as
XIV PREFACE FOR VOLUME 2
some new approaches to catalysis by polyoxometalates are described in Chap

ter 6. Use of polyoxometalates as catalysts in the chemical industry is high
lighted in Chapter 7. Finally, Chapter 8 presents information on various 1 Introduction
applications of polyoxometalates other than catalysis.
Because this is an enormous field that crosses several disciplines, it has not
been possible to describe every relevant work in detail. Consequently, I would
recommend that the interested reader consult the references for further back
ground. I have not attempted to provide a comprehensive bibliography, al
though I hope to have included most of important papers and reviews
published by the mid-2001.
CONTENTS
The author wishes to acknowledge several persons who directly or indirectly
contributed to this book. I am especially grateful to Professor Kiavdii I. 1.1 SCOPE AND DEFINITIONS.............................................................................................................. 1
1.2 N o m e n c l a t u r e ........................................................................................................................... 2
Matveev who first introduced me, in the early 1970s, to the exciting chemistry
1.3 H istorical b a c k g r o u n d ....................................................................................................... 2
and catalysis by polyoxometalates and who encouraged and supported our 1.4 I ntroduction to catalysis by polyoxometalates .......................................................... 4
research in the 1970-80s in Boreskov Institute of Catalysis, Novosibirsk. I R eferences .............................................................................................................................................. 5
wish also to thank the late Professor Kirill Zamaraev for valuable discussions
and support at that time. Sincere thanks are due to Professor Herman van
Bekkum for his friendship and most enjoyable collaboration during my 1.1 SCOPE AND DEFINITIONS
working in Delft in 1993-96.1 wish to thank Professors Yusuke Izumi, Makoto
Misono, and Yoshio Ono for their hospitality and most valuable discussions on Polyoxometalates belong to a large class of nanosized metal-oxygen cluster
catalysis by polyoxometalates during my visits to Japan. I should like to anions.11,2^These form by a self-assembly process, typically in an acidic aqueous
acknowledge Professor Michel Fournier for stimulating discussions and collab solution as illustrated by equations 1.1 and 1.2 and can be isolated as solids
oration during my stay in Lille. Professors Eric Derouane and Stan Roberts of with an appropriate countercation, for example, H +, alkali metal cation,
Liverpool University and Dr Martin Röthlisberger of John Wiley & Sons are N H 4+, etc.
thanked for their encouragement and support throughout this project.
I thank all my graduate students, postdoctoral fellows and colleagues, whose
8 H + + 7 W0 42- —> [W70 24]6_ + 4 H2O (LI)
names appear in the bibliography, for their contribution to our research. I am
grateful to Drs Geraldine Poignant and Rafiq Siddiqui who helped with the 23 H + + H P 0 42- + 12 M o0 42- -> [PM oi2O40]3' + 12H20 (1.2)
preparation of the manuscript. Finally, and most importantly, I thank my wife,
Elena, for her patience and support. Generally, two types of polyoxometalates are distinguished as based on their
chemical composition - isopoly anions and heteropoly anions. These anions
Ivan Kozhevnikov may be represented by the general formulas:^’2-1
Liverpool, 2002
[MmOy]p~ Isopoly anions
[XxMmOy]q_(x < m) Heteropoly anions
where M is the addenda atom and X is the heteroatom also called the central
atom when located in the centre of the polyanion. The distinction between the
two groups is frequently artificial, especially in the case of mixed-addenda
polyoxometalates.[2] Heteropoly compounds are by far more important for
catalysis as well as for other applications; hence this book is mainly focused
on them. Heteropoly acids - strong acids composed of heteropoly anions and
protons as the countercations - constitute a special case of heteropoly com
pounds that is particularly important for catalytic applications.
2 CATALYSIS BY POLYOXOMETALATES INTRODUCTION 3
The most common addenda atoms are molybdenum or tungsten, less fre basis for the determination of phosphorus that has been widely used since. By
quently vanadium or niobium, or mixtures of these elements in their highest 1908, approximately 750 heteropoly compounds had been reported. However,
oxidation states (d°, d 1). Much broader range of elements act as the heteroa the structure of polyoxometalates had remained a mystery for more than a
toms; as such, almost all elements of the Periodic Table can be incorporated in century since their discovery. Werner,161 Miolati,171 Rosenheim,181 and Pauling191
heteropoly anions, most typical ones being P5+, As5+, Si4+, Ge4+, B3+, etc. proposed structures based on sharing metal-oxygen polyhedra. It was Keggin
Molybdenum(VI) and tungsten(VI) are the best polyoxometalate formers as who in 1933 solved the structure of the most important 12:1 type of heteropoly
the result of a favourable combination of ionic radius and charge and of anions by a powder X-ray diffraction study of H 3[PW i2C>4o]- 5H2O .1101 This
accessibility of empty d orbitals for metal-oxygen k bonding/21 structure, now named after its discoverer, contained 12 WC>6 octahedra linked
by edge and corner sharing, with the heteroatom occupying a tetrahedral hole in
the centre. In 1948, Evans1111 determined the structure of another widespread
1.2 NOMENCLATURE type - the Anderson’s heteropoly anion (6:1 series) - by single-crystal X-ray
analysis of [re 6+M o60 24]6~ salts; this structure is now often referred to as the
A systematic nomenclature of polyoxometalates has been developed/2,31 It uses Anderson-Evans structure. In 1953, Dawson1’21 reported the next new structure
a labelling system for the metal atoms and, in some cases, for the oxygen atoms (now frequently referred to as the Wells-Dawson’s) of a 18:2 heteropoly anion
to avoid ambiguity. The resulting names, however, are too long and compli [P2W i8062]6—. This structure was shown to be closely related to the Keggin
cated; these are practically never used for routine purposes. structure. In 1968, Dexter and Silverton1131 reported the X-ray structure of
In catalytic applications, only a relatively small number of well-known types [Ce4+M oi2042]8_ and showed the large Ce heteroatom to be in a CeOi2 central
of polyoxometalates have been involved so far, largely limited to the Keggin icosahedron. By the early 1970s, the chemistry of polyoxometalates had been
compounds and their derivatives. Usually, simplified conventional nomenclat greatly expanded. This period is associated with extensive work o f many groups
ure, sometimes even trivial names, are sufficient for reporting and retrieving and especially those of Souchay (France), Ripan (Rumania), Spitsyn (USSR)
information in the field. Here we adopt the current nomenclature that treats and Baker (USA). In the 1980-90s, the number of groups involved in the field
polyoxometalates (also referred to as heteropoly anions, polyoxoanions, or increased enormously in parallel with expanding applications of polyoxometa
polyanions) as quasi coordination complexes/21 The heteroatom, if present, is lates. Recently Baker and Glick1141 reviewed the history of polyoxometalate
considered as the central atom of a complex, and the addenda as the ligands. In chemistry and contributions of various groups to date. By 1995, the X-ray
the formulas of heteropoly anions, the heteroatoms are placed before the structures of approximately 180 polyoxometalates had been reported.1’51
addenda, and the countercations before the heteroatoms; the heteropoly Among them, salts of giant heteropoly anions such as [Lai6Asi2W i480524]76-
anion is placed in square brackets and thus separated from the countercations, (ion mass ca. 40000, diameter 40 A) and others were prepared and characterised
as illustrated by the following examples: by Müller et a/.1’61 The application of modern characterisation techniques had
led to much better understanding of the structural principles of polyoxometa
[SiWi2C>4o]4~ 12-tungstosilicate or dodecatungstosilicate lates and their properties. However, there is still plenty of scope for further
work in this field, as many fundamental questions regarding the structural
H3[PMoi204o] 12-molybdophosphoric acid principles, mechanisms of synthesis and reactivity of polyoxometalates remain
unanswered.
N a5[PMoioV204o] sodium decamolybdodivanadophosphate The chemistry of polyoxometalates has been reviewed extensively. This
includes classical monographs by Souchay1’’171 and Pope121 and also by Niki
For simplicity, the countercations and the charge of polyanion and even the tina1’81 and a large number of review articles, for example Ref.1’5,19-261 Much
oxygen atoms may be omitted; for example, N a6[P2M oi80 62] may be abbrevi useful information about the chemistry and various applications of polyoxo
ated to {P2M oi80 62} or P2M oi8. metalates, including the nomenclature, synthesis of organic and organometallic
derivatives of polyoxometalates, electron-transfer reactions, very large polyox
ometalate clusters, solution equilibria, polyoxometalate-based molecular ma
1.3 HISTORICAL BACKGROUND terials, scanning probe microscopy of polyoxometalate surfaces, photo- and
electrochromism, and application of polyoxometalates in medicine, can be
The history of polyoxometalates dates back to 1826 when Berzelius[41 discovered found in the recent collections/27’281
the first heteropoly salt, ammonium 12-molybdophosphate. Later on in 1848,
Svanberg and Struve151 introduced this compound in analytical chemistry as the
1.4 INTRODUCTION TO CATALYSIS BY POLYOXOMETALATES the production of ethyl acetate using a heteropoly acid catalyst was launched by
BP Amoco (Chapter 7).
Among numerous applications of heteropoly compounds, catalysis is by far the Many reviews on catalysis by polyoxometalates have been published. Otake
most important. Presently, over 80% of the patent applications concerning and Onoda1331 (1976) reviewed early works on heterogeneous catalysis; M at
with polyoxometalates is related to catalysis.1291 First attempts to use polyox- veev1341 (1977), Matveev and Kozhevnikov135-371 (1980, 1982, 1983), Kozhevni
ometalates as catalysts can be traced back to the beginning of the twentieth kov138,391 (1987, 1998), and Jansen et a /.1401 (1994) discussed the acid and
century. Compilations of early works up to 1973 are available.1301 oxidation catalysis in liquid phase; Izumi et a lP 2] (1992) and Ono[411 (1992)
Systematic investigation of catalysis by polyoxometalates began in the early gave comprehensive survey of polyoxometalate catalysis to that date; Kozhev
1970s when the great potential of these compounds for catalytic applications nikov142,431 (1993, 1995) described catalysis for fine chemicals synthesis; Mis
became apparent. Most of pioneering work at that time was carried out in ono144,451 (1987, 1988, 1993), Moffat[46] (1987, 1989), Corma1471 (1995), Mizuno
Japan (Izumi, Misono, Ono, Otake, Yoneda and co-workers) and Russia and Misono1481 (1998), and Misono (2001 )1491 reviewed heterogeneous acid and
(Matveev and co-workers). The string of successful industrial applications of oxidation catalysis by polyoxometalates; Misono and Nojiri[311 (1990) de
polyoxometalate catalysts in the 1970-80s triggered an explosion of innovative scribed industrial applications of polyoxometalate catalysts; Mizuno and Mis-
research in this field; the rapid development has continued to date and is bound ono[50J (1998) described light alkane functionalisation by polyoxometalate
to move on in the future. catalysis; Okuhara, Mizuno, and Misono[511 (1996) published the most compre
Heteropoly compounds have several advantages as catalysts, the most hensive review of the field to that date; Papaconstantinou1521 (1989, 2001) and
important being their multifunctionality and structural mobility. On the one Yamase[531 (1998) addressed photocatalysis; Ishii and Ogawa[54] (1990) de
hand, they (heteropoly acids) have a very strong Bronsted acidity; on the scribed catalysis for hydroperoxide oxidations; Hill and Prosser-McCartha[55]
other, they are efficient oxidants, exhibiting fast reversible multielectron (1995) and Neumann1561 (1998) discussed transition metal substituted polyox
redox transformations under mild conditions. Their acid-base and redox prop ometalates as catalysts for liquid-phase oxidation; Cavani1571 (1998) described
erties can be varied over a wide range by changing the chemical composition. catalysis for vapour-phase oxidation of hydrocarbons; Kuznetsova et al.[59]
Solid heteropoly compounds possess a discrete ionic structure, comprising (1999) addressed the use of polyoxometalates for studies of catalyst active
fairly mobile structural units - heteropoly anions and countercations - unlike sites; and Misono1581 (2000) reviewed ‘green’ aspects of heteropoly acid cataly
the network structure of, e.g., zeolites and metal oxides. The structure is sis. The recent monograph by Moffat1601 describes the surface properties of
frequently preserved upon substitution or oxidation/reduction and manifests polyoxometalates and their use for heterogeneous catalysis. Centi, Cavani, and
itself to exhibit extremely high proton mobility and a ‘pseudoliquid phase’ Trifiro1611 reviewed the heterogeneous catalysis by polyoxometalates for select
(Chapter 2). On top of that, many heteropoly compounds have a very high ive oxidation in their recent book.
solubility in polar solvents and fairly high thermal stability in the solid
state.
Because of their unique properties heteropoly compounds are promising REFERENCES
acid, redox, and bifunctional (acid and redox) catalysts. The catalytic reactions
can be performed in homogeneous as well as in heterogeneous (gas-solid, 1. P. Souchay, Ions Mineraux Condenses; Masson: Paris, 1969.
liquid-solid or biphasic liquid-liquid) systems. Heteropoly compounds are 2. M.T. Pope, Heteropoly and Isopoly Oxometalates\ Springer: Berlin, 1983.
frequently used as model systems for fundamental research, providing unique 3. (a) Y. Jeannin, M. Fournier, Pure Appl. Chem. 1987, 59, 1529. (b) Y.P. Jeannin,
opportunities for mechanistic studies on the molecular level. At the same time, Chem. Rev. 1998, 98, 51.
they have become increasingly important for applied catalysis. 4. J.J. Berzelius, Poggendorffs Ann. Phys. Chem. 1826, 6, 369, 380.
In the 1970—80s, several new industrial chemical processes utilising polyox 5. L. Svanberg and H. Struve, J. Pract. Chem. 1854, 61, 449.
6. A. Werner, Ber. Dtsch. Chem. Ges. 1907, 40, 40.
ometalate catalysis were developed and commercialised in Japan.131,321 The first
7. A. Miolati and R. Pizzighelli, J. Prakt. Chem. 1908, 77, 417.
commercial process was the liquid-phase hydration of propene to 2-propanol
8. A. Rosenheim, Handbuch der Anorganischen Chemie; Abegg, R., Auerbach, F., Eds;
launched in 1972. It followed by the vapour-phase oxidation of methacrolein to Hirzel Verlag: Leipzich, 1921; Vol. 4, Part 1, ii, pp. 997-1064.
methacrylic acid in 1982, the liquid-phase hydration of isobutene for its separ 9. L. Pauling, J. Am. Chem. Soc. 1929, 51, 2868.
ation from the butane-butene fraction in 1984, the biphasic polymerisation 10. J.F. Keggin, Proc. Roy. Soc. London 1934, A 144, 75.
of tetrahydrofuran to polymeric diol in 1985, the hydration of n-butenes to 11. H.T. Evans, Jr. J. Am. Chem. Soc. 1948, 70, 1291.
2-butanol in 1989 and other processes. More recently, in 1997, the direct oxida 12. B. Dawson, Acta Crystallogr. 1953, 6, 113.
tion of ethylene to acetic acid was industrialised by Showa Denko and, in 2001, 13. D.D. Dexter and J.V. Silverton, J. Am. Chem. Soc. 1968, 90, 3589.
14. L.C.W. Baker and D.C. Glick. Chem. Rev. 1998, 98, 3. 49. (a) M. Misono, Chem. Commun. 2001, 1141. (b) T. Okuhara, N. Mizuno and M.
15. G.M. Maksimov. Russ. Chem. Rev. 1995, 64, 445. Misono, Appl. Catal. A., 2001, 222, 63.
16. (a) A. Müller, W. Plass, E. Krickemeyer, S. Dillinger, H. Bögge, A. Armatage, A. 50. N. Mizuno and M. Misono, in Catalytic Activation and Functionalisation o f Light
Proust, C. Beugholt, U. Bergmann, Angew. Chem. Int. Ed. Engl. 1994, 33, 849. (b) Alkanes. Advances and Challenges; Derouane, E.G., Haber, J., Lemos, F., Ribeiro,
A. Müller, P. Kögerler, C. Kuhlmann, Chem. Comm. 1999, 1347. (c) O. Delgado, A. F.R., Guisnet, M. Eds; NATO ASI Series; Kluwer: Dordrecht, 1998, p. 311.
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17. P. Souchay, Polyanions et Polycations; Gauthier-Villars: Paris, 1963. A. Mylonas, A. Troupis and E. Papaconstantinou, in Polyoxometalate Chemistry
18. E.A. Nikitina, Geteropolisoedineniya (Heteropoly compounds); Goskhimizdat: from Topology via Self-Assembly to Applications; Pope, M.T., Müller, A. Eds;
Moscow, 1962. Kluwer: Dordrecht, 2001, p. 417.
19. L.P. Kazanskii, E.A. Torchenkova and V.I. Spitsyn, Russ. Chem. Rev. 1974, 43, 525. 53. T. Yamase, Chem. Rev. 1998, 98. 307.
20. T.J.R. Weakley, Structure and Bonding 1974, 18, 131. 54. Y. Ishii and M. Ogawa, in Reviews on Heteroatom Chemistry; Vol. 3; Ohno, A.,
21. G.A. Tsigdinos, Top. Curr. Chem. 1978, 76, 1. Furukawa, N. Eds; MYU: Tokyo, 1990; Vol. 3; p. 121.
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24. Y. Jeannin, G. Herve and A. Proust, Inorg. Chim. Acta 1992, 198-200, 319. 57. F. Cavani, Catal. Today 1998, 41, 73.
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29. D.E. Katsoulis, Chem. Rev. 1998, 98, 359. Kluwer: New York, 2001.
30. Molybdenum Catalyst Bibliography (1950-1964); Supplement 1 (1965-1967); Sup
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Ann Arbor, MI.
31. M. Misono and N. Nojiri, Appl. Catal. 1990, 64, 1.
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Reactions; Kodansha/VCH: Tokyo, 1992.
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Trav. Chim. Pays-Bas 1994, 113, 115.
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London, 1992; p. 431.
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43. I.V. Kozhevnikov, Catal. Rev. Sei. Eng. 1995, 37, 311.
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2 Properties o f Polyoxom etalates
CONTENTS
2.1 Structures of p o l y o x o m e t a l a t e s .......................................................................................... 10
2.1.1 G eneral principles..................................................................................................................... 10
2.1.2 T he K eggin structure............................................................................................................... 10
2.1.3 The W ells-D a w so n s t r u c t u r e ........................................................................................... 12
2.1.4 The A nd erson -E van s structure........................................................................................... 13
2.1.5 The D exter-S ilverton structure.......................................................................................... 13
2.2 C rystal STRUCTURE of heteropoly com pounds ................................................................. 14
2.3 T hermal s t a b il it y ..................................................................................................................... 15
2.4 So l u b i l i t y .................................................................................................................................. 19
2.5 F ormation and state in s o l u t i o n ..................................................................................... 19
2.5.1 Stability o f p olyoxom etalates in s o lu tio n ........................................................................ 19
2.5.2 P olyoxom etalates as l i g a n d s ........................................................................................... 22
2.5.3 Isotop e e x c h a n g e ..................................................................................................................... 23
2.5.4 Kinetics and m echanism o f substitution in p o ly o x o m eta la tes................................. 24
2.6 A cid pro perties ............................................................................................................................ 25
2.6.1 Proton s t r u c t u r e ..................................................................................................................... 25
2.6.2 H eterop oly acids in s o l u t i o n s ........................................................................................... 29
2.6.3 A cidity o f solid heteropoly a c i d s ..................................................................................... 32
2.7 R edox p r o p e r t ie s ..................................................................................................................... 37
R eferences ............................................................................................................................................... 42
Properties of many polyoxometalates have been studied in detail and thor

oughly reviewed11^ (see also Section 1.3). A variety of physicochemical and
spectroscopic techniques have been applied for the characterisation of polyox
ometalates both in solution and in solid state. For methods of characterisation
in solution, the reader should consult the monograph by Pope,[1] for solid-state
characterisation, the review by Okuhara et alP c^ and the monograph by M of
f a t ^ will be most useful.
In this chapter, we will discuss some physicochemical properties of polyox
ometalates that are of great importance for their catalytic applications. These
include the structure of polyoxometalates, their thermal stability, solubility,
formation and state in solution, acid-base and redox properties.
CATALYSIS BY POLYOXOMETALATES PROPERTIES OF POLYOXOMETALATES 11
10
2.1 STRUCTURES OF POLYOXOMETALATES diameter of ca. 1.2 nm and is composed of a central tetrahedron XO4 sur
rounded by 12 edge- and corner-sharing metal-oxygen octahedra MO ö (Figure
2.1.1 GENERAL PRINCIPLES 2.1).[l’61 The octahedra are arranged in four M3O 13 groups. Each group is
Dozens of structural types and stoichiometries of polyoxometalates are known

to date. The minimum degree of condensation of addenda atoms is arbitrarily
set to be in the range of 2 to 6.1K2al The maximum can go to as high as a few
hundred. For example, the giant heteropoly tungstate [L aiöA snW ugC ^]76-
(relative molecular mass ca. 40000, diameter 4nm) includes 28 heteroatoms
(La, As) and 148 addenda atoms (W).131
Two general principles apply to polyoxometalate structures:11,41
1. Addenda atoms occupy a metal-oxygen polyhedron MOx that is most

commonly an octahedron. In this polyhedron, the metal atom is displaced
from the inversion centre towards the peripheral vertice because of m etal- Figure 2.1 Bond (a), polyhedral (b) and space-filling (c) representations of the Keggin
oxygen n bonding. structure of the [XM^CLto]*-8 anion (a isomer).111
2. Structures with M 0 6 octahedra that contain more than two free vertices are
generally not found among the typical polyoxometalates. This is known as formed by three octahedra sharing edges and having a common oxygen atom
the Lipscomb restriction,151 which may be explained as a result of the strong which is also shared with the central tetrahedron XO4. The total assemblage
trans influence of the terminal M = 0 bonds that facilitates dissociation of contains 40 close-packed oxygen atoms. The oxygens are of four types: twelve
MO3 from the polyanion. terminal M = O, twelve edge-bridging angular M -O -M shared by the octahe
dra within a M 3O 13 group, twelve corner-bridging quasi-linear M -O -M con
According to Pope and Müller,141 it is convenient to discuss the variety of necting two different M 3O 13 groups, and four internal X -O -M . These oxygens
polyoxometalate structures starting from a few highly symmetrical ‘parent’ can be discriminated by 170 NM R.[1] The corresponding bonds exhibit charac
polyanions; then many other polyoxometalate structures may be considered teristic infrared bands in the range of 600-1100 cm-1.111
as their ‘derivatives’. There are three such parent structures, with a tetrahedron, Each of the M 3O 13 groups can be rotated 60° about its 3-fold axis which
an octahedron, and an icosahedron as their central polyhedron XOn (n = 4, 6 leads to geometrical isomers. The structure shown in Figure 2.1 is the most
or 12) that determines the symmetry of the whole polyanion. These structures, common a isomer of the Keggin structure. Rotation of one of its M3O 13 groups
that have already been mentioned, are: the Keggin structure (Td symmetry); the produces the ß isomer; its structure is shown in Figure 2.2. In some cases, these
structure of a hypothetical anion {XM12O38} (Oh), that has not yet been isomers can be separated, e.g., by fractional crystallisation. Rotation of two,
observed itself but its derivatives, for example the Anderson-Evans anion three or all four M3O 13 groups produces the y, 8, and e isomer, respectively.111
|XM(,0 24}, are well known; and the Dexter-Silverton structure (Ih). These
structures will be briefly discussed below.
2.1.2 THE KEGGIN STRUCTURE
This is the First characterised161 and the best-known structure that is adopted by
many polyoxometalates. Among a wide variety of heteropoly compounds, the
Keggins are the most stable and more easily available. These, together with
some of their derivatives, are the most important for catalysis.
The Keggin heteropoly anions are typically represented by the formula a b
[XM12O40]*-8, where X is the heteroatom, .v is its oxidation state, and M is
the addenda atom (usually Mo6+ or W6+). The M6+ ions can be substituted by Figure 2.2 The Keggin structure of the [XMutTtof 8 anion: (a) a isomer and (b) ß
many other metal ions, e.g., V5+, Co2+, Zn2+, etc. The Keggin anion has a isomer.
12 CATALYSIS BY POLYOXOMETALATES PROPERTIES OF POLYOXOMETALATES 13
Lacunary derivatives of the Keggin anion result from the removal of one or
more M atoms. Examples of three lacunary derivatives (one monovacant and
two trivacant) of the a-Keggin anion are shown in Figure 2.3. The two triva-
cant species correspond to loss of a corner-shared group of MC>6 octahedra (A-
type {XM9}) or an edge-shared group (B-type {XMg}).1' 1 Such species can
assemble into larger polyoxometalate structures, either directly or with incorp
oration of metal ion linkers.
Figure 2.4 The Wells-Dawson structure of the [X2Mig062]2x 16 anion (a isomer).
2.1.4 THE ANDERSON-EVANS STRUCTURE
This example represents a different structural type with an octahedron as a

central polyhedron. The Anderson-Evans structure is adopted by 6-heteropoly
anions (e.g. [Te6+M o6024]6~).[1,81 It consists of six coplanar MC>6 octahedra
arranged in a closed ring sharing edges. The heteroatom occupies the octahe
dral pocket in the centre of the ring (Figure 2.5).
c d
Figure 2.3 The structures of the a-Keggin anion [XMi204o]x 8 (a) and its
lacunary derivatives: (b) monovacant, (c) trivacant A-{XM9}, and (d) trivacant
B-{XM9}.[1)
2.1.3 THE W ELLS-DAWSON STRUCTURE

Figure 2.5 The Anderson-Evans structure of the [Te6+Mo6024]6 anion.[11
One of these derivatives is the Wells-Dawson dimeric (2:18) heteropoly anion
[X2M i8062]2x-I6(M = M o6+ or W6+,X = P5+ or As5+). Its structure (a iso
mer) is shown in Figure 2.4. The anion consists of two trivacant lacunary Keggin 2.1.5 TH E DEXTER-SILVERTON STRUCTURE
species A-{XM<>} linked directly across the lacunae. The Wells-Dawson struc
ture contains two M3O 13 groups. A 60° rotation o f one of these groups about its A less common type of 12-heteropoly anions [XM12O42]*-12, where M is
3-fold axis gives the ß isomer. The molybdenum anion is chiral because of a molybdenum(VI) and X is cerium(IY), uranium(IV), or thorium(IV), adopt
displacement of the Mo atoms within their M o 0 6 octahedra. The tungsten this structure (Figure 2.6). In this anion, the central atom is surrounded by
complex shows no such chirality probably because of the greater rigidity of the twelve oxygen atoms that form an icosahedron as a central polyhedron. The
tungsten framework.11,71 MC>6 octahedra are arranged in face-sharing pairs.[l,9]
Figure 2.6 The Dexter-Silverton structure of the PCM12O42F 12 anion.111
Figure 2.7 Crystal packing of H3[PWi204o]-6H20 .ll4a]

2.2 CRYSTAL STRUCTURE OF HETEROPOLY COM POUNDS
Crystals of heteropoly compounds usually have very low lattice energies.
Generally, solid heteropoly compounds (heteropoly acids and salts) form ionic The anionic charge of the big heteropoly units is delocalised over a large
crystals.1101 Such solids frequently have large interstices between the big hetero number of atoms, thus greatly diminishing electrostatic attractions. The exter
poly anions which accommodate a large amount of water of crystallisation (up ior of typical heteropoly anions consists of oxygens that are strongly polarised
to 30 molecules per heteropoly unit and more) as well as the countercations. towards the addenda, and hence nonpolarisable in other directions. These
These water molecules are hydrogen-bonded together and are often zeolitic, i.e. nonbasic oxygens lack the ability to form hydrogen bonds of normal
easily and reversibly removable from the solid which can be usually done by strength.1101 As a result, heteropoly anions are weakly solvated in solution,
heating to 100-150 °C. The crystal structure of heteropoly compounds varies and the crystal structure of heteropoly compounds is frequently quite mobile
with the extent of hydration, for example 12-tungstophosphoric acid exhibits unlike the rigid network structure of metal oxides or zeolites. Such structural
different packing arrangements as the hydration water is lost (Table 2.1). The flexibility is im portant when using these compounds as solid catalysts120,11’121
hydration-dehydration process is frequently accompanied by changing (Chapters 4 and 5).
(expanding or shrinking) the volume of the crystal cell. N ot only water but Misono et al)120,11,121 advanced a special structural classification that recog
also many polar organic molecules, such as alcohols, ketones, ethers, amines, nises the importance of structural flexibility of solid heteropoly compounds. This
sulfoxides, etc., can enter and leave the structure - which can have im portant classification, which is now widely adopted in heterogeneous catalysis by poly-
consequences on heterogeneous catalysis by solid heteropoly compounds oxometalates, distinguishes the primary structure (polyoxoanion structure), the
(Section 4).l2c’n >12] The nature of organic solvates and their thermal decom secondary structure (crystal structure and packing), and the tertiary structure
position have been investigated.1131 (texture o f solids, i.e. particle size, porosity, surface area, distribution of protons,
Figure 2.7 shows a fragment of the structure of the Keggin heteropoly acid etc.). This structural hierarchy is schematically illustrated in Figure 2.8.
H 3[PW i 20 4o] • 6H20 determined by single-crystal X-ray analysis.11431 The crys
tal lattice is formed by packing heteropoly anions into a body-centred cubic
structure. Doubly hydrated protons H 5C>2+ link four neighbouring anions by 2.3 THERM AL STABILITY
forming hydrogen bonds with the terminal W = 0 oxygens.
The thermal stability of heteropoly compounds is of great importance for their
Table 2.1 Crystal structures of 12-tungstophosphoric acid hydrates. use in heterogeneous catalysis.12o,2fl Some compounds are fairly stable and can
Hydrate Space group Reference be applied as catalysts at moderately high temperatures, up to 300-350 °C. The
thermal stability, however, may not be sufficient for catalyst regeneration, for
H3[PW1204o] 29H20 cubic Fd3m 14b example, for burning coke that may form on the catalyst surface (Section 4.5).
H3[PWi20 4o] 21H20 orthorhombic Pcca 14c
triclinic PI Thermal decomposition of polyoxometalates (to eventually form a mixture
H3[PWi20 4o] 14H20 14d
H3[PW,20 4o] 6H20 cubic Pn3m 14a of oxides) is a complex multistage process.12fl The catalyst activity may be
irreversibly lost at an early stage of decomposition. For example, solid acid
Primary structure Secondary structure Tertiary structure

(anion structure) (crystal structure, crystal (texture: particle size, porosity,
packing) surface area, etc.)
Figure 2.8 Structural hierarchy of heteropoly compounds.[2c]

Figure 2.9 Derivative thermogravimetry for H3[PW1204o] hydrate.
catalysts based on tungsten heteropoly acids (e.g. H 3[PWi204o]) probably lose
activity at the onset of thermal decomposition of the Keggin structure, when of all acidic protons and the beginning of decomposition of the Keggin struc
the acid protons are lost (see below), i.e. well before the formation of WO3 and ture J2a,2c,2f’10^
P2O5 is complete. Generally, Keggin-type heteropoly compounds are the most stable among
The thermal stability is usually determined by thermal analytical methods various polyoxometalates. The decomposition temperature (°C) for the most
(thermal gravimetric analysis (TGA), differential thermal analysis (DTA), and typical Keggin heteropoly acids, as estimated from TGA, decreases in the
differential scanning calorimetry (DSC)) frequently in combination with other following series:Î6a]
techniques, such as X-ray diffraction, infrared spectroscopy, solid state NM R,
etc., Tsigdinos[15] introduced a simple method that allows estimating the ther H3[PW120 4o] < H^SiWuO«] < HatPMouCM < H^SiMouO«,]
mal stability of heteropoly compounds. This method includes heat treatment
followed by a solubility test. If, after heating, the compound is soluble in water 465 445 375 350
its structure is deemed to remain intact; otherwise the structure has decom
posed. For practical purposes, the onset of decomposition should be taken into
A great deal of caution should be taken when comparing the thermal account. Such data have been compiled[2a] and some of them are presented in
stabilities from different sources. The decomposition temperatures are subject Table 2.2.
to many parameters such as the heating rate, the amount of sample, the shape High-temperature exothermic peaks observed in DTA and DSC studies have
of crucible, the purity of the sample, the atmosphere, etc. On top of that, the been used to estimate the thermal stability of heteropoly acids.(2f] These peaks
decomposition on the surface of the sample may occur at a lower temperature
than in the bulk. Table 2.2 The onset of thermal decomposition
of solid heteropoly acids[2al.
Figure 2.9 shows the TGA profile for H3[PWi2O40] hydrate. Three main
peaks can be observed: (1) a peak at a temperature below 100 °C corresponding HPA T(°C) Reference
to the loss of physisorbed (zeolitic) water (a variable amount depending on the 400 15,17
H3[PW12O40]
number of hydration waters in the sample); (2) a peak in the temperature range H 3[PM oi20 4o] 300 15,17
of 100-280 °C centred at about 200 °C accounted for the loss of ca. 6H20 H4[SiWI204o] 370 15,17
molecules per Keggin unit, corresponding to the dehydration of a relatively H4[SiMoi2O40] 200 15
stable hexahydrate H 3IPW12O40] • 6H2O in which the waters are hydrogen- H3[BW12O40] 240 15,17
H 4[PW h VO40] 300 15,18,19
bonded to the acidic protons; and (3) a peak in the range of 370-600 °C centred 400 19
H 4[PM o h V04 o]
at about 470 °C due to the loss of 1.5 H2O molecules corresponding to the loss
may be attributed to the complete decomposition of the Keggin structure to H4[PM oii VO40] stabilises the structure, while the presence of water vapour
form a mixture of oxides. This method gives the decomposition temperatures enhances its desintegration/27b]
that are too high to represent the stability of solid heteropoly acid catalysts. For
example, for the above series of acids, Izumi et a / / l6bl reported the decom
position temperatures of 610, 540, 405, and 375 °C, respectively. Similar results 2.4 SOLUBILITY
were also reported by Varga et o/.l' 6c]
Heteropoly salts are frequently more stable than the parent acids. The relative As the lattice energies of heteropoly compounds are low, and so are the
stabilities, however, depend on the countercation. Thus, for H 3IPM012O40] and solvation energies of heteropoly anions, the solubility of heteropoly com
its salts the following decomposition temperatures (°C), estimated from DTA pounds largely depends on the solvation energy of the cation. Heteropoly
peaks, were reported/ 201 acids are extremely soluble in water and oxygen-containing organic solvents
such as lower alcohols, ethers, etc., but not in nonpolar solvents such as
Ba2+,C o2+(400) < Cu2+, Ni2+(410) < H +,C d 2+(420) < Ca2+, M n2+(427) benzene or petroleum ether. For example, the solubility (wt%) of the acid
H 4[SiMoi204o] • 8H20 is 88 in water, 86 in ethyl acetate, and 85 in diethyl
< Mg2+(437) < La3+,C e3+(457)
ether at 25 °C/ 151 However, the solubility drops sharply when anhydrous het
The acidic cesium salt C s2.5H0.5[PW i 204 o] is more stable than H3IJPW12O40]; no eropoly acids and thoroughly dried nonaqueous solvents are used. Salts with
decomposition of the salt was observed at 500 °C/ 211 The Wells-Dawson het small cations, such as Li+ or N a+, are readily soluble as well. In contrast, salts
eropoly salts K6[P2W 180 62] and K yfPiVW nC^] were found to be stable up to of large cations, e.g., K+, Cs+, NH4+, etc., are insoluble in water. Salts of large
400°C.[22] organic cations such as tetrabutylammonium are insoluble in water but soluble
Partially reduced heteropoly acids may be more stable than the fully oxidised in organic solvents/ ' 1 which is frequently used for the isolation of polyoxome-
forms. For example, 12-molybdosilicic acid reduced by two or four electrons talates as well as for catalysis in organic media (Section 5.1).
per Keggin unit was found to decompose at higher temperatures than the
oxidised form/ 2a’231
Partially decomposed 12-molybdophosphoric acid may be reconstructed 2.5 FORMATION AND STATE IN SOLUTION
under wet atmosphere/2f’24,25] As found by in situ XRD and 31P NM R, the
thermal decomposition of H 3[PMoi204o] hydrate occurs in several steps, the The majority of polyoxometalates have been obtained and studied in aqueous
first two steps being reversible, as shown in Scheme 2 .l/ 261 The compound solution. Nonaqueous chemistry, although important for various applications,
H x[PM oi20 38.5+x/2] rehydrates into H 3[PMoi2O40] hydrate upon exposure to is less developed. Nearly spherical Keggin anions have a very low negative
wet air. charge density on the peripheral oxygens, and the exterior oxygens form only
very weak hydrogen bonds. As a result, the anions are weakly solvated in
solution. Their hydrodynamic radii, as shown by viscosity and diffusion meas
2 0 0 -3 5 0 °C 385°C urements, frequently coincide with their crystallographic radii.1101 Heteropoly
H ,[P M o 120 4 o] n H 20 H 3[PM o 12O 40] - - - H x[PM o 120 38.5+x/2](x = 0 . 1- 1.0)
anions are typically very weak ligands. The latter, however, does not apply to
- n H 20
lacunary anions (see below). The Keggin heteropoly electrolytes (acids and
salts) are usually fully dissociated in solution.11,101
2.5.1 STABILITY OF POLYOXOMETALATES IN SOLUTION
In solution of a polyoxometalate, several species frequently exist in equilibrium,

Scheme 2.1 depending on the pH ,1281 as shown in Figure 2.10 for an aqueous solution
containing HPC>42_ and MoC>42_ at a molar ratio of 1:12/ 291 The compound
Substitution of one vanadium(V) for molybdenum(VI) in H 3IPM012O40] that crystallises from solution may not necessarily be the most abundant one.
increases the thermal stability; the stability decreases upon further substitution, Figure 2.11 shows the pH range of existence for various polyoxometalates in
however/2al Upon heat treatment of solid H4IPM011VO40], vanadyl and molyb- aqueous solution/ 281 Polyoxometalate solutions frequently equilibrate quite
denyl species leave the Keggin unit/ 271 Substitution of Cs+ for proton in quickly, in seconds; in some cases, however, it takes several months/ 301
20 CATALYSIS BY POLYOXOMETALATES
P R O P E R T IE S OF PO L Y O X O M E T A L A T E S 21
W(VI) > Mo(VI) > V(V).
The stability of the molybdenum(VI) heteropoly anions decreases in the series

of heteroatom s:115,281
Si4+ > Ti4+,Z r4+ > Ge4+ > P5+ > As5+.
12-Molybdophosphate exists in aqueous solution at pH < 1.5 (Figure 2.10).

As the pH increases, it undergoes alkaline hydrolysis, which occurs via the
following steps in dilute (< 10~3 mol 1_1) solution:115’281
OH“ OH- OH~

Figure 2.10 Distribution diagram for species present in fresh solutions containing
[PM o ,204 o]3~ t ± [PM o h 0 39]7“ + M o 0 42~ H[P2M o50 23]5- + M o 0 42'
[M0O4]2" and [HPO4]2' in a molar ratio of 12:1 at different pH values. The P:Mo
ratio is shown for each complex.1291 H P 0 42- + M o0 42"
In concentrated solutions (~ 10_1 mol 1_I), the hydrolysis proceeds via the
formation of the dimeric 9-molybdophosphate [P2Moig062]6_ as an intermedi
ate. The polyanions with P:Mo ratios of 1:9, 2:18, and 2:5 predominate in the
H + - M o0 42- - H P 0 42~ system at pH 1.5-6.0; their stability constants have
been determined.1291 In stronger acidic media (pH < 1.5), the heteropoly anions
undergo acid hydrolysis forming defect polyanions and oxomolybdenum(VI)
cations.
The stability of polyoxometalates increases in organic media. It has been
shown by the conductivity method that heteropoly acids such as H^PWnCX«)],
H 3[PM o12O40], H4[SiWi2O40], H4[SiMo,2O40], H4[PW „V O 40), and H4[PM on
VO40] are stable towards solvolysis in ethanol, acetone, and acetic acid at
concentrations as low as 10~5- 10~6 mol r 1.!32’331
The solution chemistry of the mixed-addenda heteropoly anions
[PMoi2_nVn0 4o](3+n)~ (HPA-n) that are used as catalysts for liquid-phase
oxidation (Chapter 5) has been studied in detail. Substitution of vanadium(V)
D ecom p osition , %
for molybdenum(VI) increases the stability of the heteropoly anion to a certain
degree.1281 Stability of the corresponding acids in aqueous solution decreases
Figure 2.11 pH range of existence of polyoxometalates:1281 (1) [PMoi20 4o]3-, with increasing n in the sequence HPA-1 > HPA-2 > HPA-3.[281 The acids with
(2) [PW12O40] , (3) [GeMoi20 4o]4-, (4) [GeW120 4o]4”, (5) [P2Wi80 62r , n > 3 have not been isolated,1341 but their salts are known. The most stable
(6) [SiWi20 4n]4 , (7) [PMou 0 39]? , (8) [P2Mo50 23]*-, (9) [H2Wi204o]6_, anion [PMon V O ^]4- begins to hydrolyse only in 0.8 mol 1_1 HC1.[301 As the
(10)[PW,iO39r .
acidity increases, the anions with n > 1 lose vanadium to give the anions with
smaller n, for example:[351
Many studies show that the typical Keggin heteropoly acids retain the
structure of polyanion in aqueous solution, at least at a relatively high concen
10 {PMO9V3O40} + H + ^ 9 {PM o 10V2O40} + 12 V 0 2+ + H P 0 42~
tration.111This has been demonstrated by XRD, IR and Raman spectroscopy as
well as by ,70 NM R (Ref.[311 and references therein). However, in dilute
In this equation, the acidic protons are omitted in polyanion formulas. The
(< 10-2 mol l" 1) solutions, degradation of polyanion may occur.
anions {PMo9V3O40} and {PMo6V6O40} are stable at the pH 2.5-5.5.[30] At the
Generally the stability of 12-heteropoly anions towards hydrolysis in aque
pH 1-3 the anions {PM oi2_nVnO40} disproportionate:[35]
ous solution decreases in the order of addenda atom s:115,281
22
2 {PM011VO40} {PM012O40} + {P M oio V20 4o}
Similar disproportionation of {PW11VO40} was found to be second order with

0 Mn(H20 )
0 Mn(02)
respect to the polyanion, the reaction rate increasing with the pH and ionic
strength.1361
The Keggin, Wells-Dawson and other types of heteropoly anions form
lacunary (defect) species in solution at an appropriate pH .11,281 The lacunary
anions have one or more vacancies created by the loss of addenda atom(s) from
the structure. For example, [PW12O40]3- forms the lacunary anion [PW11O39]
at the pH 2 in aqueous solution:
[PW1204 o]3- t± [PW90 39f - + W(VI)
The lacunary anion is stable until pH ~ 8, then further degrades to give the
trivacant lacunary species [PW9O34]9 -.111 The vacancies thus formed have great
coordination ability; numerous metal complexes with lacunary structures are
known (Section 2.5.2).11,371
either directly, as in the case of the Wells-Dawson anion (Figure 2.4), or with
2.5.2 POLYOXOMETALATES AS LIGANDS
the incorporation of metal ion linkers,1371 as shown in Figure 2.13. The latter
Two types of complex formation with polyoxometalate ligands can be distin clusters have attracted interest as oxidation catalysts (Chapter 5).
guished: (1) whole structures binding metal cations via surface terminal and M ore about complexes of polyoxometalates with metal ions can be found in
bridging oxygen atoms; and (2) lacunary structures enclosing metal cations in Refs.1' ^ 371
the vacancies.11,41
Complexes of the first type are relatively weak and infrequent. They are
favoured in nonaqueous solutions, especially if the polyoxometalate has a
high charge, and more than one oxygen atom of the anion is coordinated
to the metal cation. An example of such complex is the species [UM012O42
{Ni(H20)3}2]4_, with the Dexter-Silverton anion (Figure 2.6) acting as a
tridentate ligand through three neighbouring terminal oxygen atom s.1381
Complexes with lacunary polyoxometalate structures are numerous and of
great variety. The vacancy, e.g., in a Keggin or W ells-Dawson anion, can act as a
pentadentate coordination site, as in [(SiWn039)Co(H2 0 )]6_ with the octahe
dral Co2+, or tetradentate site, as in [(PW n039)Cu]5- with square-planar
Cu2+ .[4] Some examples of reactions of such complexes are shown in Figure 2.12.
Transition metal complexes of polyoxometalates such as [(PW u0 39)M]n+
and [(SiWn039)M]n+ have been considered as inorganic analogues of metallo- Figure 2.13 The structure of the [M4(H20 )2(PW9034)2]10- anions.1371An M4 cluster of
four metal-oxygen octahedra (M = Co2+, Ni2+, Zn2+, Mn2+, etc.) is sandwiched by two
porphyrins with the important advantage of being much more robust to oxida trivacant lacunary Keggin units B-{PW9034}.
tive and thermal degradation than porphyrins or other multidentate organic
ligands.14,39,401 Consequently, there has been a significant interest regarding
their use as catalysts for liquid-phase oxidation (Chapter 5). 2.5.3 ISOTOPE EX CHANGE
Lacunary polyoxometalates with more than one vacancy, e.g. PM 9 or
SiM9 anions, form numerous complexes with a range of structures.11-4,371 Studies with the use o f isotopes, such as " M o , 185W ,141,421 and 170 , [43] show that
Such lacunary anions may assemble into larger polyoxometalate structures, heteropoly anions exchange their addenda and oxygens with solution, the
exchange rate depending on the chemical composition of the anions. The between V 0 2+ and V(V) in polyanion is suggested to occur.1481 The reaction of
"M o exchange between [PM012O40]3 (0.01 mol l" 1) and N a2" M o 04 {PWi2- nVn04o} with V 0 2+ follows the same mechanism.[49a]
(0.1 mol I-1) in aqueous solution at 20°C and pH 1.2 is complete in The kinetics and mechanism of the formation and decomposition of Keggin
15min.[411 The heteroatom does not exchange. According to 170 NM R data, heteropoly anions have been investigated.^50-521 The formation of [PMoi2C>4o]3
the terminal, bridging, and internal oxygen atoms in Keggin anions have and [PM oioV2C>4o]5~ from phosphate, molybdate, and vanadate in acidic aque
different chemical shifts and different exchange rates with solvent.143,441 The ous solution is very fast, on the timescale of the stopped-flow technique.^521
rate of 170 exchange in [PMo]2_nVn0 4o](3+ll)-(n = 0,1,2) anions decreases by These reactions show a complex kinetics and their mechanism is not yet clear.
an order of ten per each vanadium(V) added.1431 It is suggested that the
exchange proceeds via dissociation of addenda from the polyanion followed
by the exchange of the monomeric oxometal species with solvent. 2.6 ACID PRO PERTIES
Solid heteropoly compounds exchange oxygen with water vapourt2c,ni
(Chapter 5). Many heteropoly acids, for example the Keggins and Wells-Dawsons, are
strong Bronsted acids.11,20,28,531 The acid properties of the most common Keg
gin acids both in solution and in solid state are well documented.^20,531 The
2.5.4 KINETICS AND MECHANISM OF SUBSTITUTION IN following discussion is mainly referred to acid properties of these acids. Sup
POLYOXOMETALATES ported acid catalysts are discussed in Chapter 4.
Kinetics and mechanism of addenda substitution in heteropoly anions have

been studied.145^ 91 The reaction 2.6.1 PROTON STRUCTURE
[SiW1204o]4- + V 0 2+ -» [SiW i,V04o]5' + W(VI) Structural characterisation of proton sites is an im portant step towards under
standing the catalytic activity of heteropoly acids.[2°’12,53-551 In solid heteropoly
in aqueous solution occurs in accordance with the kinetic equation r = &[SiW]2] acids, bulk and surface proton sites located respectively in the bulk and on the
[OH- ], where k — 2.8 x 1061 mol-1 s-1 at 25 °C. The substitution is suggested surface of the solid should be distinguished. The structure of these sites may be
to occur via a dissociative mechanism with the rate-limiting step of formation different. The bulk proton sites are suggested^20,121 to play a key role in ‘pseu
of the lacunary species: doliquid’ catalysis by solid heteropoly acids (Chapter 4). So far, most proton
characterisations have been done for the bulk heteropoly acids, in particular for
[SiWI204o]4- + OH" -► [SiW] 1039]8- + W(VI) the strongest acid H 3[PW i2C>4o]. The proton structure of supported heteropoly
acids is scarcely characterised.
followed by the fast migration of vanadium(IV) into the vacancy formed.[45,46] Two kinds o f protons have been found in solid heteropoly acids: (i) hydrated
Similarly [SiWnC^g]8- reacts with Co2+ to give [SiW nC ^C o]6 -.1471 In the reac protons [H(H20 ) n]+ and (ii) nonhydrated protons. The hydrated protons pos
tion of VO+, V 0 2+, M o0 2+, Fe2+, or Fe3+ cations with [PW12O40]3- the disso sess a high mobility; these are responsible for the extremely high proton
ciative pathway competes with the associative pathway, which includes the conductivity of crystalline heteropoly acid hydrates. The nonhydrated protons
formation of an intermediate complex between [PW12O40]3- and the are much less mobile; these are suggested to localise on the peripheral oxygens
cations.t46,49] of the polyanion.[531
The rate of reaction of {PMoi2- nVn04o} (n = 0 - 6 ) with V 0 2+, i.e. The location of protons in heteropoly anions has been subject of many
studies.[54,56-621 The Keggin anions have two types o f outer oxygen atoms as
PM o12_nVn5+ + V 0 2+ -» PM o12_nVn_]5+V4+ + V(V) (or M o(VI)) potential protonation centres: terminal oxygens M = 0 and bridging oxygens
M -O -M (edge-sharing and comer-sharing) (Figure 2.14). Bond length-bond
at pH 2.2-3.0 obeys the kinetic equation r = A;[PMoi2_nVn] [V02+]/[H +]a, where strength correlations1561 as well as 170 N M R data[5?1 indicate that in the free
1 < a < 2.[481 The reactivity of polyanions decreases from n = 0 to n = 6. polyanions (e.g., VioO6^) in solution, the bridging oxygen atoms, having a
The mechanism of this reaction may depend on the composition of polyanions. higher electron density than the terminal oxygen atoms, are protonated.
With PM012, the reaction probably proceeds via fast migration of V 0 2+ into Extended Hückel molecular orbital calculations showed that the bridging oxy
a vacancy of defect molybdophosphates; with PM onV, it is likely to be a gens are the most basic and thus the most likely to be protonated.1581 Recent
V(IV) for Mo(VI) substitution; in the case of n > 2, an electron transfer density functional quantum chemical calculations of optimised isolated metal
o=w
11
0
Q
H H ^w =o o=w
P H+ O
H H
Ov
•
.0
£II
II
^ w = o o= w ^
•
a b
Figure 2.15 Schematic structure of (a) bulk proton sites in H3[PWi204o]- 6H2O and
(b) Cs+ location in Cs3[PW1204o].[591
60 ppm upfield shift compared to the aqueous solution spectrum, whereas the
bridging oxygen resonances have practically the same positions in both spectra
(Figure 2.16).* Since in aqueous solution H3IJPW12O40] is completely deproto-
nated (see below), this unambiguously identifies the terminal oxygens as the
(02), and corner-bridging (03) oxygen atoms.
predominant protonation sites in the solid heteropoly acid.
oxygen clusters also show that the most energetically favourable protonation The structure of bulk proton sites in dehydrated heteropoly acids is not yet
sites in such clusters are the bridging oxygens.[6I] Hence, in the free Keggin clear. Investigation of dehydrated acids requires a strict control of traces of
anion in the gas phase, the bridging M -O -M oxygens may be assumed to be the water in the solids. Lee et al.[54a] found from infrared spectroscopy that protons
predominant protonation sites. were most likely located on the bridging oxygens. On the basis of l70 NM R
In solid crystalline heteropoly acids, the protons, hydrated or nonhydrated, results and by analogy with the structures of H3PPW12O40] • 6H 2O and
take part in the formation of the crystal structure, linking the neighbouring CS3IPW12O40] (Figure 2.15), Kozhevnikov et a lP 9] proposed a structure for
heteropoly anions. In this case, the proton locations are determined not only the dehydrated H 3[PWl204o] in which the proton migrates rapidly between four
by the basicity of the outer oxygens in the descrete polyanion but also by equivalent terminal oxygens (Figure 2.17). This structure was assumed to form
the energy of the crystal lattice. It is conceivable, therefore, that in crystalline directly from the proton structure of the H 3[PW i204 o] hydrate upon dehydra
heteropoly acid the more accessible terminal oxygens may be protonated. There tion. However, Zecchina et a lP 21 found no infrared bands characteristic of the
is one case - a relatively stable crystalline hexahydrate H 3PPW12O40] • 6H 2O - [O . . . H + . . . O] group in the dehydrated H 3PPW12O40] which is thought to be
when the link of the hydrated protons to the terminal oxygens, not to the incompatible with the structure shown in Figure 2.17. Uchida et al.,[54h] using
bridging ones, has been demonstrated by single-crystal X-ray and neutron *H, 170 and 31P MAS N M R , identified and quantitatively monitored three
diffraction.[14a] The crystal structure of H 3PPW12O40] hexahydrate is for types of protons, namely H +,H 3 0 +, and HsO^, in solid H3[PWi204o]nH20
med by packing heteropoly anions into a body-centred cubic structure. The (0 < n < 6). W ater molecules and acidic protons were found nearly uniformly
bulk proton sites in this solid are represented as diaquahydrogen ions, distributed in the solid. The relative am ounts of the three types o f protons
H5Ü2+, which are almost planar, quasi-symmetrical hydrogen-bonded species depend on the water content. The protonated dimer C D 3C N . .. H +. .. NCCD 3,
[H20 ... H + ... OH2]. Each of these links four neighbouring heteropoly anions similar to H 5O2 , was found to form upon the interaction o f CD3CN with the
by forming hydrogen bonds with the terminal W = 0 oxygens (Figure 2.15a). dehydrated H 3[PW120 4o].(62b]
Interestingly, the same structure was inferred[,4a] for the structurally similar The surface proton sites in solid heteropoly acids, apparently stronger than
anhydrous heteropoly salt CS3P W 12O40], in which the Cs+ ions each have four the bulk sites, are generally more im portant for heterogeneous acid catalysis.
equivalent terminal oxygens as the closest neighbours (Figure 2.15b). Their structure remains practically unknown, however. Crystalline heteropoly
It should be noted, however, that the protons cannot be found directly from
♦Prior to m easuring the 170 N M R spectra, the solid H 3IPW 12O40] w as dehydrated at 200 C l
X-ray data; their positions are localised on the basis of a sensible hydrogen 0.4 m m H g and w as believed to be an hyd rou s) 591 In fact, it con tain ed som e w ater because o f the
bonding scheme and the known geometry of the water molecule. Direct evi rapid rehydration even u pon brief exposure to air. T h e spectrum for ‘practically an hyd rou s’
dence of the predominant protonation of the terminal oxygens in solid H 3[P W i20 4o] reported by the au thor’s grou p1601 and also by U ch id a et a /.t54b| is m uch broader
H3[PW1204 o] and H 4[SiWi2O40] hydrates has been obtained by 170 N M R , w ith a p oorly detectable resonance for the term inal W = 0 group; this spectrum transform ed to the
on e show n in Figure 2 .16 upon exp osin g the sam ple to air. T hus the 170 N M R results1591 cannot
comparing the solution and solid-state spectra for these heteropoly acids.[59]
support the p roton structure o f anhydrous H 3IPW 12O40] (Figure 2.17) but they d o support the
The resonance for the terminal oxygen in solid H 3[PWi204o] exhibits a large proton structure o f the hydrated acid (Figure 2.15).
PROPERTIES OF POLYOXOMETALATES 29
CATALYSIS BY POLYOXOMETALATES
28
^w =o. o=w ^
H+
W =0 W-O-W h 2o ®vv=o 'o=w^^
427
Figure 2.17 Schematic structure of bulk proton sites in anhydrous HafPWÔ« ] 1591
acids possess a very low surface area ( l - 5 m 2 g_1) and low porosity
(< 0.1 cm3 g_1).*2c,2f’555 j o increase the surface area, they are frequently sup
ported on an inert porous support, e.g. silica (Chapter 4). It was suggested that
the surface proton sites in bulk and supported catalysts might be represented by
protons localised on the bridging oxygen atoms in the surface heteropoly
anions.[53]
I
2.6.2 HETEROPOLY ACIDS IN SOLUTION
In solutions, the acid properties o f heteropoly acids have been characterised in

terms o f dissociation constants and Hammett acidity function.*535 As hetero
poly acids have very high solubilities in polar solvents, such as water, lower
alcohols, ketones, ethers, esters, etc., these solvents have been primarily used in
these studies. The dissociation constants of heteropoly acids were measured in
H 20 , [63] Me2CO, EtOH, and AcOH*32,335. The Ham m ett acidity function was
determined in H 20 and H 20 -A cO H , H 20 -dioxane, H 20 -E tO H and
H 20 - M e 2C 0 mixtures.*645
In aqueous solution, heteropoly acids such as H 3[PW i2C>4o], H 4[SiW1204o],
and H 3[PM oi204 o] are strong, fully dissociated acids.*535 The [SiWi20 4o]4~ and
[PW12O40]3" anions remain deprotonated even after accepting two and three
extra electrons, respectively, upon polarographic reduction in aqueous solution
at pH 1,*65] Stepwise dissociation is not observable because of the levelling effect
of the solvent. The dissociation constants, starting with K4, have been meas
ured for some Keggin and Dexter-Silverton acids in water*535 (Table 2.3).
Nonaqueous solvents exert a differentiating influence upon the acid dis
sociation, hence they are more suitable for studying the dissociation steps of
Table 2.3 Dissociation constants of heteropoly acids in water at 20 °C*535.

Acid PK4 pK5 pK6 pK7 pK8
H5[PMo,oV204o]a 1.2 2.1
H6[PMo9V3O40T 1.3 1.6 2.0
Figure 2.16 ,7° N M R spectra for , 70-enriched H 3IPW 12O 40]: (a) ° - 52f cr,i:H
Hj [P W p O d aqueous solution; (b) and (c) magic-angle spinning spectra lor soi H8[NpMoj20 42] 3.2 3.4 3.6 4.3 5.7
H 3[PW,20 4 o] at a spinning rate o f 6.8 and 11 kHz, respectively; positions o f centre H8[CeMoi2042] 2.1 2.0 3.0 4.2
bands are indicated; spinning side bands are asterisked.[3s] Reprinted with permission
from C hem . R ev. 1998, 98, 171. Copyright 1998 American Chemical Society. H8[UMoi20 42] 2.1 3.0 4.3
a) At 25 °C
poly-protonic acids. It is also noteworthy that polyoxometalates are more Tungsten acids are stronger than molybdenum ones. The strongest acid in
stable in nonaqueous media than in water.1535 As shown by conductivity the Keggin series is H3[PW120 4o] /535 However, the difference between the
method/ 32,335 the first two protons in HjfPW^Cô] are fully dissociated and strongest and the weakest acid is quite small.
the third only partly in ethanol and acetone, while the weaker acids It is im portant to note that the acid strength decreases upon reduction of the
H 4[SiW1204 o] and H ^ P M o ^ O ^ ] are fully dissociated in the first step and heteropoly anion (cf. H 3[PMoi20 4o] and H4[PM onM o5+O40])/535 This fre
partly in the second. In the less polar acetic acid, Keggin acids behave as 1- quently accounts for the inefficiency of molybdenum acids as acid catalysts in
1 electrolytes/ 535 Table 2.4 presents the stepwise dissociation constants, pK a, reducing organic media (Chapter 4). Being much weaker oxidants, tungsten
for heteropoly acids as well as for typical mineral acids in acetone and acetic heteropoly acids are not affected by the reduction and thus generally preferred
acid. The pK a values in ethanol are very similar to those in acetone. It can be as acid catalysts/ 555
seen that heteropoly acids are much stronger than mineral acids; for example, Deprotonation of a heteropoly acid (HPA) in solution can be viewed as an
they are stronger than H2SO4 by 2-5 pK units. ionisation-dissociation process with the formation of a solvent-separated ion
The effect of chemical composition on the acid strength of heteropoly acids is pair between the heteropoly anion (HPAN) and H + as an intermediate/ 535
surprisingly weak. The heteroatom (P or Si) has a very little effect despite the fact
that the acid strengths of H 3PO4 and H4S i0 4 differ significantly (pKi = 2.1 and K Ka
9.7, respectively). Heteropoly acids are much stronger that the corresponding HPA t± H PA N " || H + t± H PA N “ + H +
acids of their heteroatoms (cf., e.g. H 3IPW12O40] and H 3PO4). This can be
explained on the basis of the electrostatic theory taking into account the large From the conductivity study/ 335it was inferred that in polar nonaqueous solvents
size of heteropoly anions and the large number o f external oxygen atoms avail such as acetone heteropoly acids are fully ionised (Kj » 1). From I70 NM R
able for the delocalisation of anion charge/ 535 d ata/ 59c5 H 3[PW]20 4o] is fully ionised even in 94:6v/v A cO H -H 20 solution; the
In polar solvents such as acetone the acid strength of Keggin heteropoly solvated protons are loosely bound to the anion as a whole rather than to a certain
oxygen atom in the anion, in contrast to the crystalline acid.
acids follows the order:
Concentrated solutions of heteropoly acids are of great interest for homoge
H3IPW12O40] > H 4[PW i 1V 0 4o] > H 5[PW ioV2040] « H 4[SiWi20 4o] > neous acid catalysis. The acidity of concentrated solutions of heteropoly acids,
in terms o f the Hamm ett acidity function (H0), depends weakly on their
H 3[PM oi20 4o] > H4[PM oj 1M o5+O40] « H 4[PM o 12VO40] > H 4[SiMoi2O40] composition (Table 2.5) and is stronger than that of equimolar solutions of
H 2S 0 4 by 1-1.5 H 0 units/ 53,645
Table 2.4 Dissociation constants o f heteropoly acids in acetone Izumi et a/./665 by measuring the chemical shift of the hydroxyl protons in
and acetic acid at 25 °C and zero ionic strength1®1. chloral hydrate Cl3CCH(OH)2, found the following order of acid strength for
Acetone Acetic acid Keggin acids in C öD sNC^ solution:
Acid pK, pK2 pK3 pKi

H 3[PW12O40] > H 3[PMoi2O40] > H 4[SiW12O40] » H4[GeW12O40] >
H3[PWi204o] 1.6 3.0 4.0 4.8 H4[SiMoi20 4o] > H 4[GeMoi20 4o]
H4[PW11VO40] 1.8 3.2 4.4 4.7
H5[PWioV204o] 4.8
5.0 This order is similar to that in aqueous solution.
H4[SiW,204o] 2.0 3.6 5.3
2.0 3.6 5.3 4.7 Drago et a/ / 675 studied the acidity of [H3[PWi20 4o] by the calorimetric
H 3[PM o 1204 o]
H4[PMO! 1 M o5+04 o] 2.1 3.7 5.5 titration with a series of bases in CH3CN solution and determined equilibrium
H4[PM oi 2V 0 4o] 2.1 3.7 5.6 4.7 constants and enthalpies for the three deprotonation steps. The results indicate
H4[SiMo120 4o] 2.1 3.9 5.9 4.8 that the three protons are not of equal strength. The enthalpies of reactions
H4[GeWi204o] 4.3 with pyridine with a series of Bronsted acids in dilute acetonitrile solution lead
H5[GeWu V04o] 4.7
4.6 to the following acidity order:
H6[GeW,oV204oJ
HCIO4 4.9
5.6 H 3[PWi2O40] > CF3SO3H > P-CH3C6H4SO3H « H 2S 0 4(97%) >
HBr
h 2so 4
6.6 7.0 C F3COOH > ClC6H4COOH
HC1 4.3 8.4
HN03 9.4 10.1
i.e. the heteropoly acid is stronger than triflic acid in CH3CN solution.
32
Table 2.5 Hammett acidity function H0 for aqueous solutions of example, pyridine adsorbed on Si02-A l20 3 fully desorbs at 300 °C, whereas on
H3[PW i204 o] and H4[SiWl204oJ[64a]-_______________________ H3[PWI204 o] it retains as pyridinium ion at much higher temperature.1721 Like
other strong solid acids, heteropoly acids are capable of generating carboca-
[HPA] Temperature, °C
tions from adsorbed olefins and arenes/ 731
mol l-1 20 25 40_______60_______ 80 As found by temperature-programmed desorption (TPD) of ammonia, the
acid strength of crystalline heteropoly acids decrease in the order (desorption
H3[PW i20 4o]
+0.27 temperatures in °C) /741
0.05
0.07 +0.11 +0.12 +0.13 +0.17 +0.24
0.10 -0.05 -0.03 +0.01 +0.03 +0.04 H 3[PW i 204 o] > H4[SiW1204o] > H 3[PMol204o] > H4[SiMo12O40]
0.15 -0.24 -0.22 -0.21 -0.17 -0.15
0.20 -0.35 -0.33 -0.32 -0.26 -0.23 592 532 463 423
0.25 -0.47 -0.46 -0.45 -0.41 -0.40
0.30 -0.56 -0.55 -0.54 -0.53 -0.52
0.35 -0.68 -0.66 -0.61 -0.59 -0.55 This order is identical to that in polar solvents (Table 2.4). The TPD data
0.40 -0.83 -0.82 -0.80 -0.78 -0.74 should be treated with caution, however. The N H 3-T P D measures the tem
0.45 -1.00 -0.96 -0.93 -0.92 -0.84 perature of decomposition of the ammonium salts of heteropoly acids to form
0.50 -1.21 -1.16 -1.14 -1.11 -0.96 N H 3, nitrogen oxides, and H 20 together with a mixture of oxides of the
H4[SiW,20 4o] heteroatom and addenda. Hence, the measured desorption temperature may
+0.23 +0.24 +0.25 +0.27 +0.34 not reflect correctly the acid strength of heteropoly acids.
0.05
0.10 -0.03 -0.01 0 +0.02 +0.11 Microcalorimetry of ammonia sorption appears to be the best technique for
0.15 -0.25 -0.24 -0.22 -0.13 -0.09 measuring the acid strength of heteropoly acids/ 75-771 According to the micro-
0.20 -0.38 -0.36 -0.34 -0.28 -0.26 calorimetric data,t75] the bulk proton sites in dehydrated H 3[PWi20 4o] are
0.25 -0.53 -0.49 -0.46 -0.45 -0.41 essentially uniform and characterised by the differential heat of ammonia
0.30 -0.70 -0.67 -0.64 -0.57 -0.54
-0.79 -0.74 -0.64 -0.62 adsorption of 180 kJ mol-1 (Figure 2.18). Other microcalorimetric studies[76,77]
0.35 -0.77
0.40 -0.98 -0.93 -0.90 -0.89 -0.83 have examined the acid strengths of a number of heteropoly acids by the
0.45 -1.10 -1.05 -1.01 -0.95 -0.90 sorption of N H 3 after pretreatment of the solids under various conditions.
0.50 -1.21 -1.15 -1.08 -1.00 -0.99 Typically, the heat of ammonia adsorption on bulk Keggin heteropoly acids
is found in the range of 180-200 kJ mol-1, which is considerably higher than
that for S i0 2-A l20 3 and zeolites. The Wells-Dawson acid Höl/^WigCta] (ca.
2.6.3 ACIDITY OF SOLID HETEROPOLY ACIDS 150kJ mol-1) was found to be significantly weaker than H 3[PWi20 4o]/77bl An
effect of activation conditions was observed in that a lower activation tempera
Generally, solid heteropoly acids form ionic crystals composed of heteropoly ture resulted in a higher differential heat of sorption.161,761 This may be ex
anions, variably hydrated protons (H+, H 30 +, H s0 2+, etc.) and crystallisation plained by an inductive effect of water on the acid strength of the proton[76] or
water (Section 2.6.1). The crystal structure of heteropoly acids depends on the by solvation of ammonia in the waters of crystallisation.1-611 The order of acid
amount of crystallisation water (Table 2.1). This water can be easily removed strengths of solid heteropoly acids, as determined by microcalorimetry is/ 61,761
on heating, whereby the acid strength is increased due to the dehydration of
protons. H 3[PW i 20 4o] > H4[SiWi20 4o] H 3[PMoi20 4o] > H4[SiMoi20 4o]
Solid heteropoly acid hydrates possess high proton conductivities/ 68-711 The
conductivity of solid H3IPW12O40] is comparable to the proton conductivity in which is in agreement with that found by temperature-programmed desorption.
water. The conductance of heteropoly acids hydrates has low activation ener Usually, relative catalytic activities of heteropoly acids are consistent with this
gies (3.3 kcal mol-1). The high conductivity is attributed to the location of order both in homogeneous and in heterogeneous systems/ 20,53,551 Density
waters of crystallisation and hydrated protons in the interstices between the functional quantum chemical calculations of optimised metal oxygen clusters
large heteropoly anions. reveal that the proton affinity of tungsten clusters is lower than that of analo
Solid heteropoly acids possess purely Bronsted acidity, as established by IR gous molybdenum clusters by 20-40 kJ mol-1 / 611
spectroscopy of adsorbed pyridine. They are stronger than conventional solid The acidity of solid 12-tungstophosphoric acid has been measured using
acids such as S i02-A120 3,H 3P 0 4/S i0 2, and HX and HY zeolites/ 20,111 For slurry calorimetry in cyclohexane with pyridine as a probe/ 781 Two types of
(1) Sol-gel S i02

(2) SiO z
(3) H2S 0 4/Si02
(4) H 3[PW 1204o]
(5) S 0 3-W 03/S i02
(6) HZSM-5
(7) AlCl3/S i02
(8) S b C yS i02
Figure 2.19 Correlation between AS (31P NMR) and AH (calorimetry of pyridine

adsorption) for solid acids.[79]
definition,1831 superacids are acids stronger than 100% H2S 0 4, i.e. they have the
Hammett acidity function H0 less than —12.2. Using titration with Hammett
indicators, Okuhara et al.[sl] found that the calcined H 3[PW i204 o] and
Cs2.5H 0.5tPW 12O40] possessed the acid sites with the Hammett acidity function
of —13.8 < H 0 < —13.2 (Table 2.6). However, the application of Hammett
indicators to characterise the surface acidity of solid acids can be misleading
because the surface acidity function H 0, in contrast to the solution H0, has no
Figure 2.18 Differential heat of ammonia adsorption onto H3[PWi204o] and 20%
H3[PWi204o]/Si0 2 measured at 150 °C after pretreatment at 300°C/10_3mmHg.[751 explicit physicochemical meaning.^84’851 Although it was demonstrated that
Reprinted with permission from Catal. Rev. Sei. Eng. 1995, 37, 311. Copyright 1995 H 3IPW12O40] is stronger than H 2S 0 453 and even than CF3SO3H67 in dilute
Marcel Dekker. solution, it does not necessarily mean that this will stand for the neat acids.
Another useful yet insufficient criterion to identify superacids is based on their
catalytic activity: superacids will catalyse the low-temperature (below 100 °C)
Bronsted sites with different strengths (137 and 82 kJ mol-1) have been found,
skeletal isomerisation of light alkanes/ 831 This test is insufficient because, when
which disagrees with the microcalorimetry of gaseous ammonia adsorption that
the result is positive, the isomerisation must be proved to occur via the genuine
shows that all protons in solid H3[PWi204o] are almost equivalent. The differ
acid-catalysed path and not a redox mechanism, e.g. one-electron transfer.
ences have been attributed to the small size and stronger basicity of ammonia.
According to this criterion, neither solid ((H3[PW i204 o] or CS2.5H 0.5
The smaller N H 3 molecule is able to occupy the interstices in the lattice without
[PW12O40]) can be regarded as superacids because they catalyse n-butane
appreciable change in lattice dimensions or energy, whereas penetration of the
isomerisation only at about 300 °C.[821 Nowinska et a /.[801 reported that bulk
solid by pyridine causes expansion of the lattice.
Osegovic and Drago[791 demonstrated that the bonding of triethylphosphine
oxide (TEPO) to the acid site of a surface produces a systematic change in th e 31P Table 2.6 Hammett acidity function H0 for solid acid catalysts2c'81.
isotropic chemical shift that is proportional to the acid strength of the acid site. Catalyst (pretreatment) pKa of indicator (H0)a
They measured the acidity of crystalline H3[PWi204o] as well as several am orph
ous solid acids and zeolites. A single parameter scale was developed based on the - 8.2 -11.4 -12.7 -13.2 -13.8 -14.5
31P chemical shift, A8, of TEPO adsorbed on solid acids, which allows a good C s 2.5H o.5 [P W 120 4o] (3 0 0 °C ) + + + + _ _
linear correlation between A8 and the enthalpies of pyridine adsorption, AH, H3[PW120 4o] (300 °C) + + + + - —
measured by calorimetry (Figure 2.19). It can be seen, however, that for HZSM-5 (535 °C) + + + — - —
H3[PW120 4o] a larger acidity is measured by TEPO than by calorimetry. S042- /Z r0 2 (370 °C) + + + + + +
Si02-A b03 (450 °C) + + + - - -
Solid H3[PW i20 4o] and its acidic salt CS2.5H0.5PPW12O40] after pretreatment
at 300-400 °C have been claimed to acquire superacid sites.[80~82] By the a) The indicator has changed its colour (+) or remained unchanged (—)
and silica-supported H ^ P W ^ O ^ ] showed a very low catalytic activity in the 2.7 REDOX PRO PERTIES
skeletal isomerisation of n-hexane at 75 °C. Therefore, for heteropoly acids, the
isomerisation test seems quite conclusive. The study by Essayem et a/ / 851 of the Redox chemistry of polyoxometalates is extremely diverse/ 1,281 It has been
H/D exchange between the deuterated solid catalysts D 3[PW i204 o] and subject of many studies and found many applications in chemical analysis
Csi 9D 1.1PPW12O40] and isobutane revealed that these solid acids are strong (Chapter 8) as well as in selective catalytic oxidation1311 (Chapter 5).
acids but not superacids. Apparently, to answer the question whether or not According to Pope/ 1,41 polyoxometalates, regarding their redox abilities, can
solid heteropoly acids are superacids we need much better understanding of be divided into two groups - ‘mono-oxo’ (type I) and ‘cis-dioxo’ (type II). This
what the solid superacids are and how to measure their acidity in the first place. classification is based on the number of terminal oxygen atoms attached to each
In this connection, recent data on sulfated zirconia are of interest/ 86,871 The addenda atom, e.g. molybdenum or tungsten, in the polyanion. Examples of
ability to perform the low-temperature alkane isomerisations has led to claims type I polyanions are the Keggins, the Wells-Dawsons and their derivatives
that sulfated zirconia is a superacid. Recently Drago et al.,[S1] by calorimetry of that have one terminal oxygen atom M = O per each addenda atom (Figures 2.1
pyridine adsorption, have found that sulfated zirconia has two types of acid and 2.2). Type II polyanions can be represented by the Dexter-Silverton
sites with strengths of 130 and 108 kJ m ol-1, which places its acidity lower than anion which has two terminal oxygens in cis positions on each addenda atom
that of HZSM-5 (170 kJ m ol-1) and about the same as that of HY (140 kJ (Figure 2.6).
mol-1). On the other hand, it has been shown that alkane conversions on sulfa In type I octahedra MC>6, the lowest unoccupied molecular orbital (LUMO)
ted zirconia may be initiated by one-electron oxidation of the alkane by sulfated is a nonbonding metal-centred orbital, whereas the LUM O for type II octahe
zirconia leading to an ion-radical intermediate, with no requirement of super dra is antibonding with respect to the terminal M = 0 bonds. Consequently,
acidity. As demonstrated by ESR spectroscopy/ 731 cation radicals are formed type I polyoxometalates are reduced easily and frequently reversibly to form
upon adsorption of arenes, such as styrene, naphthalene, and anthracene, on mixed-valence species, heteropoly blues, which retain the structure of the
H 3[PW1204 o] and H 3[PWi204o]/Si0 2 at 25-150 °C (Figure 2.20). Hence, one- parent oxidised anions. In contrast, type II polyoxometalates are reduced
electron oxidation might play a role in acid-catalysed reactions with heteropoly with more difficulty and irreversibly to complexes with yet unknown struc
acids as well. tures/ 1,41 F or this reason, only type I heteropoly compounds, by and large the
Keggins, are of interest for oxidation catalysis.
The total number of accepted electrons on reduction of type I polyoxome
talates can be quite high. As the anion structure retains upon this process, the
additional negative charge is compensated for by protonation of the anion from
solvent. Thus, the reduction is frequently pH-dependent, which can be repre
sented by equation 2.1:
[XM i26+O40]x- 8 + p e" + q H + H qpCM12_p6+Mp5+0 4o]x+q- p_8 (2.1)
where q < p . [1’28] On reduction in acidic aqueous solution at pH < 1, the

Keggin tungsten anions, e.g. [SiWi204o]4 -, can add two electrons without
protonation, i.e. the anion charge becoming - 6. In a more neutral solution,
the pH-independent reduction can proceed up to the anion charge of - 9 . The
reduced W ells-Dawson anions {X2W i8062} can bear the charge up to -1 2
without protonation/ 11
l Cyclic voltammograms of type I polyoxometalates, e.g. Keggin molybdates
H and tungstates, show a sequence of reversible one- or two-electron reduc
30 G tions11,4,281 (Figure 2.21) which yield deeply coloured heteropoly blues, the
colour intensifying with the number of electrons gained. The blues exhibit
Figure 2.20 ESR spectra: (l) 25% H3[PWi204o]/SiC>2 pre-evacuated at 200 °C; (2) strong d -d bands in the visible area in their electronic spectra.
styrene adsorbed on this catalyst at 25 °C; (3) sample 2 after heating at 150°C for ESR spectroscopy demonstrates that the unpaired electron in one-electron
0.5h.[73] Reprinted with permission from J. Mol. Catal. 1993, 79, 21. Copyright 1993
Elsevier Science. blues is weakly trapped at low temperatures, but undergoes fast hopping at
38 CATALYSIS BY POLYOXOMETALATES 39
PROPERTIES OF POLYOXOMETALATES
anion charge have been demonstrated1'1 (Figure 2.22). Heteroatoms that are
themselves strong oxidants can increase the oxidation potential significantly.
For example, for the {Co3+W i204 o}/{C o2+W i2C>4o} redox couple E = 1.0 V
(vs. standard hydrogen electrode).1881
°1---------------------------
- ° .t - Gee . . - p
'' P
- 0.2 - I'
«- - 0 . 3 - - si
Figure 2.21 Cyclic voltammogram of a-fPMoÔw]3 in 0.1 mol 1 1 HC1 (50% H2O/ u Fe
co - 0 . 4 - •'
EtOH).[4]
t -0.5- C o .- '' ' •
Co.-'* b
« - 0.6 - . .*■
room temperature. Two- and four-electron blues are ESR-silent, the additional C u-.. ' ' '
-0 .7 - CD
electrons being fully delocalised at room tem perature.11,41 r'
- 0.8 - *
The oxidation potentials, E, o f polyoxometalates depend strongly on their -0 .9 -t-------------.------------------------------1--------------
addenda and to a lesser degree on their heteroatom. Generally, the E values -7 -6 -5 -4 -3
parallel the corresponding oxidation potentials of the addenda11,4,531 (Table 2.7): Anion Charge
Figure 2.22 Plot of one-electron reduction potential E vs. anion charge for a-[XW)2
V(V) > Mo(VI) » W(VI) O4o]x-8; SCE denotes saturated calomel electrode.111
Typical heteroatoms that are not redox active affect the oxidation potential via Redox properties of the mixed-addenda anions {PMoi2_nVn04o} have been
the overall anion charge. Very good linear correlations between E and the studied in considerable detail,[1,281 especially in connection with their applica
tion for catalytic oxidation.131,89,901 These anions are remarkable because they
Table 2.7 Oxidation potentials of Keggin anions in aqueous solution (vs. possess not only a fairly high oxidation potential (ca. 0.7 V) but also their
SHEa)[531. reduced forms are very easily reoxidised by oxygen (air) in solution. These
redox reactions can be represented by the equations:
Redox system Electrons transferred E (Y)
V(V) -> V(IV) {PM o12_nVnO40} + Red + mH+ -► H m{PMoi2_nVnO40} + Ox (2.2)
PVvWu /PVIVWn 1 0.78
PVv Mo n /PVIVMo 11 1 0.68
2 0.71 H m{PM o12_nVn0 4o} + (m /4 )0 2 -> {PM o12_nVnO40} + (m /2)H 20 (2.3)
P V 2v M o 1o/ P V 2iv M o 1o
P V 3v M o 9/P V 3 IVM o 9 3 0.71
P V 4v M o 8/ P V 4iv M o 8 4 0.71 where Red is the reductant, Ox its oxidised form; typically n = 2 - 6 . The
Mo(VI) Mo(V) mechanism of these reactions will be discussed later in Chapter 5. The anions
P M o 12v i / P M o 9v i M o 3v 3 0.65 {PMoi2_nW n04o} show similar behaviour,[16bl although less readily. The re
SiMo12VI/SiMo9VIMo3v 3 0.63 duced form o f[P M o120 4o]3~ practically does not oxidise with 0 2 in solution,1311
W(VI) -* W(V) but the solid acid H 3[PM oi204 o] can be reduced and then reoxidised with 0 2 at
BW12vi/BW,iviWv 1 -0.36
temperatures above 200°C12c,11] (Chapter 5). Tungsten blues {XW i 204 o} are
GeW12VI/GeWn VIWv 1 -0.02
-0.05 very easily oxidised with 0 2 in aqueous solution.1911
SiWi2VI/SiWuvlWv 1
0.15 Electron-transfer reactions of Keggin polyoxometalates in solution can be
PW,2V,/PW11V1WV 1
Co(III) -►Co(II) viewed as the outer-sphere electron transfers,191-941 which is in line with their
CoIUW12/CouW12 1 1.0 very low solvation energies as well as their weakness as ligands. Kozhevnikov
and Kholdeeva1921 studied the kinetics of a series o f one-electron redox reactions
a) SHE is the standard hydrogen electrode
of Keggin polyoxometalates (Table 2.8) using both conventional and stopped-

R T \ n k 0 + W = - ( V 4 ) ( l + A G °'A )2 - / ? r i n Z (2.6)
flow techniques. These reactions were found to obey the rate equation
which can be applied to experimental data. In this equation k 0 is the k extrapo
r = £[Ox] [Red] lated to p = 0, W = z\z1e1/ Dr is the Coulombic work term that is calculated
from the ion charges and radii, X is the reorganisation energy associated with
where k is the rate constant (dependent on the pH and the ionic strength p), Ox electron transfer within the precursor complex, and Z = 1011 lm ol-1 s-1 is the
and Red are the oxidant and reductant, respectively. The mechanism was preexponential factor. At |AG°'| < X this equation transforms to equation 2.7:
analysed1921 using the Marcus theory,t9S1 which relates the free energy of acti
vation for an outer-sphere electron-transfer reaction, AG^, to the free energy of RT\nk0+ W = -X /4-A G °'/2-R T \nZ (2.7)
the reaction, AG0', adjusted to account for the Coulombic interaction. Apply
ing the Eyring equation (eq. 2.4)
which, for such conditions, predicts a linear dependence of R T \ n k 0 + W on
AG°‘ with a slope of -0 .5 . Values of R T \ n k 0 + W are plotted as function of
k = Z exp ( —h G ^ /R T ) (2.4) AG0' in Figure 2.23, assuming A, to be a constant throughout the reaction series.
This plot fits well a quadratic equation of the type of equation 2.6, the linear
for the bimolecular rate constant and the Marcus equation (eq. 2.5) for term having a slop of -0.50, which is in excellent agreement with the Marcus
AG^ theory. Thus these results support the outer-sphere electron-transfer mechanism
for one-electron redox reactions of polyoxometalates.1921 Recently, Weinstock1941
2 discussed thoroughly the electron-transfer reactions of polyoxometalates in
AG# = W + \ \-R T \nZ (2.5) solution and the use of the Marcus theory for these.
4
one can obtain the equation
Table 2.8 Kinetics of redox reactions of Keggin anions in water at 25 °C1921.
Entry R eaction A:(lmol 's " 1)3 ln * o b
1 [SiW 12f - + [C oniW I2]5- - [SiW I2]4" -H C o H W d 6" 7 x 106 3.8

2 [PW12]4- + [ C o in W 12]5- - [PW 12]3- + [ C o » W 12]6- 2.9 x 106 5.3
3 [PW12]4~ + F e3+ - » [PW 12]3" + F e2+ 6 x 10 6 24.9
4 [SiW 12]5" + [C om W I2]5- - [SiW I2]4" + [Cou W 12]6- 6 x 106 23.4
5 [SiW 12]5- + [F e(C N )6]3- - [SiW 12]4" + [F e(C N )6]4" 3.3 x 105 5.5
6 [PW I2]4- + [Fe(C N )6]3" - [PW 12]3" + [F e(C N )6]4- 2.2 x 10 5 6.6
7 [SiW 12]5“ + C u2+ -> [SiW i2]4- + Cu+ 9.1 x 104 19.2
8 [PW 12]4" + C u2+ - [PW 12]3- + C u+ 3.5 x 102 12
9 [PV2W 10]6' + [PV2M oiol5~ - » [PV2W 10]5 + [PV2M o,ol6 5.7 - 1 1 .9
10 [PV2W 10]5- + [PV2Moio]6- [PV2Wio]6- + [PV2M oI0]5 80 -9 .2
llc [Con W j2]6“ + [Com W 12]s- - [C on W ,2]5- + [C on iW ,2]6“ 0.24 - 12 .2
12 d H A " + [CoinW 12]3- HA* + [C onW 12]6- 2.4 x 105 8.6
13d H 2A + [CoIUW 12]5" - HA* + H + + [Con W 12]6- 1.4 x 104 9.6
14d H-iCat + [CoinW 12]5- HCat* + H + + [C ou W I2]6- 9.5 x 102 6.9
15d H 2Q + [Con iW i2]5" -> HQ* + H+ + [Con W I2]6- 77 4.3 Figure 2.23 Marcus plot for redox reaction of polyoxometalates.1921 Data points are
16 [SiW u]5' + 0 2 + H + [SiW 12]4 + H 0 2* 127 4.8 labelled as in Table 2.8.
17 [PW 12]4- + 0 2 + H+ - [PW 12]3" + H 0 2* 2.9 1.1
a) Most of the data obtained at ß = l.Omol l" 1(0.5 mol l"1 HCIO4 +0.5m oll 1 NaC104) As demonstrated by temperature-programmed reduction,1981 the activity of
b) Rate constants extrapolated to /1 = 0 solid Keggin heteropoly acids towards their reduction by hydrogen decreases in
c) From Ref.[96) the order: H 5[PMoioV20 4o] ~ H4[SiMoi204o] > H3[PM oi2O40] « H3[PMo6
d) From Ref.1971 HA" is ascorbate anion, H2A is ascorbic acid, H2Cat is catechol, H2Q is hydroquinone
42
21. K. Na, T. Okuhara and M. Misono, J. Chem. Soc. Faraday Trans. 1995, 91, 375.
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22. L.E. Briand, H.J. Thomas and G.T. Baronetti, Appl. Catal. A 2000, 201, 191.
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3 Synthesis o f Polyoxom etalates
CONTENTS
3.1 G eneral methods of s y n t h e s i s ............................................................................................ 48
3.2 K eggin polyoxometalates .......................................................................................................... 50
3.2.1 12-M olybdosilicic acid, a -H 4[S iM o i20 4o ]......................................................................... 50
3.2.2 12-T ungstosilicic acid, a -H 4[SiW i20 4 o ] ......................................................................... 51
3.2.3 12-T ungstophosphoric acid, a -H 3[PW i20 4o ] .................................................................. 51
3.2.4 12-M olybd op h osp h oric acid, a -H 3[P M o ]20 4o ] ............................................................ 51
3.2.5 12-T ungstogerm anic acid, a -H 4[G eW i20 4o ] .................................................................. 52
3.2.6 1 1-M o ly b d o -l-v a n a d o p h o sp h o ric acid, H tiP M o u V 04o ] ........................................ 53
3.2.7 1 0-M olybd o-2-van adop h osph oric acid, H 5[PM oioV 20 4o ] ........................................ 53
3.2.8 9 -M olyb d o-3-van ad op h osp h oric acid, H 6[P M o9V 30 4o ] ........................................ 53
3.2.9 T ransition-m etal-substituted tu ngstop h osp h ates, {P W n M 0 3 9 } ........................... 54
3.3 W ells- dawson p o l y o x o m e t a l a t e s ...................................................................................... 54
3.3.1 18-T ungstodiphosphoric acid, H6tP2W ig 0 6 2] ............................................................ 54
3.4 Sandw ich - type p o l y o x o m e t a l a t e s ...................................................................................... 55
3.4.1 N a I2[W Zn3(H 20 )2(Z nW 90 3 4)2] ...................................................................................... 55
3.4.2 N a i2[W C oI3I(H 20 )2(C o n W 90 3 4)2] ...................................................................................... 55
3.4.3 Kj i [W Z nR u2u ( 0 H ) ( H 20 )(Z n W 90 34) 2] ......................................................................... 56
3.4.4 K io[W Z nR h I[I2(H 20 )(Z n W 90 34)2]...................................................................................... 56
3.5 PEROXO POLYOXOMETALATES.......................................................................................................... 56
3.5.1 V enturello com p lex, { P 0 4[ W 0 ( 0 2)2]4 }3~ ......................................................................... 56
3.6 POLYOXOMETALATE CATALYSTS.......................................................................................................... 57
3.6.1 Solid acid c a t a l y s t s ................................................................................................................. 57
3.6.1.1 C s2.5 H 0,5 [PW 12O 40] ................................................................................................ 57
3.6.1.2 S ilica-supported H 3[PW i204 o] ........................................................................... 57
3.6.1.3 S o l-g e l c a t a l y s t s ....................................................................................................... 58
3.6.2 H o m o g en eo u s c a t a l y s t s ........................................................................................................... 58
3.6.2.1 M olybd o v a n a d o p h o sp h a tes, [P M o i2_ nVn0 4 o](3+n)_.................................. 58
3 .6.2.2 M o ly b d o p h o sp h o ric acid, H 3P G 1 • 6M 0O 3 ................................................ 59
R eferences .................................................................................................................................................. 59
General methods of synthesis of heteropoly- and isopolyoxometalates are well

documented.[1~5] Much current research is directed towards the development of
new synthetic strategies in polyoxometalate chemistry. These involve, among
others, synthesis in both aqueous and nonaqueous s o lv e n ts ,th e incorporation
of organic and organometallic functionalities1^ as well as sulfur[8] in polyox
ometalates, and the synthesis of extremely large polyoxometalates using pre
organised metal-oxide building blocks (synthons).[91
48 CATALYSIS BY POLYOXOMETALATES SYNTHESIS OF POLYOXOMETALATES 49
This chapter gives an overview of some general preparation methods. Sub can also be prepared from solutions of their salts by ion exchanged4’51 The
sequent sections present a collection of syntheses of most typical heteropoly etherate method and ion exchange can also be used for regeneration of hetero
compounds that are used as acid and oxidation catalysts, including some poly acid catalysts.
supported solid acid catalysts. In some cases, mixtures of polyoxometalates, Electrodialysis has attracted interest as an effective method for clean pro
that are much easier to prepare, rather than pure individual compounds are duction of heteropoly acids with high yields.112-151 The synthesis is carried out
used as catalysts. Examples of these are given in the last sections of this chapter. in an electrolytic cell separated into anodic and cathodic sides by a cation-
exchange membrane. An electric potential (ca. 12 V) is applied across the
membrane. Initially, the anodic side is in contact with an aqueous solution of
3.1 GENERAL M ETHODS OF SYNTHESIS sodium tungstate or molybdate and a salt of the heteroatom taken in an almost
stoichiometric ratio; the cathodic side is filled with distilled water. The anodic
Generally, polyoxometalates form in solutions from simple oxoanions and the side is acidified by electrolysis of water, and N a+ ions are transferred from the
necessary heteroatoms by a self-assembly process upon acidification.!1-51 For anode to cathode side by the applied potential through the cation-exchange
example: membrane to yield the pure heteropoly acid in the anodic chamber. For
example, an efficient electromembrane synthesis of H 3[PWi20 4o] from
12 W 0 42- + H P 0 42- + 23H+ -► [PW]2O40]3“ + 12H20 (3.1) N a2W 0 4 with H 3P 0 4 has been developed.!13,141 This method is illustrated
schematically in Figure 3.1. The [PWi20 4o]3- anion is formed in the anionic
11 M o 0 42- + V 0 3“ + H P 0 42- + 21 H + -> [PM on VO40]4“ + 11 H20 (3.2) side of electrodialyser in two stages. In the first stage, which is carried out in the
absence of phosphate ions, the WO4- ions are converted electrochemically into
Most polyoxometalates have been prepared in aqueous solutions. How the isopolytungstate [W70 24]6 -. Then H 3P 0 4 is introduced and the electrodi
ever, nonaqueous[61 and solid-state syntheses!101 have also been developed. A alysis process is continued until completion to yield H 3[PWi20 4o] and NaOH
few commonest heteropoly acids such as H 3[PWi20 4o], H 4[SiWi20 4o], and aqueous solutions in the anodic and cathodic sides, respectively. The hete
H 3[P M o i 20 4o], that are of great importance for catalysis, are commercially ropoly acid is isolated from aqueous solution by crystallisation with an
available as crystalline hydrates. The vast majority of polyoxometalates have to almost 100% yield based on N a2W 0 3. The NaOH so obtained can be
be synthesised in-house; the preparation techniques vary considerably used for the preparation of N a2W 0 3 from W 0 3. N o waste is therefore
depending on the type of polyoxometalate. In many cases, when the equilib formed in the process. The sodium content does not exceed 0.01 wt% in the
rium is favourable, polyoxometalates can be prepared in good yields at room final product. Similarly, other heteropoly acids such as H ^S iW Ô ^],
temperature from nearly stoichiometric amounts of their com ponents.11-51 H stPW nT iO ^], H 5[PW ,,ZrC M , H6[PW ,, BiO40], and H 6[P2W2i 0 7i] have
Otherwise, excess heteroelement and a precise reaction control are required. been obtained.!12,151
Acidification is generally achieved by addition of mineral acids such as HC1, Lacunary heteropoly anions are frequently used for the preparation of
H 2S 0 4, HC104, or H N O 3. Itc a n also be done by using an acidic ion-exchange transition metal-substituted polyoxometalates. The most common Keggin
resin (e.g. Amberlyst-15) or electrolytically.!4,51 The heteropoly anions are and W ells-Dawson lacunary polyanions are formed by adding controlled
usually isolated from aqueous solution by addition of an appropriate counter am ounts of alkali to the parent polyanions in aqueous solution.!1-51
cation, for example, an alkali metal, ammonium, or tetraalkylammonium.
Lithium and sodium salts are generally more water-soluble than those of
potassium, rubidium or cesium. Tetrabutylammonium salts are usually insol 4-9e _ A
uble in water; they can be recrystallised from solvents such as acetonitrile or 2H 20 — 4 H ++ 0 2^ 2H 20 — 2 0 H + H 2T
acetone^41
The free Keggin and Wells-Dawson heteropoly acids are sufficiently stable
Na+ —
to allow crystallisation from aqueous solution. These acids can be prepared by
the classical ‘etherate’ method developed by Drechsel.[11] This method includes W 0 42- [ W 70 24]6"
the extraction of the heteropoly acid with diethyl ether from a strongly acidified
[ W 70 24] 6-+ H P 0 42- i £ [ P W 12O 40] 3-
(e.g. with HC1) aqueous solution of the heteropoly anion to form a heavy oily
etherate of the heteropoly acid as a bottom layer. The etherate layer is drawn Membrane
off and decomposed by adding water under air stream. Then the product
heteropoly acid is crystallised from the aqueous solution. Heteropoly acids Figure 3.1 The scheme of electromembrane synthesis of H3[PWi204o].[13,141
OH
(3.3) 3.2.2 12-TUNGSTOSILICIC ACID, a-H ^S iW Ô « ]
[PW12O40]3- ------- -> [PW u 0 39]7- + W ( V D
OH - Sodium tungstate hydrate, N a2W 0 4 ■2H20 (20.0 g, 0.061 mol) was dissolved in
[P2w 18o 62]6- ------- - [ P 2W 17O61]10-+W (V I) (3.4) water (40 ml), and to this solution was added sodium metasilicate (0.0071 mol).
The mixture was stirred with a magnetic stirrer and heated to boiling
Further incorporation of a transition metal cation into the lacuna leads to the while concentrated hydrochloric acid (12 ml) was added over 90 minutes
transition metal-substituted polyoxometalate, for example: using a dropping funnel. The slight precipitate of silicic acid was filtered off,
and the mixture cooled. Concentrated hydrochloric acid was added (8 ml) and
the solution cooled again. This solution was shaken with a slight excess of
[PWn 0 39]7' + Co2+ -► [PW nCo0 39]5” (3.5)
diethyl ether, and the bottom oily layer of the ether complex was drawn off.
This complex was dissolved in 3M hydrochloric acid (20 ml) and extracted
The following sections give examples of syntheses of some typical polyox- again with diethyl ether. The ether complex was separated, and the diethyl ether
ometalates that are used as acid or oxidation catalysts. The corresponding removed by passing air over the mixture while it was heated on a water bath.
characterisation data can be found in the references provided. This was continued until crystals appeared at the edge of the liquid. The
solution was then set aside for slow crystallisation or evaporated to dryness.
This procedure was repeated until the product no longer smelled of HC1. When
3.2 KEGGIN POLYOXOMETALATES the acid was sufficiently dry, it was ground in a m ortar and dried to constant
weight at 70 °C to give a-H 4[SiWi20 4o] 6 - 9 H 20 / 16] In our hands, the yield was
3.2.1 12-MOLYBDOSILICIC ACID, a-H 4[SiMo120 4o] 80-85% based on sodium tungstate. IR (KBr, cm-1): 981 (W = 0 ), 928 (Si-O),
880 (W -O -W ), 785 (W -O -W ) / 181
The following modification of the procedures116-181 was used. Sodium molyb
date, N a2M o 0 4 • 2H20 (50 g, 0.21 mol) was dissolved in water (200 ml), and
the solution heated to 80 °C. To this solution was added concentrated hydro 3.2.3 12-TU N G STO PH O SPH O RIC ACID, a-H 3[PWi2O40]
chloric acid (20 ml). The mixture was stirred vigorously with a magnetic stirrer
while sodium metasilicate (0.045 mol) dissolved in water (50 ml) was added Sodium tungstate, N a2W 0 4 • 2H20 , (100 g, 0.303 mol) and disodium phos
dropwise over 30 min. The resulting solution turned yellow. While the stirring phate, N a2H P 0 4, (13 g, 0.090 mol) were dissolved in boiling water (150 ml)
was continued, concentrated hydrochloric acid (60 ml) was added dropwise while magnetically stirred. Concentrated hydrochloric acid (80 ml) was added
from a dropping funnel. The slight precipitate of silicic acid was filtered off dropwise with constant stirring. Tungstophosphoric acid began to precipitate
through a porous glass filter. The filtrate was cooled and extracted with when most of the acid was added. After the solution was cooled, diethyl ether
diethyl ether. The ether complex was diluted with one-half of its volume of (about 60 ml) was added until, after shaking, three layers formed. More water
water, and the diethyl ether rapidly displaced by a stream of air. Should the could be used to dissolve the sodium chloride, if necessary. The heteropoly
solution become green due to reduction, the yellow colour could be restored by etherate, which constituted the lower layer, was washed several times with
adding a small amount of concentrated nitric acid. The product crystallised water to which enough diethyl ether was added to form a third layer. It was
readily. then separated and evaporated to dryness while mildly heated under air cur
For purification, the product was dissolved in a mixture of water (50 ml) and rent. The solid material was dried to constant weight at 70 °C to give
concentrated hydrochloric acid (15 ml) and extracted with diethyl ether. The a-H 3[PWj20 4o] 6—7H20 with about 80% yield based on the sodium tung
ether was removed as previously described, and the yellow liquid was concen state/ 161 IR (KBr, cm-1): 1080 (P-O), 990 (W = 0 ), 890 (W -O -W ), 810 (W -
trated at 40 °C and crystallised at room temperature to yield 12-molybdosilicic 0 -W ).[18] 31P N M R (H20 , ppm): -1 4 .9 .[,9]
acid hydrate, a-H 4[SiMoi20 4o]xH20 . Care must be taken to guard against
reduction. A small amount of concentrated nitric acid could reoxidise the
acid and restore the yellow colour. The crystals formed contained about 29 3.2.4 12-MOLYBDOPHOSPHORIC ACID, a-H3[PMoi204o]
molecules of water of hydration. M ost of this water could be removed by
heating the acid at 60 °C under vacuum or drying in a desiccator over P2Os. This acid was prepared from its disodium salt, a-N a2H [PM oi20 4o], by extrac
The product then contained five to six molecules of water. IR (KBr, cm-1): 957 tion with diethyl ether from acidified aqueous solution/ 161 The preparation of
M o = 0 ), 904 (Si-O) 855 (M o-O -M o), 770 (M o -0 -M o ).[18] a-N a2H [PM o120 4o] was as follows. To an aqueous solution of N a2M o 0 4
(420 ml. 2.85 M) were added successively H 3PO4 (85%, 14.7 M, 6.8 ml) and 3.2.6 11-MOLYBDO-l-VANADOPHOSPHORIC ACID, H4[PM on VO40]
HCIO4 (70%, 12M. 284ml). The disodium salt a-N a2H |PM oi2 0 4o] prec
ipitated from the yellow warm solution. After the mixture was cooled to N a2H P 0 4 (7.1 g, 0.050 mol) was dissolved in water (100 ml) and mixed with
room temperature, the microcrystalline powder was filtered and air-dried to sodium metavanadate (6.1 g, 0.050 mol) that had been dissolved by boiling
yield 250 g of product. Recrystallisation in a mixture of ether/water (40 ml/ in water (100 ml). The mixture was cooled and acidified to a red colour
200 ml) gave 180 g of greenish microcrystals of the a-N a2H[PMoi204o] hydrate. with concentrated sulfuric acid (5 ml). To this mixture was added a solution
IR (KBr. cm“ 1): 1068 (P-O), 962 (M o= 0), 869 (M o-O -M o), 785 (M o-O - of N a2M o 0 4 • 2H20 (133 g, 0.55 mol) dissolved in water (200 ml). Finally,
Mo).[18] concentrated sulfuric acid (85 ml) was added slowly with vigorous stirring of
0C-H3IPM012O40] was obtained from an aqueous solution of a-N a2H the solution. With this addition the dark red colour changed to a lighter
[PM012O40] ■14H20 (250 g/200 ml), acidified by 50 ml of 12 M HC1, and ex red. The heteropoly acid was then extracted with diethyl ether (400 ml) after
tracted by ether (400 ml). The heavy layer (300 ml), added with half its volume the water solution was cooled. In this extraction the heteropoly etherate
of water, gave yellow crystals after desiccation (190 g). IR (KBr, cm-1): 1067 was present in the middle layer; the aqueous layer (bottom) was yellow and
(P-O), 975 (M o= 0), 963 (vs), 870 (M o-O -M o), 810 (M o -0 -M o ).[,8] 31P N M R probably contained vanadyl species. After separation, a stream o f air was
(H20 , ppm): -3 .9 .[19] passed through the heteropoly etherate layer to free it of diethyl ether. The
12-Molybdophosphoric acid can be prepared by a clean procedure from orange solid that remained was dissolved in water (50 ml), concentrated to
M0O3 and 85 % H3PO4 without ether extraction.1201 In our laboratory a modi the first appearance of crystals in a vacuum desiccator over concentrated
fication of this method was used. A mixture of M0O3 (100 g, 0.695 mol) and sulfuric acid, and then allowed to crystallise further. The orange crystals
H3PO4 (85%, 0.14 mol) in 500 ml of deionised water was refluxed with intense that formed were filtered, washed with water, and air-dried (28 g, 23%).
stirring for 20 h until most of the M0O3 dissolved to form a greenish solution. The am ount of water of crystallisation varied slightly from sample to
The undissolved M0O3 was filtered off. The solution was evaporated until crust sample.1211
appeared. A small amount of concentrated nitric acid was added to oxidise
Mo(V) to Mo(IV); the green solution turned yellow. The solution was set aside
for slow crystallisation that afforded a-H 3[PMoi204o] hydrate as yellow crys
3.2.7 10-M OLYBDO-2-VANADOPHOSPHORIC ACID, H5[PMo,oV204o]
tals (55-60% based on M 0O3). The product was recrystallised from water. The
filtrate after crystallisation, containing Mo(VI) and H 3PO4, could be used in
Sodium metavanadate (24.4 g, 0.20 mol) was dissolved by boiling water
further preparations.
(100ml) and then mixed with N a2H P 0 4 (7.1 g, 0.050mol) in water (100ml).
After the solution was cooled, concentrated sulfuric acid (5 ml) was added, and
the solution developed a red colour. An addition of N a2M o 0 4 • 2H20 (121 g,
3.2.5 12-TUNGSTOGERMANIC ACID, oc-H^GeWnOio] 0.50 mol) dissolved in water (200 ml) was then made. While the solution was
vigorously stirred, concentrated sulfuric acid (85 ml) was added slowly, and the
An aqueous solution of Na2W04 • 2H20 (1.25 M, 250 ml) was mixed with the hot solution was allowed to cool to room temperature. The 10-molybdo-2-
germanate solution (70 ml) containing powdered Ge metal (99.999%, 10.5 g, vanadophosphoric acid was then extracted with diethyl ether (500 ml). Air was
0.144 mol) suspended in NaOH (6.25 M, 60 ml). The mixture was heated to passed through the heteropoly etherate to free of diethyl ether. The solid
80 °C. Concentrated HNO3 (13 M, 45 ml) was added dropwise with stirring remaining was dissolved in water, concentrated to first crystal formation, as
until pH 0.5. (Cloudiness that appeared at the beginning of the addition already described for H4[PM o ii V04 o], and then allowed to crystallise further.
progressively dissolved, and the solution became clear at the pH 0.5.) After The large red crystals that formed were filtered, washed with water and air-
keeping for six hours at 80 °C to complete ß —►a isomerisation, the solution dried (35 g, 30% based on molybdate).[211
was cooled to room temperature. A further addition of H N O 3 (13M, 10 ml)
allowed the extraction with diethyl ether. After separation, the organic layer
was added with half its volume of water and put in a vacuum desiccator over 3.2.8 9-MOLYBDO-3-VANADOPHOSPHORIC ACID, H6[PMo9V30 4o]
concentrated sulfuric acid. The crystallisation was performed in a refrigerator
to yield 66 g of a-H4[GeW1204o] • 14H20 . IR (KBr, cm“ 1): 980 (W = 0), 903 N a2H P 0 4 (7.1 g, 0.050 mol) was dissolved in water (50 ml) and mixed with
(W-O-W), 818 (Ge-O), 760 (W -0-W ).[l8] sodium metavanadate (36.6 g, 0.30 mol) that had been dissolved by heating in
water (200 ml). Concentrated sulfuric acid (5 ml) was added to the cooled solution being kept at 250 ml by adding water. To prevent reduction, a small
mixture, and it attained a cherry red colour. This solution was mixed with am ount of H N 0 3 was added to the light yellow solution. The solution was
N a2M o 0 4 ■2H20 (54.4 g, 0.225 mol) dissolved in water (150 ml), and then, evaporated until crust appeared, cooled to 0 °C and the precipitate was separ
while it was being vigorously stirred, concentrated sulfuric acid (85 ml) was ated by filtration. The precipitate was dissolved in water (30 ml) and recrystal
slowly added. The hot solution was allowed to cool to room temperature. The lised at room temperature. The product was extracted with diethyl ether. By
free acid was extracted with diethyl ether (400 ml), the heteropoly etherate recrystallisation from water, yellow crystals o f H6[P2W 180 62] • 32H20 were
being the middle layer. The etherate was freed of diethyl ether by passing a obtained.124’251 IR (KBr, cm“ 1): 1091 (P-O), 962 (W = O), 914 (W -O-W ),
stream of air through the solution. The red solid remaining was dissolved in 780 (W -0 -W ).[25]
water (40 ml) and concentrated to crystal formation in a vacuum desiccator
over concentrated sulfuric acid. The red crystals were filtered and washed with
water (the yield, 7.2g).[211 3.4 SANDW ICH-TYPE POLYOXOM ETALATES
3.4.1 N a 12[WZn3(H20 )2(Zn W 90 34)2]

3.2.9 TRANSITION-M ETAL-SUBSTITUTED
TUNGSTOPHOSPHATES, { P W „ M 0 39} A solution of N a2W 0 4 ■2H20 (127 g, 0.38 mol) in water (350 ml) was treated
with nitric acid (14N , 2ml, 0.35mol) at 80-85°C with vigorous stirring until
The salts (TBA)4Hx[PW i1M (H2 0 )039]nH20 (M = Co2+, N i2+, M n2+, Fe3+, the precipitate that formed initially dissolved entirely. A solution of zinc nitrate
etc.; TBA = tetra-n-butylammonium) were synthesised by the following pro hexahydrate (29.8 g, 0.10 mol) in water (100 ml) was then added with continu
cedure1221 that is a modification of the general protocol elaborated by Toum e et ous stirring and heating at 90-95 °C (not boiling). The addition was carried out
n/.[231 An aqueous solution of the anion [PW nM (H 20 ) 0 39]5~ was prepared by first in small aliquots (ca. 3-4 ml), giving a white precipitate which redissolved
mixing N a2H P 0 4 (9.1 mmol), N a2W 0 4 • 2H20 (100 mmol) and a nitrate or rapidly (until 2/3 o f the zinc nitrate solution was added), then dropwise, more
sulfate salt of M (12 mmol) in 200 ml of water and adjusting the pH to 4.8 by and more slowly, in such a way that the mixture remained clear till the end. The
adding acetic acid or dilute nitric acid solution dropwise. An aqueous solution process required 2-3 hours. The final pH was about 7.5. If necessary, the
of TBA bromide (45 mmol) in water (20 ml) was added dropwise, with stirring, solution was filtered (a possible slight turbidity might not be filterable). A
at 80-85°C. The solid formed was filtered off and recrystallised from acetoni first crystallisation occurred on moderate cooling (to about 40 °C), affording
trile. Upon recrystallisation some insoluble material was separated and the salt a first crop as fine needles. The liquid was evaporated to half volume and left
(TBA)4H x[PW iiM (H2 0 )039]nH20 precipitated by addition of water (1:1). In unstirred, covered, at 50 °C. Overnight, needle-like crystals appeared and were
the case of iron(III)-substituted compound, a few drops of nitric acid were left to grow for 3^1 days. Thus the product (90-95 g, 65-68 %) was initially
added to the acetonitrile solution so as to turn the solution from green to yellow separated. The resulting cold filtrate was shaken with equal volume of acetone
(conversion of the dimeric anion). All salts were dried in vacuum at 100 °C. to extract the m ajor part of the sodium nitrate produced (two layers). The dense
The following compounds were prepared as hydrates: lower layer was diluted with an equal volume of water, heated to 50 °C, and
[(C4H 9)4N]4H[PW] , M n(H20 ) 0 39], [(C4H 9)4N]4H[PW! i Co(H20 ) 0 39], left at this temperature to yield an additional am ount of product. The
[(C4H9)4N]4H[PW! iN i(H 20 ) 0 39], [(C4H 9)4N]4H [PW ,iC u(H 20 )039], and process was repeated until the filtrate no longer crystallised at room temp
[(C4H 9)4N]4[PW \ i Fe(H 20 ) 0 39]. erature. A total yield of 85-90% was obtained. The collected crops were
(TBA)4H 3[PW h 039] was prepared using a similar procedure except for the recrystallised together from water to give a homogeneously hydrated product
addition of the salt of M. N ai2[WZn3(H20 ) 2(ZnW90 34)2] • 4 6 -4 8 H 20 . A similar procedure can be
carried out using different reagents (HC1 or acetic acid and chloride or acetate).
The nitric acid medium allowed, however, the best separation of the sodium salt
3.3 W ELLS-DAW SON POLYOXOM ETALATES formed.1261
3.3.1 18-TUNGSTODIPHOSPHORIC ACID, H 6[P2Wi8062]

3.4.2 N a12[WCo3II(H20 ) 2(CoIIW90 34)2]
N a2W 0 4 -2H 20 (150 g) was dissolved in hot water (150 ml), and then were
added an aqueous solution of H 3P 0 4 (85%, 125 ml) and water (30 ml) with The preparation of the cobalt(II) homologue was identical.1261 The solution was
vigorous stirring. The solution was boiled for 5 hours, the volume of the initially emerald-green, but turned olive-green on prolonged heating, indicating
the formation of the expected polyanion. A pink precipitate eventually 31.0; P, 1.31; O (active), 5.66. Molecular weight (CHC13): M r calculated 2256.7,
appeared and readily separated to give N a ^ W C o jX ^ O iX Q ^ W g C ^ ^ ] • 46 M x observed 2190. IR (neat, KBr plates, cm-1): 1088, 1058 and 1035 (sh) (P -
- 48H2O. The yield varied between 50 and 80%. O), 975 (W = O), 856 and 846 (O-O), 591 and 523 (W -O-O ); other bands at
725, 651, 576 and 549.[29]
3.4.3 K, ][WZnRuni2(0 H)(H20 )(ZnW9034)2]

3.6 POLYOXOMETALATE CATALYSTS
To a solution of N ai2[WZn3(H20)2(ZnW9034)2] • 46H20 (23 g, 3.9 mmol) in
water (10 ml) at 90 °C under argon was added Ru(DMSO)4Cl2 (4 g, 12.2 mmol). 3.6.1 SOLID ACID CATALYSTS
The solution was stirred at this temperature for 18 h and then cooled and
opened to air. A brown solution was obtained which, upon addition of potas 3 .6 .1 .1 C S2.5H o.5 [P W 12 0 4 o]
sium chloride (2 g), yielded a crude precipitate of the ruthenium-substituted
This insoluble salt was prepared simply by adding a stoichiometric am ount of
polyoxometalate (10.9 g, 46%). The product was crystallised twice from hot
caesium carbonate to H 3IPW12O40] in concentrated aqueous solution/30^ The
water to give K n fW Z n R u ^ O H X ^ O X Z n W g C ^ ] ■13H20 (24%).[27] caesium salt precipitated quantitatively, with C 0 2 evolving, and isolated by
The sodium salt N a1i[WZnRuIII2(0 H)(H20)(ZnW9034)2] ■42H20 was evaporation.
obtained by dissolution of potassium salt in 0.5 M solution of NaCl.p7J
H 3[PW12O40] + 1.25 Cs2C 0 3 -> C s2.5H o.5[PW i 204 o] + 1-25 C 0 2 + 1.25 HzO
3.4.4 K 1o(WZnRhI,I2(H20)(ZnW9034)2] A stoichiometric am ount of aqueous caesium carbonate (0.47 M) was added
dropwise with stirring to an aqueous solution of H 3[PW j20 4o] (0.75 M) at room
A similar procedure using RhCl3 • 3H20 instead than R u(DMSO)4C12 gave temperature. The white precipitate obtained was aged in water for 20 hours at
rhodium analogue Kio[WZnRhni2(H2 0 )(ZnW9034)2] • 40H2O.[28] A hot aque room temperature, then evaporated to dryness at 45 °C under vacuum
ous solution containing RI1CI3 ■3H20 (2.5 eq) and N ai2[(WZn3)(ZnW9034)2] (25 Torr). The solid obtained was ground in a m ortar and finally calcined at
(1 eq) was stirred for four hours. A colour change from deep brown to light 300 °C for 3 hours under vacuum (25 Torr). Caesium tungstophosphates with
brown was observed. After addition of KC1 and cooling, a light brown solid
various Cs/P ratios were prepared similarly.
was precipitated. The crude polyoxometalate was then purified by recrystallisa Acidic caesium tungstophosphates C sxH 3_x[PW i20 4o] were also prepared by
tion from water (27 %).
grinding a mixture of H3[PWi204o] and C s3[PW i2O40].[31] This procedure was
claimed to lead to high surface area catalysts that showed better activities for n-
butane isomerisation compared to the catalysts prepared by precipitation.
3.5 PEROXO POLYOXOMETALATES
3.6.1.2 Silica-Supported H 3[PWi2O40]
3.5.1 VENTURELLO COMPLEX, {P04[W 0 (0 2)2]4}3-
Catalysts containing 10 to 50wt% H 3[PW i2O40] on silica were prepared by
A suspension of tungstic acid (2.5 g, 10 mmol) in aqueous H 20 2 (30%, 7 ml) shaking a suspension of Aerosil 380 (Degussa) in an aqueous solution (3-5 ml),
was stirred and heated to 60 °C until a colourless solution was obtained. To this containing a certain amount of heteropoly acid, in a glass vessel overnight at
solution, filtered and cooled to room temperature, was added 40% H 3P0 4 room temperature.[32] The pH of the impregnating aqueous solution varied
(0.62 ml, 2.5 mmol), and the solution was diluted with water (30 ml). Then from 1 to 2 depending on the heteropoly acid loading. For the loadings
methyltrioctylammonium chloride (2.03 g, 5 mmol) in dichloromethane < 20 wt%, methanol was preferably used instead of water to prevent decom
(40 ml) was added dropwise with stirring over about two minutes. Stirring position of heteropoly acid. The solvent was evaporated in a rotary evaporator
was continued for an additional 15 minutes. The organic phase was then at the temperature below 60 °C. The catalysts were ground in a m ortar, calcined
separated, dried over sodium sulfate, filtered, and gently evaporated under at 150 °C/0.3 T orr for 1.5 hour and stored in a desiccator over P2O5. Similarly,
reduced pressure at 40-50 °C to give an almost colourless syrup of the salt other heteropoly acids, e.g., H4[SiWi2O40], H 3[PMoi204o], etc., can be sup
[(C8H i7)3N CH 3]3{P0 4[W0 (02)2]4} (3.7g, 98%, based on the quaternary am ported on silica or another support. Prior to use, the silica-supported catalysts
monium salt charged). Anal. Calcd for C75Hi62N3PW4024: C, 39.91; H, 7.24; may require treatment at higher temperatures (200-300 °C) to remove traces of
N, 1.86; W, 32.6; P, 1.37; O (active), 5.68. Found: C, 40.30; H, 7.39; N, 1.84; W, water.
SYNTHESIS OF POLYOXOMETALATES 59
3.6.1.3 Sol-Gel Catalysts 3.6.2.2 Molybdophosphoric Acid, H3P 0 4 • 6M0O 3

Silica-included H 3[PW,2O40] and Cs2.5Ho.5[PW,20 4o] were prepared by a sol-
An aqueous solution of heteropoly acid catalyst of the composition
gel technique through the hydrolysis of ethyl orthosilicate conducted at 40 °C
H 3P 0 4 • 6M o0 3 with excellent stability and a long shelf-life was prepared in
for one hour and then at 80 °C for three hours in the presence of
our laboratory by the following procedure.1361 Molybdenum trioxide (21.6 g,
C s2.5H o.5[PW i204 o] or H 3[PW1204o] dispersed or dissolved in ethanol.[30] The
0.15 mol) and H3P 0 4 (85%, 0.025 mol) were refluxed in distilled water (100 ml)
hydrogel obtained was dehydrated slowly at 45 °C under vacuum (25 Torr),
for 20 h until M o 0 3 almost completely dissolved to form a green solution.
followed by grinding to fine particles. In the case of salt inclusion, the dried gel
Undissolved M o 0 3 was filtered off, and the solution was evaporated to a volume
was extracted with water at 80 °C for 10 hours to remove the non trapped salt
of 30 ml to afford a dark green solution of molybdophosphates with a formal
and organics, and finally calcined at 300 °C for three hours under vacuum
composition of H 3P 0 4 • 6 M o 0 3 (98.6% yield). The catalyst solution had a
(25 Torr). As for the acid inclusion, the dried gel was once calcined at 150°C
concentration of ca. 50wt%, 1.54 g cm-3 density, and pH « 0. The catalyst
for three hours under vacuum (25 Torr) to fasten the silica network, then
was stable in a stoppered glass bottle for years. From 31P N M R, the fresh
extracted with water at 80 °C for three hours, and finally calcined at 150 °C
catalyst solution mainly contained a mixture of H3P 0 4 and H ^P M oÔ ^]-
for three hours under vacuum (25 Torr).
After two years on the shelf, it turned to be H 3P 0 4 and H6[P2Moig062].f371
This catalyst was tested in many homogeneous acid-catalysed reactions. It was
particularly effective for hydration of olefins (e.g. isobutene) and decomposition
3.6.2 HOMOGENEOUS CATALYSTS of cumene hydroperoxide into phenol and acetone.[36]
3.6.2.1 Molybdovanadophosphates, |P M oi2-nVnO 4o](3+n>~

Aqueous solutions of sodium salts of the Hs+ntPM oa-nVnO^] hetero REFERENCES
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4.1.2.1 Homogeneous sy stem s.............................................................................. 63
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31. P.-Y. Gayraud, N. Essayem and J.C. Vedrine, Catal Lett. 1998, 56, 35. 4.3.2.2 Esterification.............................................................................................. 78
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33. K.I. Matveev, N.B. Shitova, Z.P. Pai, V.F. Odyakov, O.K. Akmalova, M.H. Ulrich, 4.4.1 Heteropoly acid c a t a l y s t s ..................................................................................... 80
L.I. Kuznetsova, T.A. Basalaeva, A.V. Rumyantsev, L.P. Shadrin and M.M. Dzha- 4.4.1.1 Acid site s................................................................................................... 80
lalova, British Patent 1,508,331 (Chem. Abstr. 1979, 90, 38531). 4.4.1.2 Bulk heteropoly a c i d s ............................................................................ 80
4.4.1.3 Supported heterpoly a c id s ...................................................................... 81
34. J.H. Grate, J. Mol Catal. A 1996,114, 93.
Heteropoly acids on s i l i c a ................................................................ 81
35. V.F. Odyakov, E.G. Zhizhina, R.I. Maksimovskaya and K.I. Matveev, Zh. Neorg.
Heteropoly acids on carbon................................................................ 84
Khun. 1998, 43, 1451. Other supported heteropoly acid catalysts......................................... 84
36. I.V. Kozhevnikov, K.I. Matveev, V.E. Tarabanko, G.N. Kirichenko, R.M. Masa- 4.4.1.4 Intrazeolite heteropoly a c i d s ................................................................ 85
gutov and Yu. V. Churkin, USSR Patent 706,109, 1979 (Chem. Abstr. 1980, 93, 4.4.1.5 Heteropoly s a lt s ........................................................................................ 87
7832). 4.4.1.6 Sol-gel catalysts....................................................................................... 88
37. I.V. Kozhevnikov, Unpublished data. 4.4.2 Heterogeneous catalysis inliquid-solid systems..................................................... 89
4.4.2.1 Paraffin a lk y la tio n .................................................................................. 89
4.4.2.2 Friedel-Crafts and related rea ctio n s..................................................... 90
4.4.2.3 Esterification, hydrolysis and related reaction s................................... 95
4.4.2.4 Miscellaneous reactions............................................................................ 98
4.4.3 Heterogeneous catalysis in gas-solid s y s t e m s .................................................... 99
4.4.3.1 Hydration of olefins.................................................................................. 100
4.4.3.2 Dehydration of a l c o h o l s ...................................................................... K)0
4.4.3.3 Esterification............................................................................................. 101
62 CATALYSIS BY POLYOXOMETALATES ACID CATALYSIS BY HETEROPOLY COMPOUNDS 63
4.4.3.4 Friedel-Crafts and related reactions.................................................... 101 4.1.2 MECHANISTIC PRINCIPLES

4.4.3.5 Oligomerisation of o lefin s..................................................................... 103
4.4.3.6 Isomerisation of a l k a n e s ..................................................................... 103 Generally, reactions catalysed by heteropoly acids may be represented by the
4.4.3.7 Conversion of methanol to h yd rocarb on s........................................ 105
4.4.3.8 Synthesis of M TBE................................................................................ 106
conventional mechanisms of Bronsted acid catalysis. In a simple case of single
4.4.3.9 Nitration of b e n z e n e ........................................................................... 106 proton transfer, the mechanism may include the protonation of the substrate
4.5 D e a c t iv a t io n AND REGENERATION OF SOLID HETEROPOLY ACID CATALYSTS . . . . 107 followed by the conversion of the ionic intermediate to yield the reaction
R e f e r e n c e s ................................................................................................................................... 109 product:12,31
S i + H +^ S , H + - ^ > P + H+ (4.1)
Heteropoly acids have found numerous applications as acid catalysts, including
several industrial applications, for example, for hydration of olefins, polymer In this equation, Si and S2 are the substrates and P is the product. In accordance
isation of tetrahydrofuran, and esterification (Chapter 7). In this chapter, we with this mechanism, the catalytic activity of heteropoly acids, both in homoge
will discuss homogeneous and heterogeneous acid catalysis by heteropoly acids neous and heterogeneous systems, usually parallels their acid strength,
for organic reactions in liquid phase and gas phase. Various aspects of this i.e. H 3[PWi204o] > H 4[SiWi20 4o] > H 3[PMo12O40] > H4[SiMo12O40].[2] Being
topic have been reviewed.11-121 stronger acids and therefore more efficient proton donors, heteropoly acids
usually exhibit higher catalytic activities than conventional mineral acids. Rela
tively strong oxidants, molybdenum heteropoly acids are frequently deactivated
4.1 GENERAL OVERVIEW due to their reduction by the organic reaction medium; it is not uncommon for
them to show lower activities than those expected from their acid strengths.121
4.1.1 THE SCOPE OF APPLICATIONS
4.1.2.1 Homogeneous Systems
Table 4.1 shows some typical examples of acid-catalysed reactions with the use
of heteropoly acids as catalysts. The reactions are placed in the order of Kinetics o f several HPA-catalysed homogeneous reactions, such as hydration
decreasing catalyst acid strength required for the reaction to occur, ranging of isobutene,14,131 decomposition of cumene hydroperoxide,[141 esterification,1151
from the highly demanding reactions such as alkane isomerisation to very mild hydrolysis of t-butyl fluoride,1161 and others,[1,41 has been studied in aqueous or
additions and the Diels-Alder reaction. These reactions are carried out in nonaqueous solutions. Fairly good correlations between the reaction rates and
homogeneous or heterogeneous (gas-solid, liquid-solid or biphasic liquid- the dissociation constants or Hammett acidity function, H0, of heteropoly acids
liquid) systems. have been demonstrated.
Linear relationships between the logarithm of the observed rate constants
and H 0 with the slope of ca. 1 for the hydration of isobutene[13] and hydrolysis
Table 4.1 Reactions catalysed by heteropoly acids11,2].
of t-butyl fluoride1161 in concentrated aqueous solutions of heteropoly acids
Isomerisation of alkanes have been obtained (Figure 4.1) - which is in agreement with the mechanism of
Conversion of MeOH to olefins these reactions. Importantly, the conventional mineral acids such as
Alkylation of paraffins
H 2S 0 4, H N 0 3, and H C I0 4 also fit well these plots. This indicates that the
Oligomerisation of alkenes
Friedel-Crafts and related reactions principal mechanisms of these reactions are largely the same in the case of
Beckmann rearrangement: cyclohexanone oxime —>e-caprolactam heteropoly acids and mineral acids.
Esterification and transesterification In aqueous solution, typical Keggin heteropoly acids are fully dissociated
Hydration of alkenes 3-1 or 4 -1 polyelectrolytes (e.g. H 3[PWi20 4o] and H 4[SiWi20 4o], respectively).
Hydrolysis
Hence they can exert strong salt effects on catalysed reactions that may be
Prins reaction: alkene + HCHO —> 1,3-dioxane
Polymerisation of tetrahydrofuran significantly stronger than those in the case of mineral acids. Such salt effects
Trimerisation of aldehydes: RCHO —>l,3,5-trioxane may account for higher reaction orders with respect to H PA .1131 Thus for the
Decomposition: Ph(Me)2COOH -+ PhOH + Me2CO hydration o f isobutene,14,131 the reaction order with respect to H 3[PWi204o] and
Addition: isobutene +MeOH —>MTBE H 4[SiWi204o] was found to be 1.2-1.5 in dilute solutions (0.02-0.1 M HPA)
alkene + AcOH —>alkyl acetate and 2.0-2.2 in concentrated solutions (up to 0.5 M), whereas with nitric acid it
Diels-Alder reaction
is 1.0 regardless of the H N 0 3 concentration.
log k 4 + log k Table 4.2 Salt effects of acids on the hydration of isobutene in aqueous
solution at 25°C and 1 atm pressure1' 31.
104k0a 104A:'b B B* B-B*
1mol"1s“1 1 mol“1s“1 1mol-1 1mol“1 1mol“1
H3[PWl2O40] 20.0 ± 3 6.7 -0.87 -3.0 2.1
H4[SiWl2O40] 17.0 ± 4 4.3 -0.87 -3.0 2.1
hno3 3.8 ±0.4 3.8 - 0.02 - 0.2 0.2
a) Second-order rate constants of hydration of dissolved isobutene at unit concentration, per
1 mole I-1 of acid catalyst
b) The same rate constants, per 1 mole l-1 o f H+
It is suggested that heteropoly anions can stabilise cationic reaction inter

mediates (e.g. carbocations), thus promoting acid catalysed reactions in solu
tion and in pseudoliquid phase.11 Izumi et al. proposed such mechanism for
the liquid-phase hydration of isobutene (Section 4.2.2.1).[4]
Figure 4.1 The Hammett plots for acid-catalysed reactions: (a) hydration of isobutene in
water at 25 °C; the plot obeys an equation log k — -1.04 H0 - 3.46/31 (b) hydration of
tertbutyl fluoride in water at 25 °C; the plot obeys an equation log/: = -1.03H o - 3.52.[161 4.1.2.2 Heterogeneous Systems
Misono et alP '5,6i advanced a mechanistic classification for heterogeneous
Electrolyte salt effects on activity coefficients of nonelectrolytes (e.g. organic acid and oxidation catalysis by solid heteropoly compounds which distin
substrates),/, generally follow the empirical Setschenow equation:[17,18] guishes three types of catalysis, namely (i) surface type, (ii) bulk type I (or
“pseudoliquid”), and (iii) bulk type II (Table 4.3). The surface type is a
lo g / = B C s (4.2) conventional acid or oxidation catalysis on the gas-solid or liquid-solid inter
face, e,g. a Langmuir-Hinshelwood type process. This type applies to processes
where Cs is the molar electrolyte concentration and B is the Setschenow salt occurring on the surface of both bulk and supported heteropoly compounds.
effect parameter. Equation 4.2 is frequently used to account for salt effects on The bulk types of mechanism are largely relevant to reactions on bulk hetero
the reaction rate.[i8] For a monomolecular reaction, the conventional rate poly compounds. The bulk type I represents the acid catalysis by a bulk solid
constant k is given as heteropoly acid for the conversion of a polar substrate (e.g. alcohol, ether,
ketone, amine, etc.) that is capable of absorbing into the catalyst bulk. In this
logk = logk 0 + (B —B^) Cs (4.3)
Table 4.3 Three types of heterogeneous acid and oxidation catalysis by solid
where k 0 is the rate constant in pure solvent, B and B^ are the Setschenow salt heteropoly compounds11,5].
effect parameters for the ground state and transition state, respectively. Type Comment Example
This approach was used for the hydration of isobutene catalysed by hetero
Surface type Common type of surface reaction, e.g. Alkane isomerisation
poly acids and mineral acids (Table 4.2).[I3] It was shown that H 3[PWi20 4o] and Oxidation of aldehydes, CO
Langmuir-Hinshelwood type
H4[SiWi204o] cause ten times stronger overall salt effect on the reaction rate Rate cc catalyst surface area
(B - B^ = 2.1) than the 1-1 electrolyte H N 0 3(B —B^ = 0.2). This is in agree Bulk type I ‘Pseudoliquid phase’; reactants absorb Dehydration of i-PrOH
ment with the relative ionic strengths of these acids. All the acids salt-in both the in the solid bulk and react
ground state and the transition state of the reaction, i.e. increase the solubility of pseudohomogeneously
isobutene and decrease the energy of the transition state. For heteropoly acids, Rate oc catalyst volume (weight)
the rate constants k 0 extrapolated to zero molar concentration of acid catalysts Bulk type II Reaction occurs on the surface, with Oxidative dehydrogenation
(Cs -> 0) are greater than for H N 0 3, as expected. Based on unit proton concen the bulk diffusion of e~ and H+ Oxidation of H2
tration, however, these rate constants (k 0') are quite similar, as may be expected playing a key role
Rate oc catalyst volume (weight)
assuming the same reaction mechanism for all these acids.
case, the solid behaves like a concentrated solution (pseudoliquid phase), both 4.2 HOMOGENEOUS ACID CATALYSIS
the surface and the bulk acid sites participating in the reaction. The bulk type II
is suggested to apply to certain catalytic oxidations that largely occur on the 4.2.1 INTRODUCTION
catalyst surface, with the bulk diffusion of electrons and protons assisting the
redox process (Chapter 5). Heteropoly acids catalyse a wide variety of reactions in homogeneous liquid
Acid-catalysed reactions over bulk solid heteropoly acids occur by one of the phase offering strong options for more efficient and cleaner processing com
two mechanisms: surface-type catalysis (nonpolar substrates) or bulk-type I pared to conventional mineral a c i d s . B e i n g stronger acids, heteropoly
(pseudoliquid) catalysis (polar substrates).1'1 In the case of surface catalysis, acids will have significantly higher catalytic activity than mineral acids. In
that is common for heterogeneous acid catalysis, the catalytic activity usually particular in organic media, the molar catalytic activity of heteropoly acid is
depends on the surface acidity of heteropoly acid, i.e. the reaction rate is often 100-1000 times higher than that of H2S 04[1’31 (Table 4.5). This makes it
parallel to the number and the strength of the accessible surface acid sites. possible to carry out the catalytic process at a lower catalyst concentration and/
Polar molecules, such as alcohols, ethers, amines, etc., may react differently or at a lower temperature. Further, heteropoly acid catalysis lacks side reac
with crystalline heteropoly acids. Such molecules can absorb in large quantities tions such as sulfonation, chlorination, nitration, etc., which occur with mineral
into the catalyst bulk, forming HPA solvates^'1(Table 4.4). As the surface area acids.[2,3] As stable, relatively nontoxic crystalline substances, heteropoly acids
of bulk heteropoly acids is very low, only 1-5 m2 g_l, the absorption may be are also preferable regarding safety and ease of handling.
equivalent to dozens of m o n o la y ers.T h u s, towards polar substances, solid The relative activity of Keggin heteropoly acids primarily depends on their
heteropoly acids behave like highly concentrated solutions, i.e. all protons, acid strength. Other properties, such as the oxidation potential as well as the
both in the bulk and on the surface of heteropoly acid, participate in the thermal and hydrolytic stability are also important. These properties for the
catalytic reaction. This phenomenon is frequently referred to as ‘pseudoliquid most common heteropoly acids are summarised below:[2]
phase’.[1] Unlike polar molecules, nonpolar reactants (e.g., hydrocarbons) are
Acid strength PW > SiW > PMo > SiMo
incapable of absorbing in the bulk of heteropoly acids (Table 4.4). They
Oxidation potential PMo > SiMo > PW > SiW
interact only with the surface of the catalyst. The pseudoliquid behaviour
Thermal stability PW > SiW > PMo > SiMo
appears to be important for reactions of polar molecules at relatively low
Hydrolytic stability SiW >PW > SiMo > PMo
temperatures, i.e., when the sorption of substrate in the catalyst bulk is signifi
cant. Surface and bulk catalysis may operate with strongly differing selectiv- Usually, tungsten heteropoly acids are the catalysts of choice because of
ities.[11 On top of that, the uniformity of pseudoliquid phase allows using their stronger acidity, higher thermal stability and lower oxidation potential
spectroscopic techniques for studying the mechanism of catalytic processes. compared to molybdenum acids.[2,3] Generally, if the reaction rate is controlled
For example, probable reaction intermediates in the ethanol dehydration such by the catalyst acid strength, H 3IPW12O40] shows the highest catalytic activity
as the protonated ethanol dimer (EtOH)^, monomeric E tO H j, protonated in the Keggin series. However, in the case of less demanding reactions as well as
ether, and ethoxide were observed in the pseudoliquid H 3PPW12O40] phase by in reactions at higher temperatures in the presence of water, H4[SiWi204o],
solid-state NMR and IR spectroscopy.[11 having lower oxidation potential and higher hydrolytic stability, could be
superior to H3PPW12O40].
Table 4.4 Sorption of polar and nonpolar substances
onto bulk H3[PW1204o] at 25 °C'. Table 4.5 Homogeneous reactions catalysed by heteropoly acids[2l
Substance Sorption (molecules per Keggin unit) Reaction3 Rate ratiob T°C Ref.
Irreversible3 Total Hydration of isobutene0 2-4 40 11
Hydration of phenylacetylene 100 60 11
Pyridine 6.0 9 PhC(CH3)2OOH — PhOH + CH3COCH3 1000 25 3
Ammonia 3.2 4.3 Olefin + HOAc ester 90 110 3
Methanol 2.2 > 10 Ester —>olefin + carboxylic acid 100 128 112
Isopropanol 6.3 > 10 nTHF + Ac20 -►Ac0(CH2CH2CH2CH20)„Ac > 1000 50 11
Ethylene 0.03 0.04 Styrene + HCHO —» 1,3-dioxane 50 50 11
1-Butene 0.2 0.25
Benzene 0.1 0.5 a) Unless otherwise stated, reactions were performed in organic media
b) HPA/H2SO4 (per proton)
a) The amount irreversibly retained after evacuation at 25 °C c) In aqueous solution
68 CATALYSTS BY POLYOXOMETALATES ACID CATALYSIS BY HETEROPOLY COMPOUNDS 69
The major problem, limiting the utility of homogeneously catalysed pro

cesses, is the well-known difficulty in catalyst recovery and recycling. As the H+ A S iW 12O 404-
H
(C H 3)2C = C H 2 (C H 3)2C — c h 2 ------------- (C H 3)2C ^ C H 2 - • - S iW 120 4l

cost of heteropoly acids is higher than that of mineral acids, the recycling of
HPA catalysts is the key issue to their application. Only a few homogeneous 1 1
reactions allow for easy recycling, for example, hydration of olefins (see below). (C H 3) 3C + (C H 3)3C +. . . s . w 12c v -
In some cases, heteropoly acid can be recovered from polar organic solution
without neutralisation by precipitating with a hydrocarbon solvent. Heteropoly 1 h 2o J h 2o
acid can also be extracted from an acidified aqueous solution of its salt with a (C H 3)3C O H + H + (C H 3)3C O H + H S iW I2( V -
polar organic solvent. Even though the neutralisation of heteropoly acid is
necessary, the amount of alkali needed and hence the amount of waste formed Path I Path U
thereupon is much less than with mineral acids. A more effective way to Figure 4.2 The mechanism of hydration of isobutenej4'191
overcome the separation problem is the use of biphasic systems or solid acid
catalysts, which will be discussed in Sections 4.3 and 4.4. In the subsequent
sections are given selected examples of HPA-catalysed homogeneous reactions. above complex. From this mechanism, the rate of isobutene hydration can be
More can be found elsewhere.11^4,7’8' 10'111 expressed as:
r = ^![01][H30 +] + £2[01][H30 +][HPAn-] (4.5)

4.2.2 ACID-CATALYSED REACTIONS
where k\ and k2 are the rate constants of paths I and II, and [Ol] and [HPAn ]
4.2.2.1 Hydration of Olefins are the concentrations of olefin and heteropoly anion, respectively. This equa
tion is in agreement with the experiment.1191
The HPA-catalysed hydration of C3- C 4 olefins (eq. 4.4) is an industrially On the other hand, as found by Kozhevnikov et a/.,1131 the rate of iso
important reaction, the hydration of propene being the first commercial process butene hydration catalysed by heteropoly acids obeys the Hammett plot
based on heteropoly acid catalysis.1121 (Figure 4.1):
RCH=CH2 + H20 RCH(OH)CH3 (4.4) \ogk = —1.04 H0 —3.46 (4.6)
The hydration of isobutene is used for the separation of isobutene from the This plot is also valid for mineral acids such as H2S04, HCl, HNO3, and
C4 hydrocarbon stream produced by cracking. As the catalyst, a concentrated HCIO4, which indicates that with both heteropoly acids and mineral acids the
aqueous solution of heteropoly acid is used. Compared to mineral acids, such reaction proceeds via the same principal mechanism which may be represented
as H2S 04, HNO3, and HCIO4, heteropoly acid is 2-4 times more active per by path I. The high order with respect to heteropoly acid is explained as a result
equal H30 + concentration and shows a higher selectivity, minimising side of the strong specific salt effect of highly charged heteropoly anions[13] (Section
reactions such as isobutene oligomerisation.119,201 Izumi et a/.14,191 showed that 4.1.2.1).
the reaction order with respect to heteropoly acid depends on the HPA concen Heteropoly acids were reported to be more efficient catalysts than H2S 04
tration: first-order in dilute solution and nearly second-order in concentrated and HCIO4 for the hydration of phenylacetylene141 (eq. 4.7).
solution. In contrast, the reaction with mineral acids is first-order in the
catalyst. The solubility of isobutene also significantly increases with increasing PhC=CH + H20 -►PhCOCH3 (4.7)
the concentration of heteropoly acid. On these bases, a two-path reaction
mechanism is suggested (Figure 4.2).14,191 Path I is a common mechanism with Cycloalkenes are hydrated to cycloalkanols with 99 % selectivity in the pres
the formation of the intermediate carbenium ion. This mechanism operates ence of a catalyst consisting of a concentrated aqueous solution of an arylsulfo-
with mineral acids. Path II includes the formation of a complex of heteropoly nic acid and tungsten heteropoly acid.1211 H3[PWi204o] and H4[SiWi2C>4o] are
anion with the carbenium ion. It is path II that is assumed to be responsible for efficient catalysts for the homogeneous hydration of camphene to isobomeol
promoting the reaction by stabilising the intermediate carbenium ion in the (eq. 4.8), which is an intermediate in the synthesis of camphor.1221
studied.1231 All three substrates give a-terpineol as the main product along
with a-terpenyl acetate. The reaction rate increases in the order: limonene
< a-pinene < ß-pinene. At room temperature under optimised conditions, ß-
pinene and a-pinene form a mixture of a-terpineol and a-terpenyl acetate with
85 % selectivity at 90% substrate conversion. Limonene gives a-terpineol and a-
terpenyl acetate with 85 % selectivity at 50% conversion, with the main product
being a-terpenyl acetate in acetic acid and a-terpineol in HOAC/H2O (90/10 v/
v) solutions. Virtually no oligomerisation of monoterpenes occurs under the
optimised conditions. The catalyst can be separated without neutralisation and
may be reused. H3IPW12O40] shows a much higher catalytic activity than
H2SO4 and Amberlyst-15.
4.2.2.2 Esterification and Related Reactions

These reactions have been extensively studied in the presence of Keggin and
Wells-Dawson heteropoly acids as homogeneous catalysts.12,4,241 Generally,
The liquid-phase hydration and acetoxylation of limonene, ß-pinene and such reactions are performed in organic media, and water greatly affects the
a-pinene (Scheme 4.1) catalysed by dissolved and silica-supported heteropoly reaction rate.1-241 The catalytic activities of heteropoly acids usually follow the
acid H 3[PWi2O40] in acetic acid and acetic acid/water solutions have been order of their acid strengths, as expected for Bronsted acid catalysis. However,
molybdenum acids may exhibit a lower activity than that expected from their
acid strengths due to reduction by the reaction medium.12,41
H+ -H +
Misono et a/.1241 have studied a series of homogeneous reactions such as
decomposition of isobutyl propionate, transesterification of isobutyl propionate
with acetic acid and n-propanol, and esterification of propionic acid with
ß-pinene a-pinene isobutanol (eq. 4.9-4.12).
C2H 5COOCH2CH(CH3)2 -►(CH3)2C=CH2 + C2H5COOH (4.9)
C2H5COOCH2CH(CH3)2 + CH3COOH) 10)

-► CH3COOCH2CH(CH3)2 + C2H 5COOH
C2 H 5 COOCH2 CH(CH3 ) 2 + n-C3 H7OH -> C2 H5 COOC3 H 7 ^

+ (CH3)2CHCH2OH
(CH3 )2 CHCH2OH + C2 H5 COOH -►C2 H5 COOCH2 CH(CH3 ) 2 + H20

(4.12)
In reaction 4.9, heteropoly acids are 60-100 times more active than H2S 04
or p-toluenesulfonic acid (TsOH). The activity is in the order: H3[PWi20 4o]
> H4[SiW1204o] > H4[GeWI2O40] > H 5[BWi2O40] > H6[P2W 180 62] > H6
a-terpineol a-terpenyl acetate [CoWi20 4o]. The same activity pattern is observed for reaction 4.10 in the
absence of water. The addition of water greatly accelerates reaction 4.10 and
Scheme 4.1 probably changes its course to proceed via the hydrolysis of isobutyl propionate
to propionic acid and isobutanol, followed by the esterification of isobutanol Methyl t-butyl ether (MTBE) - a gasoline octane booster - is produced
with acetic acid. On the other hand, for reactions 4.11 and 4.12 no significant industrially on a large scale by reacting isobutene with methanol in the presence
difference in activity between heteropoly acids and H2SO4 is observed probably of an acid catalyst, usually acidic ion-exchange resin (eq. 4.15).
due to the levelling effect of the reactant alcohols on the acid strength of the
catalysts. (CH3)2O C H 2 F CH3OH — CH3OC(CH3)3 (4.15)
Dialkyl phthalates, utilised as plasticisers, have been obtained by esterifying
phthalic anhydride with C s -Q o alcohols at 100-120 °C in the presence of
Heteropoly acids and their salts also catalyse this reaction in homogeneous and
H3[PW1204 o] (1-2%) as a homogeneous catalyst.1251 The catalytic activity of
heterogeneous systems.171 Maksimov and Kozhevnikov1271 showed that in the
heteropoly acid is significantly higher than that of H 2SO4 and TsOH. Hetero
homogeneous reaction at 42 °C, Keggin acids such as H3[PWi204o] and
poly acid supported on activated carbon can also be used as a heterogeneous
H 4[SiWi204o] are 2-4 times more active than the conventional catalysts per
catalyst. Although the carbon-supported heteropoly acid is less active than the
unit proton site. Interestingly, the Wells-Dawson acid, H6[P2W 18062], shows
homogeneous catalyst, it can be easily separated from the reaction mixture and
two times higher activity than H 3[PW|204oJ. However, regarding the activity
reused.
per unit catalyst weight, H2SO4 is the most active catalyst. Liquid-phase
Synthesis of glycosides catalysed by heteropoly acid is of industrial im port
synthesis of MTBE1281 and ethyl t-butyl ether1291 by HPA-catalysed etherifica
ance.111121 Glycosides are used as effective and biodegradable surfactants.
tion of t-butanol with methanol and ethanol, respectively, has been studied.
Heteropoly acid is several times more active than the conventional catalysts
such as TsOH and ZnCl2. Thus acetylated monosaccharides readily interact
with alcohols in a homogeneous phase in the presence of 2 % of heteropoly acid 4.2.2.3 Condensation
with respect to sugar derivative at 70-130 °C, yielding 70-90% of glycosides1261 Heteropoly acids have long been known as catalysts for condensation reac
(eq. 4.13). tions, e.g., the condensation of acetone to mesityl oxide and alkylbenzenes.12,301
Bisphenols are obtained by the condensation of ketones and phenols in the
presence of heteropoly acids (eq. 4.16).131,321
OAc OAc
AcO "" ^ \^ -O A c + ROH AcO"" + AcOH

OR
AcO OAc AcO OAc
(4.13)
Me
Heteropoly acid is more active and more selective catalyst than H 2SO4 and
H 3[PW1204o] and its Cs+ and N H | salts encapsulated into MCM-41 molecular
TsOH for the homogeneous alcoholysis of epoxides (epichlorohydrin, 1,2- sieve also catalyse reaction 4.16, the Cs+ salt being the most selective towards
epoxybutane, isobutene oxide, styrene oxide, etc.) under mild conditions
para, para' isomer form ation.1331
(45 °C, excess alcohol)141 (eq. 4.14). In contrast to heteropoly acid, H 2SO4 is
Kozhevnikov et a /.134,351 have shown that heteropoly acid is an efficient
rapidly deactivated probably due to the formation of alkyl sulfate, resulting in catalyst for condensations in the syntheses of vitamins E, Ki and C. Thus,
loss of acidity. Likewise, in the acetolysis of epoxides, tetrahydrofuran, and
H 3[PW i 20 4o] and H 4[SiWi20 4o] catalyse the condensation of isophytol with
linear esters, performed in excess of acetic acid, heteropoly acid is far more 2,3,5-trimethylhydroquinone (TMHQ) to a-tocopherol (eq. 4.17), which is the
effective than other acid catalysts such as TsOH and BF3 • H 20 . The activity of active form of vitamin E .[341 The reaction is carried out in homogeneous phase
TsOH decreases in the early stage of the reaction due to the formation of a tosyl (in butyl acetate or acetic acid) or in heterogeneous system (in toluene) with ca.
ester.[4]
1 wt% HPA based on TMHQ. With heteropoly acid, the yield and quality of
vitamin E are practically the same as those with ZnCL which is a commercial
catalyst. The drawback to ZnCl2 is that it is used in stoichiometric quantities,
r 'r 2c - c h 2 + ROH — R'R 2C - C H , + R ^ C -C H ,
\ / (4.14) generating large am ount of waste. Heteropoly acid can be recovered after
o OR OH OH OR reaction and reused.
Me
Me
(4.19)
W ater formed in the reaction is removed by distillation or absorption with NaA

a-Tocopherol Vitamin E zeolite. In industry, this reaction is carried out with excess oleum to yield ca.
(4.17) 80% DAS, the oleum serving as both the catalysts and the desiccant. The major
drawback to this process is the formation of large amount of sodium sulfate by
oleum neutralisation. The use of heteropoly acid allows increasing the DAS
A solid-acid catalyst 30% WO3/S 11O2, which may contain a surface-
yield, the amount of waste being greatly reduced.[35]
bound heteropoly acid, has been found to be active in the synthesis of a-
tocopherol, albeit less efficient than H 3[PWi204o].[36] The catalyst can be reused Heteropoly acids catalyse the Prins reaction of alkenes with formaldehyde to
without loss of its activity. Heteropoly acids are also efficient in the related yield 1,3-dioxanes. For example, in the reaction of styrene (eq. 4.20), Keggin-
condensation of isophytol and l-acetoxy-4-hydroxy-2-methylnaphthalene type acids were shown to be superior to H2S 0 4 and TsOH, the activity differing
only slightly in the series of heteropoly acids.[4]
(eq. 4.18) which is a key step in the synthesis of vitamin K i .[34] Heteropoly
acids are almost 50 times more active than Z 11CI2 or aluminosilicates in this
reaction. h 2c - ch2
PhCH=CH 2 + 2 HCHO -------- - PhHC O (4.20)
O—CH2
OAc
rV
.Me OH /
r ^ \ OH- Condensation of formaldehyde and methyl formate to methyl glucolate and
+
methylmethoxy acetate using heteropoly acids and salts has been reported.[37]
Me Me h HPA
OH 4.2.2.4 Miscellaneous Reactions

O (4.18)
Izumi and Fujita[38] reported that an iminium salt, prepared by interacting
Me
if iJ N,N-dimethylformamide with epichlorohydrin in the presence of H 3
° 2,
II \\ ^ . [PW,2O40] or H4[SiWi204o], effectively catalyses the liquid-phase Beckmann
rearrangement of cyclohexanone oxime to e-caprolactam (eq. 4.21) under mild
o Me Me conditions (50-60 °C). The product lactam was found to poison the catalyst,
V itam in K ,
though reversibly. The turnover of the catalyst attained 200.
NOH
The acetonation of L-sorbose - a step in the synthesis of L-ascorbic acid
(vitamin C) - occurs in acetone solution in the presence of 0.1-0.35% of
H3[PW12O40] or H4[SiWi20 4o] to yield 85% of diacetone-L-sorbose (DAS)
(eq. 4.19).
Heteropoly acids have long been known as very efficient catalysts for the sic systems consisting of two immiscible liquid phases - a catalyst phase and a
decomposition of cumene hydroperoxide to phenol and acetone114,39,403 (eq. product/reactant phase - with intense mass transfer between them. Heteropoly
4.22). acids due to their special solubility properties, i.e., high solubility in a variety of
polar solvents and insolubility in nonpolar solvents, are promising catalysts for
PhC(CH3)2OOH -> PhOH + CH 3COCH3 (4.22) operating under phase-transfer conditions.123 There are two types of such
biphasic systems: 1) initially homogeneous a reaction system separates in two
Similarly, 1,3,5-trihydroxybenzene is formed via the decomposition of 1,3,5- liquid phases in the course of the reaction; 2) a reaction system is biphasic from
triisopropylbenzene hydroperoxide at 50-100 °C with 97% selectivity at 89% the very beginning. The catalyst phase, usually the lower one, is a solution of
hydroperoxide conversion (eq. 4.23).[41] heteropoly acid in a polar reactant. The reaction predominantly proceeds in the
catalyst phase, and the product formed is transferred to the less polar product
OOH phase. The am ount of heteropoly acid in the product phase must be negligible
to allow easy catalyst separation.
4.3.2 BIPHASIC REACTIONS
4.3.2.1 Polymerisation of Tetrahydrofuran

1,2-Diols (1,2-propanediol, 2,3-butanediol and 2,3-dimethyl-2,3-butanediol) Polymerisation of tetrahydrofuran (THF) is used for the preparation of poly-
readily undergo the pinacol rearrangement to yield the corresponding carbonyl oxytetramethyleneglycol (PTMG), which is used for manufacturing Spandex
compounds (propanal, 2-butanone and 3,3-dimethyl-2-butanone, respectively) fibres and polyurethanes. PTM G is commercially produced by a two-step
in the presence of H 3PPW12O40], H ^S iW nO ^], H 3PPM012O40], or H 4[SiMoi2 process, including ring-opening polymerisation of TH F with acetic anhydride
O40] (eq- 4.24). Under such conditions, 1,4- and 1,5-diols selectively form cyclic catalysed by HCIO4, followed by hydrolysis of the terminal acetate groups in
ethers.1423 the prepolymer. Izumi et a/.[45] found that heteropoly acid is more active than
HCIO4 in the polymerisation of TH F. Aoshima et a/.[46a] developed a one-
OHOH O R step process for the T H F polymerisation to directly yield PTM G (eq 4.25). This
11
R -C -C -R
11 1
-------- R - C - C - R + H20
(A
(4-24) process is used commercially in Japan.t4,123
I I I
R R R
n + H20 ------- H0-[-(CH 2)4-0-]n-H (4>25)
The hydrolysis of sucrose in the presence of H 4[SiWi204o] has been XC)
reported.1433
Kortz and Pope[443 have synthesized and fully characterised two new poly- PTM G is obtained by ring-opening T H F with water in the presence of
oxomolybdate-diphosphate complexes with the formula [(OsP X P C ^ M oöO is H 3IPW12O40] at 60 °C. The H 2O /H 3P W 12O40] molar ratio is critical for the
(H2 0 )4]4_(X = O or CH2). The polyanion with X = O is a possible intermed process, controlling the reaction rate and molecular weight of polymer.
iate in the molybdate-catalysed hydrolysis of pyrophosphate. When the H 2O /H 3IPW12O40] molar ratio is above 15, a homogeneous phase
forms, and no reaction takes place. When the ratio is below 15, the solution
separates in two liquid phases - a T H F (upper) phase and a H 3IPW12O40] -
4.3 ACID-CATALYSED REACTIONS IN BIPHASIC LIQ U ID -L IQ U ID T H F -H 2O (lower) phase. The polymerisation starts when H 20 /H 3[PWi204o]
SYSTEMS ratio is decreased below 10. The polymer is formed in the HPA phase
and transferred to the T H F phase. The reaction rate increases with decreasing
4.3.1 INTROD U CTIO N H 20 /H 3[PWi204o] ratio, and so does the molecular weight of polymer. The
process is performed continuously. The PTM G with a molecular weight of 500-
Separation of products and recovery and recycling of catalysts often becomes 2000 and a narrow molecular weight distribution is obtained from the THF
much easier when homogeneously catalysed reactions are performed in bipha phase. Various improvements to this process have been claimed.14615”4663
Similarly. H ^P W Ô ^] and HjfPMouCô] catalyse the polymerisation of 4.3.2.3 Other Reactions

cyclic formaldehyde acetal and trimer, 1,3-dioxolane and 1,3,5-trioxane, re
spectively. For example, in the polymerisation of 1,3,5-trioxane, the compar Keggin-type heteropoly acids such as H3IPM012O40], H 3[PW i 204 oL and
able reaction rates can be obtained with 25 times less heteropoly acid weight H4[SiW1204o] catalyse the cyclotrimerisation of aldehydes, such as ethanal,
than for conventional catalyst like BF3 • O R2J47^ propanal, butanal, 2-methylpropanal, etc., to produce 2,4,6,-trialkyl-1,3,5-
trioxanes in high yields (eq. 4.28), as reported by Sato et a/.[49,50] Catalyst
turnover number is more than 10000 for the propanal cyclotrimerisation. At
4.3.2.2 Esterification high conversions of aldehyde, the reaction mixture spontaneously separates
Esterification of p-nitrobenzoic acid is a step of the anaesthetic synthesis. Ethyl into two phases, a product phase and a catalyst phase, which, depending on
p-nitrobenzoate is obtained in 99% yield by esterification of p-nitrobenzoic aldehyde, can be solid or liquid. For the propanal cyclotrimerisation, the
acid with ethanol (eq. 4.26) in the presence of H ßtPW Ô ^] (3-7 wt%) at reaction mixture separates into two liquid phases, and the recovered catalyst
7 5 ° c P l] Water formed in the reaction course is separated by azeotropic phase can be easily reused. The vapour-phase trimerisation of formaldehyde to
distillation with toluene. Initially homogeneous, the reaction mixture becomes trioxane catalysed by H4PPM011VO40] supported on silicon carbide at 110°C
a two-phase system in the end of reaction. The upper phase contains the has been studied.[51]
product, the lower phase is a concentrated solution of heteropoly acid in
ethanol. The catalyst phase is easily separated and can be reused. RY ° y R
3RCHO ------- ► q q (4.28)
COOH C 02Et
R
+ EtOH + h 2o (4.26)
Sato et alP 2* examined various acetal formation reactions between
monoalcohols or diols and a range of aldehydes or ketones catalysed by Keg
NO, N 02
gin-type heteropoly acids in comparison with other acid catalysts. The reaction is
strongly inhibited by water produced in the reaction course. The catalyst
Acetoxylation and hydration of dihydromyrcene (DHM) give dihydromyr- activity was found to decrease in the order: H4[SiWi204o] > H 3[PM oj20 4o]
cenol (DH M -O H) and dihydromyrcenyl acetate (DHM -OAc) (eq. 4.27), re > H 3PPW12O40] > TsOH > H 2S 0 4. For several reactions between a carbonyl
spectively, which are useful as perfume ingredients. These reactions occur compound and a diol, the reaction mixture is spontaneously separated into two
simultaneously in a two-phase system in the presence of H 3IPW12O40] at liquid phases, enabling easy catalyst recycling.
14-30 °C.[48J The upper phase mainly consists of DHM and the lower phase is Timofeeva and Kozhevnikov[53] reported the alkylation of hydroquinone
a concentrated solution of heteropoly acid in aqueous acetic acid. Acetic acid with isobutene to yield 2-t-butylhydroquinone and 2,5-di-t-butylhydroquinone
is approximately equally distributed between the two phases. The reaction (eq. 4.29) catalysed by H 3[PW i204 o], H 6[P2Wi8062] and H6[P2W2iC>7i] under
proceeds in the catalyst phase to form D H M -O H and D H M -O A c, which are phase-transfer conditions in a biphasic system, including toluene (upper phase)
transferred to the DHM phase. The process reaches equilibrium at ca. 30% and a dioxane heteropoly etherate (lower phase). In this case, the two phases
DHM conversion and is strongly complicated by acid-catalysed isomerisation are immiscible from the very beginning, and the products are obtained from the
and cyclisation of DHM. The selectivity to D H M -O H and D H M -O A c totals toluene phase. The yield of 2-t-butylhydroquinone increases in the series:
90% at 21 % DHM conversion. The catalyst phase can be reused without loss H 6[P2W i 8062] < H 6[P2W2i0 7 ,] < H 3[PW12O40]. With H 3[PW12O40], a 70%
of activity. yield is obtained (85 °C). H 3[PWi20 4o] shows a higher efficiency than H 2S 0 4
or H 3PO4.
AcOH + HzO
(4.27)
/ K /N
OAc OH OH OH
OH
4.4 HETEROGENEOUS ACID CATALYSIS neous and in heterogeneous systems.12,31 Like other strong solid acids, hetero
poly acids are capable of generating carbocations from adsorbed olefins and
Heterogeneous acid catalysis by heteropoly acids has attracted much inter arenes.1561 The drawback to the bulk acids is their low surface area (1-5 m2 g-1)
est.11 7,91 Generally, solid heteropoly acids have greater catalytic activities and low porosity (< 0.1 cm3 g“ 1).
than conventional solid-acid catalysts such as mixed oxides, zeolites, etc. The
downside of heteropoly acids is their relatively low thermal stability, which may 4.4.1.3 Supported Heteropoly Acids
cause problems with regeneration of these catalysts. This section describes the
Supported heteropoly acid catalysts have much greater surface areas; hence
heterogeneously catalysed reactions in liquid-solid and gas-solid systems with
they are more important for applications.11“121 The acidity and catalytic activity
the use of solid heteropoly acid catalysts.
of supported heteropoly acids depends on the type of carrier, the HPA loading,
conditions of pretreatment, etc. Acidic or neutral substances such as S i02,1571
active carbon,125,581 acidic ion-exchange resin,1591 etc., are suitable as supports,
4.4.1 HETEROPOLY ACID CATALYSTS
the most often used being S i02. Basic solids like MgO tend to decompose
heteropoly acids.13,601 Adsorption of heteropoly acids onto silica, alumina and
4.4.1.1 Acid Sites
active carbon from aqueous and organic solutions has been studied.161“631
Bulk and supported heteropoly acids and salts are used as catalysts in hetero
geneous acid-catalysed reactions. Several types of acid sites are present in these Heteropoly acids on silica S i02 is relatively inert towards heteropoly acids, at
catalysts:111 least above a certain loading level, although some chemical interaction takes
place between heteropoly acids and S i02 (see below). The thermal stability of
1. Proton sites in heteropoly acids (e.g. H 3UPW12O40]). heteropoly acids on S i02 seems to be comparable to or slightly lower than that
2. Proton sites in acidic salts (e.g. Cs2.5Ho.5[PWi204o])- of the parent H PA .15,641 On the other hand, thermally decomposed Keggin
3. Lewis acid sites in salts (metal countercations, e.g. in Lain[PMoi204o]). structure of molybdenum acids on the silica surface may be reconstructed on
4. Proton sites generated by dissociation of coordinated water: exposure to water vapour.165,661
Ln(H20 ) 3+ - Ln(H20 ) n(0H )2+ + H+ At low loadings, H 3[PW i 204 o] and H4[SiWi204o] form finely dispersed
5. Proton sites generated by reduction of salts: species on the S i02 surface; HPA crystal phase on silica (200-300 m2 g-1) is
Pd2[SiW1204o] + 4 {H} - 2 Pd° + H4[SiWi20 4o] developed at HPA loading above 20 wt%.[57,61] Various HPA forms were ob
6. Protons generated by partial hydrolysis of poly anions: served on the silica surface by transmission electron microscopy (TEJV1): dis
[PW12O40]3- + 2 H20 -> [P W „0 39]7“ + {W 03} + 4 H + crete molecules, clusters 50 A in size and large crystallites of 500 A. Their
relative amounts depend on the HPA loading.1611
4.4.1.2 Bulk Heteropoly Acids !H and 31P magic-angle spinning (MAS) NM R studies indicate a chemical
interaction of H 3IPW12O40] with SiO2.167“70] Impregnating S i02 with an aque
Solid heteropoly acids possess purely Bronsted acidity and are stronger than ous solution of H 3PPW12O40] gives catalysts with, in general, two HPA species
such conventional solid acids as S i02—A120 3, H 3P 0 4/S i0 2, and HX and HY which are characterised b y 31P MAS NMR: one at - 1 5 ppm with intact Keggin
zeolites.154,551 The acids H 3IPW12O40], H4[SiWi20 4o], H 3[PMoi20 4o], and structure (A) and the other at -1 4 ppm with a different structure (B) (Figure
H4[SiMoi20 4o] are readily available and most frequently used as catalysts, 4.3).169,701 The relative amount of species A and B depends on HPA loading,
usually the first two being preferred. These acids have fairly high thermal with A dominating. At higher loadings, 30-50 %, A is practically the only one
stabilities, decomposing at 465, 445, 375, and 350 °C, respectively121 (Chapter present on the S i02 surface; at lower loadings, both species exist, the amount of
2). Decomposed molybdenum acids may be reconstructed under exposure to B increasing as the HPA loading decreases. In contrast, catalysts prepared by
water vapour.[1] For much less labile tungsten acids such reconstruction is impregnation with a methanol solution of H 3PPW12O40] contain exclusively
unlikely. Keggin-type A over the whole range of HPA loading.1701 Forms A and B
The acid strength of crystalline heteropoly acids decreases in the series: were assumed to be bulk crystalline H 3[PW120 4o] and the ‘interacting’
species ( = SiOH^)(H2[PWi204o]“), respectively.1691 More recently evidence
H3[PW i2O40] > H4[SiW120 4o] > H 3[PMoi2O40] > H 4[SiMoi2O40] has been obtained that B may be H 6[P2W i8062] or H6[P2W2i07i], formed
from H 3[PW1204o] in the course of catalyst preparation.1701 Species B was
which is identical to that in solutions (Chapter 2).[1,31 Usually relative catalytic found more active than A in liquid-phase dealkylation of alkylphenols.1701 The
activities of heteropoly acids are consistent with this order both in homoge
’H MAS NMR study[67] also shows the interaction of H3[PWi20 4o] with silica
and the formation of a new type of proton sites on the silica surface.
As shown by microcalorimetry,1711 when loading H3[PW i 204 o] (20wt%) on
S i02, the proton sites become weaker and less uniform. Only 20 % of the total
amount of proton sites remain as strong as in bulk H3[PW1204o]. The rest have
the differential heat of ammonia adsorption about 120kJ/mol, approaching
that for acid sites of HX and HY zeolites (Figure 2.18, Section 2.6.3). The
recent study[721 showed that the initial heat of ammonia adsorption on
H 3[PWi20 4o]/Si02 increases with HPA loading in the range of 5-25 wt%.
Like for bulk heteropoly acid, the differential heat of N H 3 adsorption on
S i02-supported HPA strongly depends on the pretreatment temperature.1731
According to the ammonia thermal desorption data/ 711 the acid strength of
supported H 3[PWi204o] decreases in the series of carriers: S i02 > a-Al20 3 >
activated carbon (Figure 4.4). The catalysts comprising H 3[PWi2O40] sup
ported on various porous silicas have been characterised.^74,751
S i0 2-supported molybdenum heteropoly acids, such as H4[SiMo]20 4o],
H 3[PM oi20 4o], and H 5[PM oi0V2O40], retain the Keggin structure at high load
ings but decompose at very low loadings due to their strong interactions with
surface silanol groups J64,65,76-791 A correlation was established between the
catalytic behaviour in the methanol oxidation/dehydration reaction and the
state of HUISiMonOio] and H 3[PMo12O40] on the silica surface.[64,76,78,791 At
Figure 4.3 31P MAS NMR spectra for H3[PWi204o] and H3[PWi204o]/Si02 at various Figure 4.4 Ammonia thermal desorption from supported H3[PWi204o] catalysts.1711
HPA loadings.121 Reprinted with permission from Chem. Rev. 1998, 98, 171. Copyright Reprinted with permission from Catal. Rev. Sei. Eng. 1995, 37, 311. Copyright 1995
1998 American Chemical Society. Marcel Dekker.
ACID CATALYSIS BY HETEROPOLY COMPOUNDS 85
high loadings, supported heteropoly acids behave similarly to bulk acids. In this partially decomposed to form a highly dispersed PW9 species, which, neverthe
case, acid catalysis predominates to yield dimethyl ether. In contrast, at low less, shows a higher catalytic activity and selectivity in dehydration of n-
loadings, when heteropoly acid decomposes to M0O3, loosing the acidity, only butanol than the bulk heteropoly acid at 230-250 °C.
redox catalysis is observed to give formaldehyde. The intercalation of a variety of transition-metal-substituted polyoxometa-
Iates into ZnAl—NO3 and MgAl-Cl host clays has been reported.195,961 The
Heteropoly acids on carbon While weaker acids, heteropoly acids supported pillaring of MgAl layered double hydroxides by [H2W I2O40]6-, [P2W180 62]6-
on certain activated carbons are considered to be promising fixed-bed acid and [Co4(H20 )2(PW90 34)2]10 anions has been accomplished by ion-exchange
catalysts for liquid-phase reactions, e.g., esterification, because of their high reaction.1971 Polyoxometalate-intercalated hydrotalcites show catalytic activ
stability towards HPA leaching from the carrier.125,581 However, as shown by ities for the liquid-phase oxidation of cyclohexene with 0 2[98] and shape-select
microcalorimetry/ 801 the acid strength of H3[PW i204 o] is greatly reduced when ive epoxidation of alkenes with H20 2.1991
loading on activated carbon. As evidenced by IR and 31P MAS NMR, Heteropoly acid immobilised into an organic polymer, e.g., PMo-polysulfone,
H3[PW,204 o] and H4[SiWi204o] supported on a chemically (H3PO4) activated PMo-polyethersulfone,11001 PMo-polyacetylene[I0I], PM o- and PW - polypyr
carbon retain the Keggin structure at the HPA loading > 5 wt% but decompose role11021, SiW-polyaniline,1103,1041 and PM o-and PW-poly( 1,4-phenylenemethy-
at lower loadings. Heteropoly acids form finely dispersed species on the carbon lidynenitrilo-l,4-phenylenenitrilomethylidyne),11051 have been prepared and
surface; no HPA crystal phase is developed even at the HPA loading as high characterised. These are claimed to have an improved catalytic activity compared
as 45 wt%J81] In 31P MAS NMR spectra of carbon-supported H3[PW120 4o], to bulk heteropoly acid in gas-phase ethanol conversion. H3[PMoi2O40]-polymer
a great line broadening is observed due to a strong interaction of the composite film catalysts have been tested for the liquid-phase hydration of
HPA with carbon.18'1 The acidity of a series of bulk and carbon-supported isobutene.11061
tungsten heteropoly acids has been studied by ammonia adsorption micro-
calorimetry.[82] The bulk acids exhibit strong acidity, decreasing in the order
4.4.1.4 Intrazeolite Heteropoly Acids
H3[PW1204 o] > H4[SiWi2O40] > H5[BW]20 4o]. For carbon-supported acids
at high HPA loadings (55-63%), the order of acid strength remained the Incorporation of heteropoly acids into zeolite pores to obtain shape-selective
same, the strength slightly reduced, however. Carbon-supported acids catalysts has long been a challenge.121 However, conventional zeolites are not
H3+n[PMoi2_nVn04o] have been studied as catalysts for liquid-phase oxida- suitable for this because their pores are too small to adsorb large (12 A) HPA
tion.183,841 Scanning tunnelling microscopy and tunnelling spectroscopy studies molecules. H 3[PW i204 o] encapsulated into a mesoporous pure-silica molecular
of heteropoly acids supported on graphite have been reported.185-871 Recently, sieve MCM-41 (BET surface area 1200 m2 g_I, uniform pores 32 A in size) has
H3[PW1204 o]/C and H4[SiW]20 4o]/C have been characterised by various spec been prepared1107,1081 and characterised by nitrogen physisorption, XRD, Four-
troscopic techniques.1881 ier-transform infrared spectroscopy (FT-IR), TEM, a n d 31P MAS NM R.170,1071
The H 3[PW1204 o] J MCM-41 compositions with HPA loadings from 10 to
Other supported heteropoly acid catalysts Catalysts comprising 12-tungsto- 50wt% have ~30A uniformly sized mesopores (Figure 4.5). Heteropoly acid
phosphoric acid supported on titania1891 and zirconia190,9'1have been character retains the Keggin structure on the MCM-41 surface at an HPA loading above
ised. 20 wt%. At lower loadings a partial decomposition of H3[PW120 4o] is observed,
Pillaring hydrotalcite-type anionic clays (layered double hydroxides) by as in the case of amorphous Si02,1701 Heteropoly acid forms finely dispersed
polyanions to form expanded layered catalysts for redox reactions has attracted species on the MCM-41 surface. No HPA crystal phase is observed at HPA
considerable interest. These materials are often used as precursors for molecu- loadings as high as 50wt%. As shown by TEM,1701 the H 3[PWi20 4o] species are
larly mixed oxide catalysts, which possess basic and/or redox properties.1921 mainly located inside the MCM-41 pores rather than on the outer surface
Pillared layered double hydroxides have been prepared by ion-exchange reac (Figure 4.6). H3[PW i20 4o]/MCM-41 has a higher catalytic activity than
tion of [Zn2Al(0H)6]N 0 3 • nH20 with Keggin-type heteropoly anions.1931 H2S 0 4 or bulk H3[PWI204o] and exhibits shape selectivity in liquid-phase
Complete replacement of N O j is achieved for the Keggin anions, such as phenol alkylation.11071 H3[PWl204o]/MCM-41 has been characterised by ‘H
[PW9V3O40]6-, H2[Wi204o]6-, [SiW9V30 4o]7-, etc., with the charge of - 6 or and 31P MAS NMR and tested in the gas-phase conversion of 1,3,5-triisopropyl
higher. No exchange was observed for anions such as [PWi204o]3- and benzene.11091 This catalyst is very active in n-hexane cracking, albeit deactivate
[SiWi2C>4o]3-. The intercalated anions are accessible for catalytic chemical rapidly due to coke deposition on the acid sites.11101 H4[SiWt204o]/MCM-41 has
conversions below 200 °C, e.g., for photocatalytic oxidation of isopropanol to been characterised and tested in the esterification of acetic acid with n-buta-
acetone. The intercalation of H3[PWi20 4o] into Z n A l-C 0 3 hydrotalcite has nol.11111 This catalyst is very similar to H3[PW i204 o]/MCM-41. Caesium salt of
been studied.1941 Upon interacting with the clay, H 3[PW i204 o] is probably H 3[PW120 4o] supported on MCM-41 mesoporous silica has been studied.11121
1.2 The encapsulation of H 3[PW i204 o] in the cage of synthetic faujasite has been
claimed/ 1131 however, more characterisation is needed to prove it; no prepar
ation details has been disclosed. H 3P W 12O40] supported on dealuminated
1.0
zeolite Y has been characterised and tested in isomerisation, disproportionation
and dealkylation of m-xylene/ 1141
0.8 ^,0 The synthesis of 12-molybdophosphoric acid in the supercages of Y-type
1 zeolite has been reported/ 1151 This ‘ship-in-the-bottle’ catalyst has been used for
w liquid phase reactions/ 1161 The effect of the Si/Al ratio and the countercation in
0.6 ^
< zeolite Y on the encapsulation of Keggin heteropoly acids has been studied/ 1171
4.4.1.5 Heteropoly Salts

The nature of countercation in heteropoly salts is critical to their acidity,
0.2 solubility, porosity, and thermal stability. Salts with rather small cations re
semble the parent heteropoly acids; they are readily soluble in water, nonpor-
0 ous, and possess surface areas under 10 m2 g_1 (Table 4.6). In contrast, salts
with large monovalent cations, such as N H 4 , K +, Cs+, etc., are water-insol
uble, have a rigid microporous/mesoporous structure and can be prepared with
surface areas over 100 m2 g-1 / 1181 Even if these solids are maid (by precipita
Figure 4.5 Pore size distribution for 40% H3[PWi204o]/MCM-41 from N2 physisorption from aqueous solutions) to be stoichiometric, residual quantities of
tion.[2] Reprinted with permission from Chem. Rev. 1998, 98, 171. Copyright 1998 protons still remain, which are apparently responsible for the catalytic activity
American Chemical Society.
of these salts/ 1191Parent and Moffat1120-1221 investigated the effect of substitution
of protons in Keggin heteropoly acids by 1A, IB, and 3B group monovalent
cations on their catalytic properties in alcohol dehydration and double
bond migration. As demonstrated by Misono, Okuhara et a/ ./ 123,1241 the acidic
Cs salt, C s2.5H o.5[PW,204 o], has strong acid sites and high surface area
( 100-200 m2 g-1) and is a very efficient solid acid catalyst for a variety of
Table 4.6 Physicochemical properties of heteropoly salts.

Cation Ionic radius, A Solubility3 Surface area, m2 g 1
Li+ 0.68 S < 10
Na+ 0.97 S < 10
Ag+ 1.26 S < 10
Mg2+ 0.66 S < 10
Ca2+ 0.99 s < 10
Cu2+ 0.72 s < 10
Zn2+ 0.74 s < 10
Al3+ 0.51 s < 10
Fe3+ 0.64 s < 10
La3+ 1.02 s < 10
Ce3+ 1.03 s < 10
K+ 1.33 N > 100
Figure 4.6 TEM images of the same area of 40% H3[PWi204o]/MCM-41: (a) before Rb+ 1.47 N > 100
and (b) after amorphisation/ 701 The same structure observed before and after amorphi- Cs+ 1.67 N > 100
sation is a clear indication that heteropoly acid is mainly located inside the MCM-41 NHJ 1.43 N > 100
pores. Reprinted with permission from Chem. Rev. 1998, 98, 171. Copyright 1998
American Chemical Society. a) Solubility in water: S, soluble; N, insoluble
organic reactions, especially promising for liquid-phase reactions. The pore 4.4.1.6 Sol-gel Catalysts
size of salts CsxH3-x[PW|20 4o] can be controlled by the Cs content. Cs2.2H0.8 Izumi et u/.1127,14*1 reported that Cs2.5H 0.5[PWi20 4o] and even water-soluble
[PWi2O40] possesses micropores of 6.2 to 7.5 A diameter and exhibits shape H 3[PW]20 4o] itself can be included in the silica matrix by means of a sol-gel
selective catalysis in liquid-phase reactions.11251 Izumi et tf/J126,127^ reported that
technique to become water-insoluble and easily separable microporous solid-
Si0 2-bound Cs2.5Ho,5[PW1204o], prepared through the hydrolysis of ethyl ortho
acid catalysts. The catalysts thus obtained have large surface areas (400-
silicate in the presence of colloidal C s2.5H o.5[PW i20 4o] in ethanol, is catalyt-
800 m2 g“ 1), fairly strong acidity and are thermally more stable than Amber
ically more active than Amberlyst-15 and H-ZSM-5 per unit acid site.
lyst-15. They catalyse the hydrolysis of ethyl acetate in aqueous phase, showing
Catalysts obtained by loading heteropoly acids on their insoluble salts, e.g., H 3
higher turnover frequencies than Amberlyst-15 and HZSM-5. Remarkably, the
[PM o12O40] /K 3[PM oi2O40], have been studied.1128' 1291 Various methods of the
incorporation of H 3[PWi20 4o] into the silica matrix effectively suppresses HPA
preparation of bulk and supported heteropoly salts have been described.1130,1311
leaching during the hydrolysis, whereas in the case of the usual silica-supported
The preparation of silica-supported Cs+ salts of H3IPW12O40] with the egg-white H 3[PWi20 4o], the heteropoly acid completely dissolves in the reaction medium.
morphology has been reported.11321The surface acidity of CsxH 3_x[PW 12O40] has It is expected that silica-included heteropoly compounds may find applica
been characterised by F T -IR measurement of the low-temperature adsorption of tions for acid-catalysed liquid-phase reactions in aqueous media as alternatives
CO. The intensity of the 2165 cm“ 1 band for CO adsorption on H + changes in
to H 2S 0 4 and ion-exchange resins.11411 The Keggin-type heteropoly acids
parallel with the catalytic activity for surface-type reactions.11331The proton sites
H n[XM 12C>4o] (where n = 3, 4; X = Si, P; M = Mo, W) immobilised into a
in H3[PW!20 4o] and its caesium salts have been characterised by *H, 2H, 31P silica matrix by sol-gel technique and have been tested in Friedel-Crafts
MAS NMR and inelastic neutron scattering11341 and in situ F T -IR .11351The 129Xe alkylations11421. However, the sol-gel HPA catalysts, because o f stronger inter
NMR technique has been applied to characterise the pore structure of actions between their protons and the silica matrix, probably have a weakened
NH4\ K +, and Cs+ salts of H 3[PW i2O40], H 3[PM oi2O40], and H4[SiWi2O40] strength compared to silica-supported HPA.
and confirmed the presence of microporosity in these salts.11361
Certain ‘neutral’ heteropoly salts can also gain proton sites upon interaction
with reaction medium. Two mechanisms of the proton generation in heteropoly 4.4.2 H ETEROG EN EOU S CATALYSIS IN LIQ U ID -SO L ID SYSTEMS
salts are distinguished: the dissociation of coordinated water (for salts with the
cations like Al3+, Zn2+, etc.) and the reduction of the metal cation (e.g. In this section, reactions in liquid-solid systems catalysed by bulk and supported
Ag+, Cu2+, and Pd2+).[5’7] heteropoly acids and their insoluble salts are discussed. In heterogeneous as well
as in homogeneous systems, heteropoly acids are generally more efficient than
Al3+ + H20 -*■ Al(OH)2+ + H + conventional catalysts, such as S i0 2—A120 3, zeolites, etc., which is in line with
their relative acid strengths.1' -41 Obvious advantage of heterogeneous systems
Ag+ + V2H 2 - Ag° + H +
over homogeneous is the easy separation of catalyst from reaction products.
Furtherm ore, since heteropoly acids are soluble only in wet nucleophilic solvents
Ono et a/.17' 1371 have studied the Pt(II) and Pd(II) salts of H 3[PW]20 4o]; these
levelling the acid strength (dehydrated heteropoly acids are scarcely soluble in
are capable of acting as bifunctional catalysts in alkane isomerisation. ’H
dry polar media), their intrinsic strong acidity cannot be fully utilised in hom o
NMR studies of protons in the catalysts consisting of Pd° metal and
geneous systems. Hence, for catalysing highly demanding reactions, e.g., the
H 3[PW120 4o] show that the presence of H 2 and Pd° greatly modifies the
Friedel-Crafts reaction, heteropoly acid must be used as a solid-acid catalyst in
dynamic nature of protons in H 3[PWi2O40].[1371 Under H 2 at 60 °C, the inter
a dry nonnucleophilic medium. To enhance the acid strength, solid heteropoly
conversion occurs between the hydrogen atoms on Pd° and protons in
acid catalysts are usually dehydrated at 150-300 °C.12,31
H 3[PW]20 4o] and that hydrogen atoms formed on Pd° spill-over to the sur
rounding heteropoly anions. Two types of protons are observed by 'H MAS
4.4.2.1 Paraffin Alkylation
NMR at 6.4 and 9.3 ppm in Ag3[PWi20 4o] when the salt is reduced by hydro
gen.11381 The protons at 6.4 ppm exist only when hydrogen is present in the gas The paraffin/olefin alkylation is used in industry for obtaining higher-octane
phase. They are mobile even at room temperature and catalytically more active paraffins which are blended into gasoline. H 2S 0 4 or H F are used as homoge
than the protons at 9.3 ppm. The exchange between the two kinds of protons neous catalysts in this process. Heteropoly acids and salts have attracted
proceeds upon raising temperature. Combining the salt Cs2.5H 0.5[PWi20 4o] interest as catalysts for this reaction.1108,143-1471 H 3[PWi204o] supported
with noble metals such as Pt enhances the catalytic activity for the n-butane (75%) on a series o f carriers, such as mesoporous molecular sieve MCM-41,
isomerisation to isobutane in the presence of H 2 at 300°C.[139’1401 am orphous silica, and alumina, has been studied as the catalyst for the
A C ID C A T A L Y S IS BY H E T E R O P O L Y C O M P O U N D S 91
isobutane/2-butene alkylation in comparison with a MCM-22 zeolite.1'081

species which might be formed by the interaction between H3[PMoi20 4o] and
The reaction was performed in a stirred autoclave at 120 °C and 30 atm with
benzoyl chloride. In contrast to H3[PMo12O40], the acids H4[SiW|204o] and
a 50:1 isobutane/2-butene feed. The greatest olefin conversion (87%) is ob
H3[PW i20 4o] both effectively catalyse the acylation and remain unchanged on
served with H?[PW1204 o]/MCM-41. The alkylate quality (trimethylpentane
the S i02 surface after the reaction. But in a more polar reaction medium such
to dimethylhexane ratio) observed with H3[PWi204o]/MCM-41, albeit
as chlorobenzene even H4[SiW120 4o] leaches from the silica support and de
worse compared with MCM-22, is better than with H3[PW1204o]/Si0 2 or
composes in the course of reaction like H3[PMo|20 4o]. Benzoic anhydride can
H3[PW)204o]/Al203. Isobutane/2-butene alkylation catalysed by potassium
be used as an acylating agent with the H4[SiWI20 4o]/Si02 catalyst, but benzoic
salt of H3[PW,20 4o] under supercritical conditions has been studied.1' 471
acid cannot. A weaker solid acid, H4[SiWi204o]/carbon, can also catalyse the
4.4.2.2 Friedel-Crafts and related reactions acylation, but less efficiently than H4[SiWi20 4o]/Si02.[4]
Cs^sHo.sIPWnCTK)] shows high efficiency in acylation of activated arenes,
The Friedel-Crafts reactions (aromatic alkylation and acylation) are the major such as p-xylene, anisole, mesitylene, etc., by acetic and benzoic anhydrides and
route to alkylaromatics and aromatic ketones. The conventional homogeneous acyl chlorides (Table 4.7). This catalyst provides higher yields of acylated
catalysts for these reactions, such as AICI3, BF3, and H2S 0 4, bring about arenes than the parent acid H3[PW]20 4o], the latter being partly soluble in
serious environmental and operational problems - high toxicity, corrosion, the reaction mixture.1' 521
spent acid disposal, difficulty of separation and recovery, etc.141 Heteropoly Silica-supported 12-tungstophosphoric acid and its Cs+ salts catalyse the
acids and their salts are promising solid-acid catalysts that could replace the acylation of toluene, p-xylene and m-xylene with crotonic acid (eq. 4.30).l' 53a’bl
conventional catalysts in some Friedel-Crafts reactions. Some alkylation of aromatic compounds with crotonic acid is also observed.
Izumi et al.[4i found that silica-supported H3[PW i204 o] is a very active Heteropoly acid is more active than zeolites HY and Beta.
catalyst, superior to other heteropoly acids, for the alkylation of benzene
with 1-octene. At a low reaction temperature of 35 °C and an excess of ben
zene, the major product is 2-phenyloctane (50-80 mol%), 3- and 4-phenyloc-
tanes also being formed. The catalytic activity depends on the pretreatment
temperature and the HPA loading. In contrast, in the alkylation of arenes with
benzyl chloride, the most efficient catalyst is H 3[PMoi204o]/Si0 2.
As found by Soeda et a/.,1' 481 bulk H 3[PWi204o] shows a better performance
than the conventional liquid (H2S 0 4, CF3COOH) or solid (Amberlyst-15,
Si02- A l20 3) catalysts for the selective alkylation of p-xylene with isobutene
at 30 °C to afford t-butyl-p-xylene - a precursor for liquid crystalline polymers
- with 75% selectivity.
Misono, Okuhara et a/.[149,1501 reported that the salt Cs2.5H0.5[PWi20 4o] is Heteropoly acid H3[PW12O40] has been shown to be a very efficient and
more active catalyst than the parent acid H 3[PW i 20 4o] for the alkylation of environmentally benign catalyst for the Fries rearrangement of phenyl acetate
1,3,5-trimethylbenzene by cyclohexene. It is suggested that the higher hydro- in homogeneous or heterogeneous liquid-phase systems at 100 - 150°C.tI53cl
phobicity of the Cs salt compared to HPA is beneficial for the adsorption of the Bulk and silica-supported tungsten heteropoly acids are very efficient
nonpolar reacting molecules. In addition, it is claimed that the Cs+ cation could and versatile catalysts for alkylation, dealkylation, and transalkylation of
favourably change the softness of heteropoly anion, thus enhancing the stabil phenols1154-16'1(eqs 4.31 -4.33). Such reactions are widely used for the preparation
isation of the intermediate cyclohexyl cation by the polyanion.
H3[PW i2O40] supported on zirconia doped with iron(III) and treated with Table 4.7 Friedel-Crafts acylation1' 521.
sulfuric acid was reported to be a very active catalyst for the alkylation of Substrates Product yield"
benzene with propene to isopropylbenzene (100-150 °C, 4 MPa). This catalyst
Acylating agent Arene C s 2 .5 H o. 5 [P W 12 0 4 o] H3[PW12O40]
gives a low yield of n-propylbenzene and can be regenerated under an air flow
at 350°C for 2h.[151] (PhCO)20 p-xylene 57 3
In the acylation of p-xylene with benzoyl chloride H3[PM oi2O40] in the (PhCO)20 anisole 85 69
A c 20 anisole 89 50
P M o/Si02 catalyst was found to decompose during the reaction.[41 Probably,
«-C7H 15COCI mesitylene 80 44
the real active species is not the supported ^ [P M o ^ O ^ ], but some soluble
a) Acylating agent/arene/catalyst = 5/100/0.01 mmol, reflux, 2h
of antioxidants, bioactive substances as well as for positional protection in This procedure allowed obtaining 2,6-dicyclohexylphenol in 77% yield
organic synthesis. As found by Kulikov et tf/.,ll54' 157] H3[PWi2 0 4o] is much (eq. 4.35). Heteropoly acids are insoluble in the reaction mixture, readily
more active and generally provides higher yields of products in these reactions separated and can be reused.
than conventional acid catalysts, such as H 2SO4, ion-exchange resin, alumino
silicates, etc. Even Nafion-H®, a perfluorinated ion-exchange resin comparable
in its acid strength to 100% H 2SO4, is less active than H 3[PW|204o].[1571
(4.35)
The alkylation of TBP apparently proceeds via a mechanism involving the

formation o f phenyl ethers as the primary products followed by their rearrange
ment to the more stable C-alkylation products (eq. 4.36). This was confirmed
by the observation of the ethers in the initial stage of reaction.
OH
OH
R R (4.36)
The alkylation of p-fe/T-butylphenol (TBP) with cyclohexene, 1-hexene, 1

styrene, and benzyl chloride in the presence of bulk or silica-supported acids 1
H 3[PW i204 o] or H4[SiW120 4o] (1 % relative to TBP) at 100-150°C affords 2,6-
The alkylation of p-cresol with isobutene (eq. 4.31 where R = CH 3 and
dialkyl-4-?er/-butylphenols in 63-90% yield (eq. 4.31). In the reaction with
R' = C(CH3)3) with the use of H3[PW i204 o][I621 has been commercialised in
styrene the yield reaches 90% at 100% TBP conversion (100-110 °C, 1 h). In
Russia.[!0bJ It is a step in the synthesis of antioxidants. The use of heteropoly
the case of a-methylstyrene, monoalkylation occurs preferentially to yield 70 %
acid instead of H2S 0 4 in this process provides a higher selectivity (by 7-10%)
4-tert-butyl-2-cumenylphenol.
and almost completely eliminates toxic water pollution.
The alkylation of TBP with olefins in the presence of heteropoly acids in
Phenols can be alkylated with a terminally unsaturated olefin polymer in the
o-xylene, which is a good acceptor of the text-butyl group, makes it possible to
presence of heteropoly acid. Thus ethylene/1-butene copolymer (M„ 3300) can
obtain 2,6-dialkylphenols directly without isolating 2,6-dialkyl-4-tert-butylphe-
be used to alkylate phenol in o-dichlorobenzene with H 3IPW12O40] precalcined
nol. The tert-butyl group is eliminated quantitatively by reaction 4.34.
at 300 °C as the catalyst. The alkylphenols so formed are useful as precursors
for the preparation of fuel and lubricant additives.1160]
OH Me OH Me
H 3[PW i20 4o] supported (20-50 wt%) on a mesoporous pure-silica molecular
sieve MCM-41, having 30 A uniformly sized pores, exhibits a higher cataly
tic activity than H 2S 0 4 or bulk H 3IPW12O40] and shows shape selectivity in
alkylation of 4-tert-butylphenol with olefins[107] (eq. 4.31 where R = C(CH3)3).
In the alkylation with styrene, H 3[PWi20 4o]/MCM-41 provides a higher yield of
(4.34) the monosubstituted product 2-(l-phenylethyl)-4-terr-butylphenol (I) than bulk
H,[PW 1204 o] or heteropoly acid supported on amorphous silica, at the expense This may be explained by the interaction of heteropoly acid with support
of the more bulky disubstituted product 2,6-bis-( 1-phenylethyl)-4-/erf-butylphe- reducing the acid strength. The rate based on the total number of protons in
nol (ID (Table 4.8). HPA/MCM-41 may be a promising solid-acid catalyst for HPA increases with increasing HPA loading, passing a maximum at ca. 30 wt%
conversion and formation of organic compounds of large molecular size. HPA loading. This dependence is explained as a result o f the competitive
The dealkylation of rerf-butylphenol derivatives is widely used in organic influence of enhancing the acid strength and reducing the number o f the surface
synthesis, e.g. for the synthesis of antioxidants. H3IPW12O40] and H4[SiWi2C>4o] proton sites as the HPA loading increases. Similar dependencies have been
are very efficient catalysts for reaction 4.32 in homogeneous and heterogeneous reported for gas-phase reactions such as dehydration o f isopropanol, esterifica
systems, where R = H, Me, Et, CH 2CH2COOMe, etc.1155 1561 The heteroge tion of acetic acid with ethanol,141 and cumene cracking.11631 The effect of
neous reaction occurs at 130-150 °C with less than 1% catalyst in the substrate ArH on the rate o f reaction 4.33 is typical of electrophilic aromatic substitu
melt. Under such conditions, molybdenum heteropoly acids are rapidly deacti tion as illustrated by the rates o f different ArH relative to benzene (2wt%
vated because of their reduction by the reaction medium. Heteropoly acids are H 3[PW12O40], 20 °C):11581
tens of times more active than other solid acid catalysts such as ion-exchange
resin, Al20 3- S i 0 2. etc. The homogeneous reaction is even more effective. Thus ArH PhH PhMe PhBu1 o-Me2C6H4 m-Me2C6H4
in acetic acid solution, the dealkylation proceeds at 80 °C. The catalytic activity AWfcphH TO 6.9 1.5 12 0.95
of heteropoly acids is in line with their acid strength and is a factor of 100
higher than that of sulfuric acid. 4.4.2.3 Esterification, Hydrolysis and Related Reactions
Heteropoly acid-catalysed transdealkylation of 2,6-di-rm-butylphenols (eq.
4.33) has been studied in detail.1157,1581 This reaction is useful for regioselective There is a strong demand for new solid-acid catalysts, having advanced charac
introduction of functional groups in phenols. Aromatic compounds (ArH) such teristics, to replace conventional liquid and solid catalysts, such as sulfuric acid
as benzene, toluene, o-xylene, naphthalene, etc. are frequently used as acceptors and ion-exchange resins, in the title reactions.141 Sulfuric acid, as already men
of the /crt-butyl group and H2S 0 4, 4-MeC6H4S0 3 H, M eS03H, CF3SO3H. tioned, poses serious environmental and operational problems. Acidic ion-ex
zeolites, and Nafion-H* as catalysts. Bulk and supported tungsten hetero change resins such as Amberlyst-15 are widely employed, but only at
poly acids are versatile solid catalysts for the trans-de-tert-butylation of phe temperatures below 100°C because of their low thermal stability. It should be
nols (eq. 4.33), where R = H, Me, Et, CH2CH 2COMe, CH2CH2COOMe, noted that in these reactions in which water participates as a reactant or a
CH2CH2CH2OCOMe, CH2CH2CH2C1, and CH2CH2CH 2 0 COCl7H 35. These product, there are only a few solid acid catalysts that may meet the criteria of
reactions occur at 100-140 C and the ArH/phenol molar ratio of 2:1 in 0.2-4 h activity and stability. As demonstrated by Izumi et a/.,14,1271 certain supported
with 92-98 % yield, the best tert-butyl acceptors being toluene and o-xylene. heteropoly acid catalysts as well as insoluble heteropoly salts have advantages as
Heteropoly acids are more active than many conventional acid catalysts includ catalysts for liquid-phase reactions in aqueous media because they are practic
ing N afion-H *. The HPA catalyst can be separated from the reaction mixture ally insoluble, thermally more stable than acidic resins and have strong acidity.
and reused. Active carbon strongly adsorbs a certain amount of heteropoly acid, and
The trans-de-rert-butylation of phenols (eq. 4.33; R = Me, ArH = PhMe) is carbon-supported acid catalysts thus obtained catalyse liquid-phase esterifica
first-order with respect to both phenol and heteropoly acid.11581 With tion and related reactions in polar media.141 The maximum HPA loading tightly
H3[PW12O40]/SiO2 catalysts, the rate depends dramatically on HPA loading. retained on carbon in water or methanol is ca. 10wt%, slightly depending on
The catalysts with the HPA loading less than 10 wt% show a negligible activity. the type of carbon and its pretreatment. The carbon-supported H3[PWi204o]
catalyse the formation of butyl t-butyl ether from n-butanol and t-butanol
at 106'C and the esterification of acetic acid with n-butanol at 60 'C .[41
Table 4.8 Alkylation of p-rm -butylphenol (TBP) by styrene catalysed Schwegler et al.1251 applied this catalyst for the esterification of phthalic anhyd
by H3[PW1204o]/MCM-4 1tl07]a. ride with C8- C 10 alcohols at 100-120 °C to yield dialkyl phthalates. In all
Catalyst Selectivity, mol% these reactions, the catalyst can be reused, no HPA leaching from carbon
being observed. However, the carbon-supported HPA catalysts have a rather
I II Other products low catalytic activity because of their weak acidity. In addition, active carbon
H3[PW120 4o] 23 68 9 strongly adsorbs polar organic substances which makes the work-up more
40% H 3[PWI204 o]/MCM-41 66 21 13 difficult.
40% H3[PWP 04o]/Si02 24 64 12 Dupont and Lefebvre11641 have studied the esterification of propanoic acid
a) 4.0wt% catalyst, in n-octane, 105 :C, 90% TBP conversion by butanol or 2-ethylhexanol catalysed by H4[SiWi20.io] and H3[PWi204o],
pure or supported on carbon supports. In the homogeneous reaction, the of the DA diester (118°C, 3h). The acidic Ce3+ salt, Ceo.87H04[PWI204o],
reaction rate is proportional to the concentration of protons. Accordingly, practically insoluble in butanol, has been found to be fairly active as a hetero
H4[SiW12O40] shows slightly higher activity than H3[PW|20 4o]. Carbon-sup geneous catalyst to give a 100% yield of the DA diester (5.4 wt%, 118 °C. 4 h).
ported heteropoly acids in all cases exhibit lower activity than the pure hetero Although less active than the parent heteropoly acid, C eo^H o.^PW Ô ^] can
poly acids, the activity depending on the carbon support and the HPA loading. be easily separated and reused. Insoluble NH4+, K+, and Cs+ salts of
In addition, a deactivation occurs during the recycling of these catalysts be H3[PW12O40] showed only moderate activities in this reaction.
cause of the leaching of heteropoly acid from support.
Izumi et alP 26i showed that the insoluble salt Cs2.5Ho.5[PW]20 4o] is an
active solid-acid catalyst for esterification and hydrolysis. For example, it is + 2 BuOH + 2 H20
much more active than zeolite H-ZSM-5 for the hydrolysis of ethyl acetate and h o 2c c o 2h B u 0 2C CO?Bu
esterification of acetic acid with ethanol.[126] However, this salt consists of very
fine particles (ca. lOnm) and readily forms a colloidal solution in water or (4.37)
alcohol, which makes it inseparable by filtration. The salt C s2.5H o.5[PW i204 o]
was found to be much more active than H-ZSM-5, N b2Os, or S 0 2- /Z r 0 2 in The esterification and acetalisation of steroids (eq. 4.38 and 4.39) occur with
hydrolysis 2-methylphenyl acetate in excess water.[165] quantitative yields in the presence of bulk or silica-supported H^PW^CXjo]
Izumi et a/.[127,141] reported that the sol-gel silica-included H 3[PW i2O40] and (1.5-9%) in MeCN, CH2C12, or benzene (40-82 °C, 0.5-4 h):[169]
CsisHo.sIPWÔ^] (Section 4.4.1.6) effectively catalyse the hydrolysis of ethyl
acetate in aqueous phase, showing higher turnover rates than Amberlyst-15 and Me R1
H-ZSM-5. Remarkably, the immobilisation of H 3[PW i2O40] into the silica Me Ri
OH -------------OCOR2
matrix effectively suppresses the HPA leaching to as low as 0.3% during the Me
hydrolysis reaction (60 °C, 3 h). It should be noted that in the case of the usual (R2C 0)20 + R2COOH
silica-supported H 3[PW)204o] catalyst, the acid completely dissolves in the
reaction medium. Interestingly, the catalytic activity of the silica-included O'
heteropoly acid is higher than that of the homogeneous acid. It is suggested (4.38)
that H3[PW120 4o] is entrapped in the silica network as a highly concentrated
aqueous solution, and the silica network is probably narrow enough to prevent
the Keggin anion from leaching outside.
Okuhara et al. used Cs2.5Ho.s[PWi20 4o] for the liquid-phase hydration of
olefins such as 2,3-dimethyl-2-butene and cyclohexene.1[166,167^
In the acetoxylation of dihydromyrcene (DHM) (eq. 4.27), the 40%
H3[PW]20 4o]/Si0 2catalyst shows a comparable activity with the homogeneous
H3[PWi204 o] catalyst, while the selectivity of the solid catalyst is higher.[48J The
latter is probably because it is more difficult for the carbenium-ion intermediate
to isomerise on the catalyst surface than in solution. With a stoichiometric 1:1
DHM-AcOH mixture, no HPA leaching from the catalyst is observed. The where R 1 = H or COMe and R2 = Et or Am. These reactions represent steps in
H3[PW1204o]/Si02 catalyst can be reused, a gradual deactivation being ob the synthesis of modified hormones. In benzene, where heteropoly acid is
served, however. Bulk H3[PW i204 o] has a very low activity probably because of insoluble, the reactions proceed heterogeneously; the catalyst can be separated
the small surface area and the blocking of proton sites by DHM oligomers. from the reaction mixture without neutralisation and reused. The catalytic
Okuhara et a/.[I50] reported that C s2.5H o.5[PW i20 4o] is more active for liquid- activity of heteropoly acid is much greater than that of 5-sulfosalicylic acid
phase decomposition of cyclohexyl acetate than other solid-acid catalysts such and similar to that of HC104.
as Nafion-H, HY, and H-ZSM-5 zeolites, and S04_/Z r0 2. 12-Tungstophosphoric acid supported on montmorillonite has been found
Timofeeva et al.[l6S] found that the esterification of dipicolinic acid (DA) to be a very efficient catalyst, in comparison with several conventional acid
with butanol (eq. 4.37), which is a step of the synthesis of pharmaceutics, is catalysts, for the etherification of phenylethyl alcohol with a variety of alkanols
catalysed by H3[PWi20 4o] as well as by its insoluble salts. H 3[PW i 20 4o] (1 wt%) (eq. 4.40).[170] The reactions are 100% selective towards the ethers that are
as a homogeneous catalyst is almost as efficient as sulfuric acid, yielding 100% useful in the perfumery industry.
PhCH2CH2OH + ROH -> PhCH2CH2OR + H20 (4.40) O
Keggin and Wells-Dawson heteropoly acids catalyse the addition of alco ]] + H20 (4.44)
hols to cyclohexenone (eq. 4.41, R = Me, Et, iso-Pr, t-Bu).[I711 H3[PWi204o]
and H4[SiWi204o] show much higher activities than Cs2.5H0.5[PW|20 4o], H-
O O
ZSM-5, and SC>42~ /Z r0 2 and almost 100% selectivities. Evidence is provided
that the reactions occur in pseudoliquid phase.
o o 4.4.3 HETEROGENEOUS CATALYSIS IN GAS-SOLID SYSTEMS
(4.41) Gas-phase reactions over heteropoly acids have attracted much interest.11,3,91
+ ROH
Acid catalysed reactions in gas-solid systems are carried out using bulk or
R
supported heteropoly acids and salts. The reaction temperatures are limited by
catalyst thermal stabilities and normally do not exceed 350-400 °C. Supported
12-Tungstophosphoric acid on titania can be used as a catalyst for separat
heteropoly acids (usually on silica) are generally preferred because of their high
ing isobutene from mixed C4 hydrocarbon streams. The procedure involves the
surface area. HPA loadings vary from about 20 to 50 wt% or even higher, which
etherification of the C4 mixture with a diol, such as ethylene glycol or 1,2-
corresponds to a coverage of more than one monolayer. At lower loadings, the
propylene glycol, over the HPA catalyst to give the glycol mono-t-butyl ether
acidity of heteropoly acid decreases because of interaction with support; such
(eq. 4.42), followed by deetherification of the monoethers at higher tempera catalysts are also quite sensitive to poisoning by impurities that may be present
tures to yield pure isobutene and regenerated glycol.[172] in the support or feed. For these reasons, the catalysts containing less than
10wt% HPA usually show poor activities and are rarely used.11,21 Chemical
(CH3)2C = CH2 + HOCH2CH2OH - (CH3)3COCH2CH2OH + H 20 (4.42)
modification of the surface of support could reduce the negative effect
of support on the HPA acidity and lead to lower HPA loadings in practical
4.4.2.4 Miscellaneous Reactions catalysts.
Silica-supported H3[PW)204o] has been found to be an active and recyclable Control of water content in heteropoly acid catalysts is essential for their
catalyst for the Diels-Alder reaction (eq. 4.43) in toluene medium, providing a efficient performance. This can be achieved by thermal pre-treatment of the
70-80% yield.1173’1741 The Ce3+ salt, Ce0.87Ho.4[PWi20 4o], shows a fairly high catalysts, typically at 130-200 °C. The effect of water may be attributed to the
activity too, while C s2.5H 0.5[PW i20 4o] is practically inactive. Bulk H 3[PW i2O40] HPA acid strength and the number of proton sites as well as to catalyst
exhibits a very low activity probably because of the small surface area and site deactivation. Excess water causes a decrease in the HPA acid strength - and
blocking by diene polymers. thus in its activity. Dehydration of the catalyst increases the acid strength but
decreases the number of acid sites, which may reduce the overall catalytic
O O activity unless the reaction is highly demanding for catalysts acid strength. In
addition, too strong acid sites thus created tend to deactivate (coke) faster.121
Two types of mechanism of catalysis have been proposed for heteroge
neously catalysed reactions over solid heteropoly acids - surface type and
bulk type I (Section 4.1.2).t1,61 In most cases, the acid-catalysed conversions
of organic molecules probably occur via the conventional surface catalysis.
With bulk heteropoly acids at relatively low temperatures, small polar mol
Sol-gel derived H3[PW]20 4o] on silica has been applied for Diels-Alder reac- ecules possessing a high affinity to heteropoly acid (e.g. lower alcohols) may
tionsJ1751 react pseudohomogeneously in the catalyst bulk.[11 With supported heteropoly
Silica-supported Keggin heteropoly acids have been found to be efficient and acids, reactions of polar substrates are more likely to occur via the surface type
recyclable catalysts for the dehydration of alcohols, such as 1,2-diphenyletha- catalysis. This is backed by the observation that both polar and nonpolar
nol, l-(3,4-dimethoxyphenyl)-2-phenylethanol and cholesterol, in liquid pha- substrates show similar dependencies between the catalytic activity and the
se [i76a] h 3[PW i204 o] can be used instead of sulfuric acid as the catalyst for the surface area of supported heteropoly acid catalysts. Typically, for gas-phase
dehydration of o-benzoylbenzoic acid to anthraquinone.[I76b] reactions of both polar and nonpolar molecules, the catalytic activity increases
with HPA loading, reaching a plateau or passing a maximum at 25-40 wt% detail by Misono et a /J ' 1with the aim of proving the bulk type I (pseudoliquid
loading. This is observed for the alkylation of benzene with ethylene, the ester phase) mechanism. H 3[PWi204o] was found to be much more active for the
ification of acetic acid with ethanol, and the dehydration of isopropanol over dehydration o f isopropanol than Si0 2- A l2C>3 (a factor o f 30 by weight) at
H3[PW,204 o] or H4[SiW1204o] on silica,[4] as well as for the cracking o f cumene 25 °C. The activity o f heteropoly acids decreases in the series: H3[PWi204o]
and the disproportionation of toluene over H 3IPW12O40] on silica or alu > H4[SiW12O40] > H 5[PW ioV204 o] > H 3[PM o12O40] > H 5[PM o10V20 4o] « H4
mina,^ 631 Such a behaviour is explained as a result of decreasing the HPA [SiMoi20 4o] which is in line with their acid strengths. Using a transient re
surface area as the loading increases. Water-insoluble heteropoly salts (e.g. sponse method and the deuterated isopropanol, it was demonstrated that a
C s2.5H o.5[PW i 2C>4o]) are incapable of absorbing polar molecules into the bulk; large am ount of alcohol, corresponding to about 100 surface monolayers, is
they exhibit surface-type catalysis towards both polar and nonpolar molecules.111 present in the bulk of crystalline H3[PWi204o] during the course of dehydration
Like other solid-acid catalysts, the solid heteropoly acids tend to deactivate at 80 °C. It was also estimated that the rate of isopropanol absorption and
during organic reactions because of the formation of carbonaceous deposit desorption is about 50 times greater than the reaction rate. These results were
(coke) on the catalyst surface. Subsequent regeneration of heteropoly acid considered to support the dehydration proceeding pseudohomogeneously in
catalyst is difficult. The conventional regeneration by burning coke at 500- the catalyst bulk. These observations do not prove, however, that the bulk
550 °C, which is routinely used in the case of aluminosilicates and zeolites, is protons are the true catalytically active sites. It is conceivable that the reaction
not applicable to heteropoly acids because their thermal stability is low. This might predominantly occur on the more accessible and stronger surface
problem remains to be solved to put heterogeneous heteropoly acid catalysis in protons rather than on the bulk protons, with the catalyst bulk serving as a
practice. Supporting heteropoly acid on a carrier may inhibit the formation of reservoir supplying the alcohol molecules to the surface acid sites.
coke,141 while bulk heteropoly acids, having very strong acid sites and low Izumi et n/J41 found no straight correlation between the HPA loading and
surface area, coke more rapidly. the catalytic activity for the dehydration of isopropanol catalysed by silica-
supported H 3[PWi2O40] and H 4[SiWi20 4o] at 150°C; the activity levelled at the
4.4.3.1 Hydration of Olefins HPA loading of 25-30 wt%, as usual. This shows that the bulk catalysis is not
efficient in the case of supported heteropoly acids.
Supported heteropoly acids are known for long time as the efficient catalysts
for gas phase hydration of olefins such as ethylene and propylene to the 4.4.3.3 Esterification
corresponding alcohols.[177,1781
Bulk and supported heteropoly acids are active catalysts for the esterification of
oh
acetic acid with ethanol.[4] Typically, supported acids are more active than bulk
(4.45) ones. Various supports such as silica, active carbon, alumina, and titania have
r -c h = c h 2 + h 2o r -c h -c h 3
been studied. Among them, silica and active carbon give better activities and
selectivities. Tungsten acids are more active than molybdenum ones; the latter
More recently, several heteropoly acid catalysts for this reaction have been tend to reduce during the reaction (Table 4.9). No catalyst deactivation is
patented, including heteropoly acids supported on niobia,[179] acid-treated observed after 7h on stream. The catalyst activity o f silica-supported
clay,111801 and siliceous supports.1181,1821 These may challenge the industrial H 3[PW120 4o] and H4[SiWi20 4o] for the esterification of acetic acid with ethanol
catalyst H 3P 0 4/S i0 2 which has a drawback of polluting phosphoric acid. at 150°C increases with the HPA loading until 25-30 wt% and remains un
The gas-phase hydration of isobutene over bulk H4[SiWi20 4o]tl831 and sup changed at higher loadings. This indicates that the esterification mainly occurs
ported H3[PWi20 4o] and H4[SiWi20 4o][1841 has been studied. Baba and Ono[184] via the surface type catalysis.^41
found that the activity of supported H 4[SiWi204o] decreases in the following The synthesis of ethyl acetate by the direct addition of acetic acid to ethylene
order of supports: Amberlyst-15 > activated carbon > S i0 2 > T i0 2. The max catalysed by silica-supported H4[SiW 12040] in vapour phase has been de
imum activity was found for 30% H4[SiWi204o]/Amberlyst-15. veloped by BP Amoco (Chapter 6).t1851
4.4.3.2 Dehydration of Alcohols 4.4.3.4 Friedel-Crafts and related reactions
Solid heteropoly acids and salts also efficiently catalyse the dehydration of The alkylation of benzene with ethylene in vapour phase with heteropoly
alcohols - the reverse reaction of olefin hydration. The dehydration of isopro acid catalysts occurs at temperatures below 200 °C.[4] At higher temperatures
panol - a standard test reaction in heterogeneous acid catalysis - was studied in an increased coke formation is observed. This is a clear example of surface
Table 4.9 Esterification of acetic acid with ethanol over heteropoly acid shows no activity in these reactions.[1631 A continuous gas-phase catalytic
catalysts (How reactor, 150°C, 1atm, EtOH/AcOH = 2.5)[4]. acetylation of phenol with acetic anhydride to phenyl acetate followed by
Catalyst AcOH Selectivity51, % simultaneous Fries rearrangement to yield ortho- and para-hydroxyacetophe-
nones (eq. 4.46) over a silica-supported heteropoly acid has been described.^,86^
conversion, % EtOAc Et20 Alkenes
5% H,[PW 12O40]/SiO2 90.1 91 9 0

5 % H 4[SiW,2O40]/SiO2 96.2 88 12 0
5% H,[PM oi204o]/SiC>2 55.4 91 9 0
5% H4[SiMoi2O40]/SiO2 60.7 91 9 0
H,[PW 12O40] 57.0 72 27 1
H4[SiWpO40] 60.7 69 30 1
COCHj
H 3[PM o ,2O40] 26.9 86 14 0
H4[SiMoi20 4o] 44.6 85 15 0
A complete conversion o f phenol to phenyl acetate is achieved at 140 °C. Upon
a) Selectivity based on EtOH increasing the temperature to 200 °C, the phenyl acetate formed isomerises into
hydroxyacetophenones with 10% yield and 90% selectivity to the para isomer.
reaction as both the substrates have weak affinity towards heteropoly acid, and
the HPA is insoluble in hydrocarbons. A comparative study[4^ has shown that
4.4.3.5 Oligomerisation of Olefins
tungsten acids such as H3IPW12O40] and HUfSiW^Cô] supported on silica
catalyse the gas-phase alkylation of benzene more effectively than other typical 12-Tungstosilicic acid catalyses the oligomerisation of propene to distillate
solid acids such as silicoalumina and supported phosphoric acid (Table 4.10). fuels.[187] The catalytic activity depends upon the calcination temperature, the
The activity is comparable to that for zeolites CaY and LaY, which are highly optimum activity being achieved for the catalyst calcined at 240 °C.
active catalysts for the alkylation of benzene. With the tungsten heteropoly H4[SiWi204o] supported on bauxite has been found to coke less rapidly than
acids, the selectivity for monoalkylation is higher as compared with the zeolite the bulk acid. At 170-180 °C and a pressure of 12 MPa a 95% conversion of
catalysts. In the case of zeolites, the product ethylbenzene probably undergoes propene over H4[SiWi20 4o] is achieved. The selectivity to the C+2 fraction is
further ethylation more easily as it resides for longer time inside zeolite micro higher than in the case of the classical oligomerisation catalyst H 3P0 4/S i0 2.
pores than on the surface of supported HPA catalyst. Among the sup The activity of bulk 12-tungstophosphoric acid and its salts for propene
ports studied, silica is the best for this reaction. Molybdic acids such as oligomerisation at 220-230 °C and a propene pressure of 5 MPa in a flow
H 3[PM o i 204 o] and H4[SiMoi204o] were totally inactive for this reaction prob reactor decreases in the order of countercations (Table 4.11): Al3+ > Co2+
ably due to their reduction during the reaction. The effect of HPA loading on > Ni2+ > N H | > H +, Cu2+ > Fe3+, Ce3+ > K +.tl88J Fast catalyst deactiva
the alkylation activity has also been studied. The activity reaches a maximum at tion is observed due to strong coking. Diluting the catalyst with acid-washed
HPA loadings of 15-20 wt% and remains unchanged at higher loadings. sand greatly increases the liquid product yield and the catalyst lifetime, the
12-Tungstophosphoric acid supported on silica or y-alumina catalyses activity order remaining the same as for the undiluted powders. The aluminium
cumene cracking at 150°C with 90% conversion and toluene disproportiona salt is the most active, achieving 90 % conversion at 230-240 °C and 5 MPa, the
tion at 250 °C. The catalytic activity increases with increasing HPA loading, main product being the trimer. The sand-diluted aluminium salt achieves 100%
reaching its maximum in the loading range of 38-50 wt%. H 3[PWi204o]/MgO conversion under these conditions with no deactivation after 150 h on stream.
Table 4.10 Alkylation of benzene with ethylene over solid acids^4]a. 4.4.3.6 Isomerisation of Alkanes
Catalyst Temperature, °C C6H6 conversion, % EtPh selectivity, % The skeletal isomerisation of linear alkanes is important for increasing the
2 3 % H 3[PW pO40]/SiCL 200 3.8 85 octane number of gasoline. The isomerisation of n-butane is a direct route to
2 3% H 3[SiWi204o]/Si(Y 200 3.9 80 isobutane, a feedstock for the olefin/paraffm alkylation and MTBE synthesis.
CaY 200 4.5 66 The alkane isomerisation requires very strong acid sites in the catalyst. Hence,
LaY 200 3.6 45 heteropoly acids, because of their strong acidity, have attracted much interest
Si02—A120 3 250 0.6 100
23% H3P 0 4/S i0 2
as the catalysts for this reaction.[72’l08,163’I89_196] Bulk and supported tungsten
300 0.3 100
acids, H3[PW i20 4o] and H4[SiWi204o], as well as heteropoly salts, e.g.
a) Reaction conditions: C J ^ /C iH .) = 0.5, 1 atm C s2.5H o.5[PW120 40], neat or doped by platinum group metals, have been used.
CATALYSIS BY POLYOXOMETALATES ACID CATALYSIS BY HETEROPOLY COMPOUNDS 105
104
Table 4 11 Propene oligomeristion catalysed bv heteropoly acids and Bulk Cs2.5H0.5tPW 12O40] catalyses the isomerisation of n-butane at
salts (flow reactor, 220-230°C, 5 MPa, WHSV = 12h ')1' 881. 300°C.[,89] This salt, because of its high surface area, has a higher activity
Initial Steady state than the bulk parent acid H3IPW12O40]. Acidic salts CsxH 3-x[PW12C>4o] pre
Catalyst Cl2+
conversion3, % conversion, % wt% pared by grinding mixtures of H3[PWI2O40] and Cs3[PWi204o] showed a higher
catalytic activity in n-butane isomerisation at 200 °C than the salts prepared by
H 3[PWI20 4o] 17 - 68 precipitation.11941
(NH4),[PW ,204 o] 22 21 44
11 — 55 Bifunctional catalysts, comprising a Pd(II) salt of heteropoly acid or Pt-
K3[PWI2O40]
C u3/2[PW12O40] 15 - 41 doped Cs2.5Ho.5[PW[20 4o], in the presence of hydrogen exhibit high activities in
C o3/2[PW12O40] 28 22 41 n-alkane isomerisation as well as better stabilities to deactivation.[190~1931 In this
Ni3/2[PWi2O40] 35 20 41 case, the process occurs through the dehydrogenation of alkane on Pt or Pd,
NiH[PW,2O40] 24 20 44 followed by the acid catalysed skeletal isomerisation of the alkene formed and
Fe[PW1204o] 11 10 56
51
finally by hydrogenation.
Ce[PWi204o] 9 7
42 87 36 Methylcyclopentane is ring-expanded and cyclohexane is ring-contracted to
AltPWÔ.oJ
H3[PWi2O40]/AJ2O3 26 20 47 methylcyclopentane (eq. 4.47) on 12-tungstophosphoric acid supported on
H4[SiW12O40] 40 25 47 silica and on microporous acidic silver salt Ag3-xHx[PWi204o]. The conversions
of the two substrates increase with the loading of heteropoly acid on silica while
a) Conversion of propene to liquid product after 1 h
achieving significantly higher values on the silver salt. The conversions pass
through a maximum as the Ag+/H + ratio increases; at 250 °C, a maximum
Nowinska et a/.[1631 reported the isomerisation of n-hexane over H 3PPW12O40]
conversion of cyclohexane of 18 % with 92 % selectivity to methylcyclopentane
supported on silica or alumina at 75 °C, however, with a very low activity.
is obtained for A g u H u lP W ^ O « ].11971
H3[PW1204 o] supported (75wt%) on MCM-41 molecular sieve (800m2 g~‘
surface area) has been reported to efficiently catalyse the isomerisation of n-
butane, with much higher selectivity to isobutane compared to H-ZSM-5 (Table
4.12).[1081 In the case of H-ZSM-5, the main process is the cracking of n-butane.
Bardin and Davis[72J found that the catalytic activity of bulk and silica- (4.47)
supported H3P W 12O40] for n-butane and n-pentane isomerisation at 200 °C
decreases with increasing pre-treatment temperature, which suggests that the
level of hydration is important. After pre-treatment at 300 °C, a well dispersed
catalyst 5% HPA/Si02 was inactive, apparently lacking sufficient acidity re
quired for this reaction, while higher loaded samples (10 and 25wt%) were
active. Ammonia sorption microcalorimetry results are well in line with reactiv 4.4.3.7 Conversion of Methanol to Hydrocarbons
ity, showing a significant increase in the acid strength as the loading increases Similar to zeolites, heteropoly acids and salts catalyse the conversion of
from 5 to 25 %. Catalyst deactivation was observed during the reaction, sup methanol to hydrocarbons.1198~201] Ono et al.im] found that H3[PWi20 4o],
posedly due to dehydration of the surface of heteropoly acid. Addition of water H4[SiWi20 4o], and their silver(I) and copper(II) salts catalyse this reaction at
to the feed recovered the catalytic activity. 300 °C, the main products being the C2- C 5 aliphatic hydrocarbons (Table
4.13). The silver(I) salts show the highest activity, the copper(II) salts perform
Table 4.12 Isomerisation of n-butane over H 3[PW12O40]/MCM-41 (flow reactor, similarly to the parent heteropoly acids. As compared to H-ZSM-5 zeolite, the
54 atm, WHSV = 1)[108]. activities of heteropoly compounds are lower and so is the yield of aromatics
Catalyst Temperature Conversion Selectivity, wt% (<2.5%). It is suggested[1991 that the active proton sites in the heteropoly salts
are generated by reduction with hydrogen that forms by dehydrogenation of
°C wt% Q -C 3 i-C 4 c 5+ methanol:
75% H3[PW12O40]/MCM-41 178 23.9 2.1 94.1 18~
75% H3[PW12O40]/MCM-41 263 35.5 2.4 92.5 5.1 Ag+ + V2 H2 —>Ag + H+
H-ZSM-5 260 34 40 24 36
Cu2+ + Vi H2 - Cu+ + H +
ACID CATALYSIS BY HETEROPOLY COMPOUNDS 107
Table 4.14 Synthesis of MTBE over solid acid catalysts in gas phase at 110 °C[202’203].
Tabic 4.13 Product distribution for the conversion of methanol to hydrocarbons (flow
reactor, 300 "C)[19S1. __________________________ Catalyst2 Yield, % Selectivity6, % Selectivity0, %
Catalyst H 6[P2W 180 62]/S i0 2 14.2 99 82
H 3[PWi20 4o]/Si02 7.7 96 52
H 3[P W 120 4 o] Cu3/2[PWi20 4o] Ag3[PW120 4o]
H4[SiW12O40]/SiO2 7.0 98 70
H4[GeW,2O40]/SiO2 13.4 99 69
Product distribution. %
1.2 0 H 5[BW12O40]/SiO2 10.0 99 76
MeOH 1.3 H6[CoW12O40]/SiO2
37.3 2.0 13.7 100 94
MeOMe 38.6
61.5 98.0 H6[P2W 180 62] 7.2 80 98
Hydrocarbons 60.1
H3[PW12O40] 6.6 100 96
Hydrocarbon distribution, %
5.2 9.0 H4[SiW12O40] 4.6 100 97
CH4 3.7
9.5 9.0 H 4[GeWi2O40] 11.2 100 99
C 3H 4 11.3
0.8 5.2 H 5[BW12O40] 7.2 100 100
c 2h 6 0.9
c 3h 6 8.3 8.5 3.8 H6[CoWi20 4o] 5.7 100 98
13.4 34.0 Amberlyst-15 8.1 69 50
C3H s 16.1
39.2 26.1 S i0 2—A120 3 11.5 55 80
c4 39.3
12.5 13.7 7.2 H-ZSM-5 8.9 21 100
C5
Cs 7.9 9.7 5.7
a) Catalyst weight: 0.5 g; HPA loading on Si02: 20wt%
b) Selectivity based on methanol at 2h
c) Selectivity based on isobutene at 2 h
Cesium salts of heteropoly acids exhibit better selectivities to C2- C 4 olefins,
up to 64% for C s2.5H o.5[PWi204 o]-[2011 conventional liquid-phase nitration by mixed acid comprising concentrated
nitric and sulfuric acids.[208]
4.4.3.8 Synthesis of MTBE
The synthesis of MTBE in the gas phase using solid heteropoly acid catalysts + hno3 n o 2 + h 2o (4.48)
has been of considerable interest in the last couple of decades.11,202_206] A range
of bulk and silica-supported (20 wt%) Keggin and Wells-Dawson acids have
been examined in a flow reactor at atmospheric pressure and 50-110 °C (Table Partially substituted thallium and cesium salts of H3[PW1204o], H4[SiWi204o],
4.14).[202,203] The supported heteropoly acids show similar activities to Amber- and H 3[PMoi204o] catalyse the vapour-phase nitration of benzene with dilute
lyst-15, Si0 2- A l203, and H-ZSM-5 per unit catalyst weight and are twice as (70%) nitric acid.[209J With the salt Csi.5Hi.5[PMoi204o] in a fixed bed flow
active as the bulk heteropoly acids. The selectivities based on both methanol reactor at atmospheric pressure and 160°C, an initial yield of nitrobenzene of
and isobutene are significantly higher for heteropoly acids than for Amberlyst- 90 % (based on nitric acid) was obtained which, however, declined to 70 % after
15, Si02- A l20 3, and H-ZSM-5. Interestingly, the Wells-Dawson acid 200 h on stream. The mixed oxide T i0 2- M o 0 3 catalyst treated with sulfuric
H6[P2Wi8062] is more active than the Keggin acid H 3[PWi20 4o] despite the acid showed a stable catalytic activity for more than 500 h on stream providing
fact that the latter is stronger. The same was found for MTBE synthesis in 87 % yield of nitrobenzene.
homogeneous liquid phase.[27]
Heteropoly acids have also been used as catalysts for the synthesis of MTBE
from tert-butanol and methanol (Ref.[,] and references therein). 4.5 DEACTIVATION AND REGENERATION OF SOLID
The performance of shell- and tube-type membrane reactors equipped with HETEROPOLY ACID CATALYSTS
heteropoly acid-polymer composite catalytic membranes for the vapour-phase
decomposition of MTBE has been described.[207] A serious problem with the solid heteropoly acid catalysts is their deactivation
during organic reactions because of the formation of carbonaceous deposit
4.4.3.9 Nitration of Benzene (coke) on the catalyst surface. Conventional regeneration by burning coke at
The vapour-phase nitration of benzene over solid acid catalysts has been 500-550 °C, which is routinely used in the case of aluminosilicates and zeolites,
investigated extensively for some decades as a cleaner alternative to the is not applicable to heteropoly acids because their thermal stability is not high
enough/ 21 Therefore, for heteropoly acids to be more widely used for heteroge
neous acid catalysis an efficient and reliable methodology of their regeneration
would be beneficial. In particular, the development of a technique leading to a
reduction in the temperature of coke removal is of importance for the regener
ation of deactivated solid heteropoly acid catalysts.
The coking and regeneration of silica-supported H3[PW i204 o] during pro-
pene oligomerisation has been studied/ 2' 0,2111 Coke formation causes rapid
deactivation of the catalyst. The coked versus fresh catalysts have been charac
terised by 31P and 13C MAS NMR, XRD, XPS and TGA/TPO to reveal that
the Keggin structure of the catalysts remains unaffected by coke deposition.
The Pd doping has been shown to affect the nature of coke formed, inhibit
ing the formation of polynuclear aromatics. Co-feeding water to the propene
flow greatly inhibits coke formation. The removal of coke from HPA catalysts
has been attempted using solvent extraction, ozone treatment and aerobic
oxidation. The aerobic burning of coke on the undoped H3[PWi204o]/Si02
proceeds to completion at the temperature of 500-560 °C, which is higher than
the temperature of H3[PW i204 o] decomposition. Doping the catalyst with Pd
significantly decreases this temperature (Figure 4.7) to allow catalyst regener
ation at temperatures as low as 350 °C without loss of catalytic activity (Figure
Figure 4.8 Catalyst performance of fresh and regenerated 2.5% Pd-doped 20% PW/
4.8). Si02 for propene oligomerisation/210’211'
Generally, prevention of catalyst deactivation is preferable to catalyst regen

eration because the latter is usually difficult and expensive. In the case of gas-
phase oligomerisation of propene catalysed by H4[SiWi204o], the catalyst cokes
less rapidly when supported on silica than in the pure form/ 1871 Diluting bulk
heteropoly acid catalyst with acid-washed sand (1 part catalyst to 10 parts
sand) dramatically increases the product yield and catalyst lifetime in the gas-
phase oligomerisation of propene (230 °C, 5 MPa) / 1881 Treatment of the deacti
vated heteropoly acid catalyst for the 1-butene and n-pentane isomerisation
with water recovers activity, whereas treatment in air or N20 is ineffective. It is
suggested that water treatment regenerates acid sites by rehydrating partially
decomposed Keggin units/ 721 Co-feeding water is crucial to the stable activity
of the silica-supported FL^SiWÔ^] catalyst for the industrial synthesis of
ethyl acetate from ethylene and acetic acid (Chapter 7) / 1851
Figure 4.7 TGA/TPO for 20 % PW/Si02 coked with propene at 200 °C for 1h/210,2111
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210. M.R.H. Siddiqui, S. Holmes, H. He, W. Smith, E.N. Coker, M.P. Atkins and I.V. 5.1.1.5 M ech an ism ............................................................................................... 131
Kozhevnikov, Catal. Lett. 2000, 66, 53. 5.1.2 Oxidation with hydrogen peroxide............................................................................ 136
211. I.V. Kozhevnikov, S. Holmes and M .R.H. Siddiqui, Appl. Catal. A 2001, 214, 47. 5.1.2.1 Venturello-Ishii system.............................................................................. 137
212. U.S. Patent 5,716,895, 1998. Epoxidation of a lk e n e s ......................................................................... 137
Miscellaneous oxidations......................................................................... 144
5.1.2.2 Other polyoxometalate s y s t e m s ............................................................. 144
Epoxidation of a lk e n e s ......................................................................... 144
Oxidation of alkanes.............................................................................. 146
Oxidation of aromatic compounds........................................................ 147
Oxidation of sulfur compounds............................................................. 148
5.1.3 Oxidation by organic p e r o x id e s ............................................................................ 148
5.1.4 Miscellaneous o x id a tio n s ....................................................................................... 149
5.2 G a s - p h a s e o x i d a t i o n ......................................................................................................... 149
5.2.1 General overview........................................................................................................ 149
5.2.2 Oxidation c a ta ly sts.................................................................................................. 150
5.2.3 R eaction s................................................................................................................... 151
5.2.3.1 Oxidation of methacrolein to methacrylic a c i d ....................................... 152
5.2.3.2 Oxidative dehydrogenation of isobutyric a c i d ....................................... 156
5.2.3.3 Heterogeneous Wacker r e a c tio n ............................................................. 156
5.2.3.4 Oxidation of ethylene to acetic a c i d ........................................................ 157
5.2.3.5 Oxidation of a l k a n e s .............................................................................. 158
R e f e r e n c e s ...................................................................................................................................... 159
Selective (partial) oxidation of organic compounds catalysed by heteropoly

compounds, both homogeneous and heterogeneous, has attracted much
attention in the last three decades. Two types of processes are feasible: (i)
oxygenation, i.e. oxygen atom transfer to a substrate, and (ii) oxidative
118 CATALYSIS BY POLYOXOMETALATES POLYOXOMETALATES AS CATALYSTS FOR SELECTIVE OXIDATION 119
dehydrogenation. In liquid-phase oxidation a broad range of oxidants, such as veloped a new type of polyoxoanion-supported organometallic catalysts in
dioxygen, hydrogen peroxide, alkylperoxides, etc., can be used, whereas in gas- which a metal complex is bound to the surface of a polyoxometalate. This
phase reactions mostly O2 and infrequently N 2O have been applied. In contrast type can be exemplified by [(l,5-C O D )Ir • P2Wi5Nb3062]8_ (M = Ir1 or R h1,
to acid catalysis, where easily available classical Keggin-type heteropoly acids COD = cyclooctadiene) where the M ion is probably bound to the {NbjOu}
dominate (Chapter 4). in catalytic oxidation, a wide variety of transition metal- cap in the Wells-Dawson anion. These systems show a high activity in cyclo
substituted polyoxometalates (POM) are used. In this chapter, we will mainly hexene oxidation with oxygen. Although little catalytic chemistry has been
discuss liquid-phase and gas-phase oxidations with the use of the most im port reported so far for such systems, they may be promising for future studies.
ant and environmentally benign oxidants - dioxygen and hydrogen peroxide.
Several reviews on catalysis by polyoxometalates for selective oxidation are 5.1.1.1 General Principles
available.11' 171
In liquid-phase oxidation, HPA-n with n = 2-6 are used. These polyanions are
capable of acting extremely efficiently as a reversible redox system in conjunc
tion with dioxygen (or air) under mild conditions.11,101 Generally reactions
5.1 LIQUID-PHASE OXIDATION
catalysed by HPA-n proceed via a stepwise redox mechanism represented by
equations 5.1 and 5.2:
The liquid-phase oxidation of organic substances catalysed by polyoxometa
lates is usually carried out in homogeneous or biphasic systems. Heterogeneous
HPA-n + Red + m H + -> H m(HPA-n) + Ox (5.1)
liquid-solid systems are also used but less frequently. Amongst various oxidants
that can be used in these reactions, dioxygen and hydrogen peroxide are by far H m(HPA-n) + m /4 0 2 - HPA-n + m /2 H 20 (5.2)
the most important. In regard to catalytic oxidation, polyoxometalates are
frequently viewed as robust, oxidation-resistant inorganic analogues of metal- This mechanism includes stoichiometric m-electron oxidation of the substrate.
loporphyrins because the polyoxometalate ligand in transition-metal-substi Red, by HPA-n to form the product, Ox, followed by reoxidation of the reduced
tuted polyoxometalates is not susceptible to oxidative degradation and form of the oxidant, Hm(HPA-n), with dioxygen, where H m(HPA-n) =
generally is thermally more stable than porphyrins or other macrocyclic H m[PMoi2-n6+Vn-m5+Vni4+04o](3+n) . The presence of a certain number of
ligands.18,9,12,17,18’191 However, the solvolytic stability of polyoxometalates V5+ ions in the heteropoly anions is essential. Thus, the parent molybdenum
may be a problem in liquid-phase reactions. For example, in oxidations with anion [PM012O40]3- (HPA-0) fails to possess such redox properties under mild
hydrogen peroxide, the decomposition of polyoxometalates by interaction with conditions in solution, and so does HPA-1 for reasons that will be discussed
H2O2 is frequently observed. The state of polyoxometalates in solution is later. Reactions 5.1 and 5.2 involve the reversible V5+ V4+ transformations
generally complicated by a series of pH-dependent equilibria, involving a that are responsible for the redox properties of HPA-n. The reduction of HPA-n
variety of polyanions and mononuclear metallospecies. These equilibria are in solution is accompanied by protonation to maintain the charge of the poly
largely unknown; consequently, relatively little exact knowledge of mechanisms anion. In aqueous solution, HPA-n are generally used in the pH range from 0.5
of POM-catalysed oxidation is available. to 3.5, where they are relatively stable.
Operationally, reactions 5.1 and 5.2 can be carried out in the same reactor
(one-stage process) or separately as a combination of two stoichiometric reac
5.1.1 OXIDATION WITH DIOXYGEN tions (two-stage process).11,10,211 In the two-stage process, the direct contact
between the organic substrate and O2 is excluded, hence this process is usually
This section mainly reviews the application of Keggin-type mixed-addenda preferred for safety reasons.
heteropoly anions [PMoi2- nVn04o](3+n) (HPA-n) as catalysts for liquid-phase As the catalysts, either one-component or two- and multicomponent systems
oxidation with O2. Here HPA-n can mean either anion or acid as well as a are used. The most important two-component system includes HPA-n and
partially protonated anion. The HPA-n system was first used for liquid-phase Pd(II).11,2,7,10,211 This is analogous to the redox system Q 1CI2 + Pd(II) that is
oxidation by Matveev et a/.11,201 This is the most efficient and versatile system in used for the industrial oxidation of ethylene to acetaldehyde (the Wacker
the polyoxometalate series for oxidation by o 2.[1,2,7,10,12,21,221 Discussed in this process). The important advantage of the HPA-n + Pd(II) system is that it
section are the HPA-n-catalysed oxidations in homogeneous, biphasic, and can work in the absence of Cl- ions, hence it is more selective and less
heterogeneous systems as well as mechanistic aspects of the HPA-n catalysis. corrosive. Other two-component systems are also known, for example, those
Numerous attempts have been made to perform aerobic oxidations by other including HPA-n and T1(III)/T1(I), Pt(IV)/Pt(II), Ru(IV)/Ru(III), Ir(IV)/Ir(III),
kinds of polyoxometalates; for a review, see.18,12,151 Finke et a/.1191 have de B n /B r“, or I2/ I —J12,71 In two-component systems, the substrate is usually
oxidised by the co-catalyst, and the polvoxometalate enhances the reoxidation cally. The active oxidants are probably the V 0 2 ions which form by dissoci
of the co-catalyst by reactions 5.1 and 5.2. The two-component systems POM + ation of HPA-n. The rate of oxidation decreases in the order of arenes: durene
Pd(II) and POM + Rh(l) have been used for carbonylation, hydroformylation > mesitylene > p-xylene > toluene, i.e. in parallel with their ionisation poten
and hydrogenation reactions.123-281 tials. The reaction is suggested to proceed via the formation of aromatic radical
The thermodynamic condition for the occurrence of reactions 5.1 and 5.2 cation intermediates.
can be represented using redox potentials of the substrate, HPA-n, and dioxy-
gen:^7' 101
E(Red) < E(HPA-n) < £ ( 0 2)
The reduction potential £(HPA-n) is ca. 0.7 V versus standard hydrogen elec
trode (SHE) for HPA-n with n = 1-4 at pH 1,129,301 and the standard reduction
potential of oxygen £ ( 0 2 / 2 ^ 0 ) is 1.23 V at 25 °C and 1 atm. Hence the above
Many synthetically attractive oxidations of hydrocarbons catalysed by
condition fulfils for a wide variety of organic substrates as well as for many
HPA-n have been developed to date. Neumann et alP l] reported highly effi
inorganic redox systems to be used as co-catalysts with HPA-n. Some other
cient dehydrogenations with HPA-2 as a catalyst in CH2ClCH2Cl/tetraglyme
polyoxometalates having similar properties, for example [PM06W6O40]3 -, can
solution. For example, reaction 5.5 yields 98% anthracene (70 °C, 16h).
also be used for this purposed311
5.1.1.2 Homogeneous Oxidation I l l + H,o (5 ‘5)

One-component HPA-n system A range of hydrocarbons can be homoge
neously oxidised with HPA-n as catalyst under mild conditions. HPA-n cata
The HPA-2-catalysed dehydrogenation of a-terpinene to p-cymene in acet
lyse the oxidation of alkanes to oxygenates by 0 2. Arzamaskova et alP 21 and
onitrile solution was found to be zero-order in a-terpinene, first-order in
Geletii and Shilov1331 reported the oxidation of alkanes by HPA-6 under mild
dioxygen, and second-order in HPA-2.1421 On the basis of these kinetic results
conditions in the presence Ru(III), Ir(III)1321 and Pt(II).1331 Lyons et alP4]
and spectroscopic data, a reaction mechanism was formulated. This involves
oxidised alkanes by 0 2 with HPA-n as one-component catalyst. F or example,
the formation of a stable substrate-catalyst complex in the catalyst reduction
propane is oxidised in AcOH - H 20 solution in the presence of HPA-n at
stage 5.1 and a p-peroxo catalyst intermediate in the catalyst reoxidation stage
150 °C to give a mixture of isopropanol and acetone in 42% and 52% selectiv
5.2 where dioxygen is reduced in a four-electron redox reaction. However, the
ity, respectively (eq. 5.3).
above kinetic evidence may not be sufficient to support the p-peroxo catalyst
intermediate.
C3H 8 + 0 2 -► CH3CH(OH)CH3 + CH 3COCH3 (5.3) Oxidation of 2-methylnaphthalene to quinone (eq. 5.6) is a step of the
vitamin K 3 synthesis. In industry it is carried out with highly toxic C r 0 3 as a
The mixed-addenda HPA-n are more efficient catalysts than the all-molyb stoichiometric oxidant with a low yield (ca. 50%). With HPA-n, it occurs
denum heteropoly anions. catalytically in AcOH - H20 solution at 120-140°C with 82% selectivity at
Other types of polyoxometalates are also active in alkane oxidation, for 78% conversion.1431
example, a trisubstituted Keggin anion [PW9Fe2N i0 37]7 -.1351 As shown by
Mizuno et a/.,1361 this polyanion also catalyses the oxidation of cyclohexane, o
adamantane, cyclohexene, and ethylbenzene. The dimanganese(III) anion
[SiWio03gMn2]6- is efficient in the oxidation of cyclohexane with 0 2.[371 N eu
+ h 2o (5.6)
mann et a/.138,391 reported that the Ru(III)-substituted sandwich type polyanion,
[(WZnRu2)(0 H)(H20 )(ZnW90 34)2]ll_ , catalyses the hydroxylation of alkanes
by 0 2. o
The HPA-n anions stoichiometrically oxidise methylbenzenes in acetic acid
solution to form mixtures of aromatic alcohols, aldehydes, and di-and poly- Gorodetskaya et al.l44] reported the oxidative bromination of a range of
arylmethanes (eq. 5.4).[401 In the presence of 0 2, the reaction occurs catalyti- aromatic compounds catalysed by HPA-n with HBr as a brominating agent
and O2 as a terminal oxidant. Neumann et al.[45] reported the oxidative bromi- 16% of isobutyraldehyde is used to form cyclooctanol and cyclooctanone, 72%
nation of phenols in the para-position (eq. 5.7) in a homogeneous HPA-2/ is oxidised to isobutyric acid without oxidation of cyclooctane, and 12% is
CH 2ClCH2CTtetraglyme system with a remarkably high 99% yield (20 C, 5 h). decomposed to acetone and C 0 2. A free radical mechanism is suggested with
acyl peroxo radicals as active oxidising intermediates (Scheme 5.1).
OH OH
RCHO
+ HBr + y202 + h 2o (5.7)
P O M /O ,
Br
V * RCOOH + C -R
The antimony-substituted Keggin polyoxomolybdate [P M o u C ^S b 111]4- has •o
been synthesised and used as a catalyst for aerobic oxidation of benzylic OH
alcohols to aldehydes.1461
Ishii et a/.*471 have studied a number of oxidations with O2 in the presence of C 0 2 + R*
an aldehyde, e.g., 2-methylpropanal, as a sacrificial reductant and (NH4)5
H4[PM o6V604 o] as a catalyst in dichloroethane solution. The addition of R’H O O RCOOH + O,
aldehydes is a well-known method to promote the liquid-phase free radical R’OH
oxidation of organic compounds by 0 2. Many metal complexes, such as O'A "o-o> *
Co(III), Mn(III), Cu(II), Fe(III), etc., can initiate such reactions.*481 The alde R’OH + RCOOH
hyde-initiated epoxidation of olefins proceeds at 25 °C with a very high select
ivity of 81-100% (eq. 5.8). A carboxylic acid as a co-oxidation product from Scheme 5.1
the aldehyde is also formed. In addition, the Baeyer-Villiger oxidation of cyclic
ketones to lactones was accomplished with 78-87 % selectivity using benzalde- When H 5[PM oioV204 o] supported on MCM-41 is used, the co-oxidation
hyde as the sacrificial aldehyde (25 °C, 20 h, 1 atm O2). These reactions may be occurs similarly, although with a lower catalytic activity.*531
synthetically useful if the carboxylic acid is a useful product, provided a less A variety of oxygenates, e.g., aldehydes, ketones, phenols, etc., can be
harmful solvent instead of CH 2CICH2CI is employed. oxidised with HPA-n under mild conditions with very good yields. Bregeault
et alP 4] reported the oxidative cleavage of cyclic ketones. For example, the
cleavage of 2-methylcyclohexanone is catalysed by HPA-4 in aqueous solution
> = < 0 i/R C H ° . )& < _ + RCOOH (5.81 to yield 97 % of ketoacid (60 °C, 8 h) (eq. 5.9).
o
Mizuno et a/.*491 reported that the selective epoxidation o f olefins by O2 in
the presence of an aldehyde is also catalysed at 25 °C by transition metal- (5.9)
substituted 12-tungstophosphates [P W n C ^ M f- , where M = Co(II), Mn(II), +o
Fe(III), Cu(II) or Ni(II), whose activity decreases in that order. The order of
the effectiveness of the aldehydes is: pivalaldehyde > isobutyraldehyde »
butyraldehyde > acetaldehyde > valeraldehyde > benzaldehyde. The catalytic HPA-n-catalysed oxidation of cyclohexanone to adipic acid was studied as an
activity of polyoxometalates is solvent dependent. Thus the activity of alternative to the industrial nitric acid oxidation.*541 The reaction was found to
[PW11O39C0]5 decreases in the series: CHCI3 > CH2C12 > 1,2-C2H4C12 > be solvent-dependent, aqueous acetic acid being the best solvent, yielding 50%
CH 3CN > C6H 6 > D M F > DMSO. There is evidence that the POM-catalysed adipic acid together with 19% glutaric and 3 % succinic acids at 99% cyclohex
co-oxidative epoxidation o f olefins with 0 2 in the presence of aldehyde pro anone conversion (HPA-4, 1 atm 0 2, 70 CC, 7h). Adipic acid was found to be
ceeds by a radical chain mechanism.147,50,511 stable to degradation by the H PA -n/02 system. This system has the advantage
The co-oxidation of alkanes and isobutyraldehyde with oxygen in the pres over the nitric acid oxidation of being less corrosive and no nitric oxides evolve.
ence of H 5[PM o , oV204 o] has been shown to occur with a significant nonpro However, the selectivity to adipic acid is still not high enough for practical
ductive oxidation of aldehyde.1521 Thus in the oxidation of cyclooctane only application.
124 CATALYSIS BY POLYOXOMKTALATES POLYOXOMETALATES AS CATALYSTS FOR SELECTIVE OXIDATION 125
Ishii et alP7] studied the oxidation of aldehydes to carboxylic acids with the Step 5.13 involving the formation of the phenoxyl radical is probably rate-
use of the NH4+ salt of HPA-6 as a catalyst (eq. 5.10). The reaction proceeds limiting. Subsequent transformations of the phenoxyl radical give TMBQ via
under very mild conditions (25 °C, 1 h) in dichloroethane with 96-100% select HMBP and HMDQ. V 0 2+ either interacts with HPA-n by electron transfer
ivity at 60 78% aldehyde conversion. (eq. 5.15) or enters the lacunary species H P A -(n -l) (eq. 5.16) to form the
reduced heteropoly anion H(HPA-n). Eventually, H(HPA-n) is oxidised by
RCHO + y20 2 -* RCOOH (5.10) 0 2 (eq. 5.17) by a multielectron-transfer mechanism which will be discussed
later. It should be noted that the free V 0 2+ ion is not oxidised by 0 2 in acidic
Kholdeeva et a/.1561 and Neumann et alP 71 reported the oxidation of alkyl- solution.
phenols by HPA-n. The oxidation of 2,3,5-trimethylphenol (TMP) to tri- Interestingly, the tungsten analogues of HPA-n, [PWi2..nVnO]4of3+n)“ , which
methylbenzoquinone (TMBQ) (eq. 5.11) is of practical interest as a step to are much less labile than [PMoi2_nVnO]4(/ 3+n)- in aqueous solution,1581 show
synthesise vitamin E. This reaction yields TMBQ with 86% selectivity at 100% a very low activity in the oxidation of TM P1561 as well as in some other
TMP conversion (HPA-4, A cO H -H20 , 50°C).[56] reactions, for example, oxidation of H 2S.t59] A possible reason for this is that
in the case of {PW]2_nVn}, reactions 5.12 and 5.16 are too slow.
The oxidation of sterically hindered phenols to benzoquinones with oxygen
catalysed by manganese(II) complexes of heteropolytungstates has been investi
gated.1601
The oxidative coupling of 2,6-dialkylphenols to diphenoquinones (eq. 5.18)
catalysed by copper amine complexes is used for the synthesis of antioxidants. In
this reaction, HPA-n shows a higher activity than copper complexes. The oxida
tive coupling proceeds in H 20 , AcOH - H20 , or MeOH - H20 as solvents at
25-50 °C and under 0 2 pressure of 1-5 atm. Diphenoquinones, insoluble under
2,2/,3,3'.6,6'-Hexamethyl-4,4'-bisphenol (HMBP), the product of the oxidative these conditions, can be readily isolated from the reaction mixture by crystallisa
coupling of TMP, is also formed under these conditions. The product selectivity tion. Thus, 2,2',6,6'-tetramethyl- and 2,2',6,6/-tetra-r-butyl-diphenoquinones
depends on the water concentration in the reaction mixture. With [H20] are obtained in a nearly 100% yield. The catalyst can be recycled without loss
increasing, the yield of HMBP increases at the expense of TMBQ. The of its activity.1611
HMBP itself undergoes oxidative conversion into TMBQ via the intermediate
formation of hexamethyldiphenoquinone (HMDQ). Evidence has been OH
obtained that the oxidation occurs by the V 0 2+ ions which form as a result
of dissociation of HPA-n. A mechanism has been proposed involving the one- + o2 --------- - o
electron oxidation of TMP by V 0 2+ followed by the oxidation of vanadiu-
m(IV) to vanadium(Y) by oxygen inside of HPA-n1561 (eq. 5.12-5.17, where
ArOH stands for TMP).
Oxidation of sulfur compounds with oxygen can be efficiently carried out
HPA-n i± V 0 2+ + HPA-(n - 1) (5.12) with HPA-n. For example, the oxidation of H2S to sulfur1621 and thioethers to
sulfoxides and sulfones1631 proceed with nearly 100% yield.
V 0 2+ + ArOH + H + ------- * ArO’ + V 0 2+ + H 20 (5.13)
slow
h 2s + '/2o 2 — s + h 2o (5.19)
2 ArO* -+ HMBP -+ HM DQ -►TMBQ (5.14)
2 RSH + % 0 2 — RSSR + H20 (5.20)
V 0 2+ + HPA-n + H 20 ? i V 02+ + H(HPA-n) + H + (5.15)
R2S + lA 0 2 - h. r 2s o (5.21)
R 2 SO + V2 O 2 ^ R 2S 0 2 (5.22)
V 0 2+ + HPA-(n - 1) + H + ^ H(HPA-n) (5.16)

The HPA-n-catalysed oxidation of diethyl sulfide with 180? in
4 H(HPA-n) + 0 2 4 HPA-n + 2 H20 (5.17) CH 3C 160 2H - H 2160 solution at 96 °C leads to the incorporation of 44-54%
180 in the product sulfoxide. The process is accompanied by isotope exchange of As such, this method allows producing a paper quality bleached pulp and is
dioxvgen. On these bases, a radical mechanism (Scheme 5.2) is suggested.^ claimed to be an effective alternative to the chlorine bleaching. Evtuguin
et al.[681 have studied in detail the one-step delignification by 0 2/HPA-n system.
R;S + {PMol2.nVvnO40} --------- ► R2S+ + {pMo12.nVvn.,Vlv0 4o} Two-component system HPA-n + Pd(H) The two-component redox system
slow HPA-n + Pd(II)[1] has attracted considerable attention. A wide variety of
stoichiometric oxidations of organic compounds (RH 2), e.g., olefins, alcohols,
arenes, etc., by Pd(II) can be carried out catalytically with the use of HPA-n as
R2S+ + H2160 [(R,S)+ 16O H ] + H+
a cocatalyst and O2 as an oxidant[2,7' 10,2I’69] (eq. 5.24).
[(R2S)+ 16OH'] + I80 2 ------- ^ 1(r 2S -l8°2)+ I6o h -]

R H 2 + '/2 0 2 — P + H 20 (5.24)
‘jo. Generally, such reactions proceed via a stepwise redox mechanism (Scheme
[<R,S -180 ,) + 160H ] + {P M o ^ V ^ O « } ------- - R2S< 180 + H+ + {PMo12.nV vn.iViVO40} 5.3).[2,10’21] It is analogous to the Wacker-type oxidation with Q 1CI2 - PdCl2 as
18q
the catalyst. But the HPA-n + Pd(II) catalyst can work in the absence of or at a
very low concentration of C L ions. Consequently, this redox system has the
advantage of being higher selective and less corrosive.[1,21]
R2S<j iso ------ - R,SlsO + 160 180 or R,Sl60 + 180 2
"o '
RH2x / Pd(II) / H2(HPA-n) . 1/2 0 ,
4 {PMo^ v V jV1^ } + 0 2 + 4 H+ ------ - 4 {PMo12.nVvnO40} + 2 H20
Scheme 5.2
Pd(0) HPA-n H ,0
Harrup and Hill[651 have reported POM-based catalyst systems - [PWu
0 39Z n ]^ [ S iW „ 039]8“ JS iW ii039Zn]6-,[N a P 5W 3oOiio]14~,_etc. - for the se
lective aerobic oxidation of H 2S in aqueous solution to yield a high purity Scheme 5.3
(>99.5 %) sulfur. Selective oxidation of tetrahydrothiophene to the correspond
ing sulfoxide by O2 is achieved in high selectivity (>99% ) at 95 °C in the M ost interesting is the application of the HPA-n + Pd(II) system for the
presence of HPA-2 as a catalyst.[66] Wacker-type oxidation of olefins (eq. 5.25):
Another interesting field is the application of HPA-n redox catalysis for
environmentally benign delignifying wood pulp.[67] Lignin - a complex polymer RCH = CH2 + Vi 0 2 -* RCOCH3 (5.25)
derived from aromatic alcohols - is, besides cellulose, one of the main constitu
ents of wood. Delignification is a step in manufacturing paper. Currently, it The Wacker process is industrially employed for manufacturing acetaldehyde
is typically done by treatment of the pulp by chlorine, which poses a great from ethylene, the CuCl2 + PdCL redox system being used as a catalyst.[70]
environmental concern. Weinstock, Hill et a l have developed a new method However, this process has several drawbacks such as formation of chlorinated
of removing residual lignin from wood pulp by a two-step process involving the byproducts and strong corrosion of the reaction vessel. So the development of
oxidative degradation of lignin by polyoxometalates, e.g., HPA-2, followed by chloride-free oxidants to replace CuCl2 has long been a challenge. Mat-
separation of bleached pulp and reoxidation of the reduced polyoxometalate by veev[1,20,7l] first used HPA-n as a chloride-free oxidant in the Wacker reaction.
a nonpolluting oxidant, such as air, O2, H20 2, etc. The process can be repre The oxidation of ethylene can be represented by equations 5.26-5.28.
sented by equations 5.1 and 5.2 where Red is now the pulp and Ox is the
bleached pulp. The net reaction is the selective oxidative removal of lignin from C2H4 + Pd(II) + H 20 CH 3CHO + Pd(0) + 2 H + (5.26)
wood yielding only high quality cellulose, CO2 and H 20 : Pd(0) + HPA-n + 2 H + -> Pd(II) + H 2(HPA-n) (5.27)
Wood (cellulose + lignin) + 0 2 -> cellulose + CO2 + H 20 (5.23) H 2(HPA-n) + % 0 2 -> HPA-n + H20 (5.28)
Later on, Catalytica32’3 has developed a new technology for the Wacker Passoni et a lP 5h^ reported the oxidation of benzene to phenol by 0 2 catalysed
oxidation of ethylene with the use of the HPA-n + Pd(II) system. In order to by the Pd(II) + HPA-n redox system with 70% selectivity at 15% benzene
enhance the reaction rate and stabilise Pd(II) in solution, the reaction is yet conversion and 800 Pd(II) turnovers (130 C, 60 atm 0 2, in AcOH - H20).
carried out in the presence of Cl- ions, but at a very low concentration, much
low?er than in the conventional Wacker process (Table 5.1). In the Catalytica’s OH
process, over 99 % of the production of chlorinated by products is eliminated,
decreasing to less than 0.01% yield on ethylene. The practical production of y2o 2
aqueous HPA-n for use at large scale as well as in the laboratory and the
reoxidation of aqueous reduced HPA-n by 0 2 has been described,3723 There is
no evidence of commercial use of this process, however. When H 3ITM09V3O40] supported on MCM-41 is used as a catalyst for this
Other homogeneous oxidations catalysed by the HPA-n + Pd(II) system reaction, the heteropoly acid leaches from the support, and the reaction occurs
have been reported. These include the acetoxylation of ethylene to vinyl acetate homogeneously.37503
and of propylene to allyl and propenyl acetates,3733 the oxidation of primary
and secondary alcohols,3743 the acetoxylation,375*3 hydroxylation375b,c3 and oxi Multicomponent systems Three-component redox system, including HPA-n,
dative coupling1763 of aromatic compounds, and the arylation of olefins3773 (eq. hydroquinone (HQ) and Pd(II), was found to be an efficient homogeneous
5.29-5.34). catalyst for Wacker-type oxidation of alkenes.378,793 In this system, HPA-n
smoothly oxidises HQ to benzoquinone; the latter rapidly oxidises Pd(0) to
CH2 = CH2 + HOAc + % 0 2 ------> CH 2 = CHOAc + H 20 (5.29) Pd(II), thus greatly enhancing the overall reaction rate. Addition of Cu(II) to
the HPA-n -I- Pd(II) redox system can also benefit Wacker-type oxidation.380,813
CH2 = CH-CH3 + HOAc + V20 2 ---- ►CH2 = CH-CH2OA c + H 20 (5.30) Pd(II) -I- HPA-n is an efficient homogeneous catalyst for the oxidative coupling
of arenes (eq. 5.33) which is a useful route to the synthesis of biphenyl deriva
RR'CHOH + Vi 0 2 ------►RR 'C H O + HzO (5.31) tives (for a review, see3823). Hg(II) is often employed as a promoter in the
coupling of alkylbenzenes to improve the activity and selectivity to 4,4'-
OAc
isomers. The oxidative coupling of methyl benzoate catalysed by Pd(OAc)2+
(5-32) HPA-n, yielding 2,2'-biphenic acid dimethyl ester with unusually high selectiv
II + HOAc + l/202 I + h 2o ity (80%), has been reported.3833 An ortho cyclopalladated intermediate is
suggested to be responsible for this. Addition of Hg(OAc)2 increased greatly
the conversion of methyl benzoate without impairing the selectivity to the 2,2'-
isomer.
2^ ) * K°2
+ c h ,= c h 2 + Y2o2 I + h 2o (5.34)
Table 5.1 Catalyst solutions for W acker oxidation o f ethylene to

acetaldehyde321].
Catalytica’s system CuCl2 + PdCl2 system 5.1.1.3 Biphasic Oxidation

Pd(II) 0.1 mM Pd(II) lOmM The advantage of biphasic systems is that they combine a catalytic reaction and
Cl" 5-25 mM Cl" 2M product separation in one unit, which allows avoiding difficult separation
[P M 0 1 0 V 2 O 40 ]5' 0.3 M CuCl2 1M problem. Like in acid catalysis discussed in Chapter 4, polyoxometalates can
be profitably used as catalysts for selective oxidation in biphasic systems.
M a tv eev et n / / 841 rep orted tw o -sta g e o x id a tio n o f 2 -m eth y l-1 -n a p h th o l to R e a ctio n 5.39 p roceed s via the o x id a tiv e d eh y d ro g en a tio n o f benzyl am in e to
m en a d io n e in a high yield (eqs 5.35 and 5.36). S tep 5.35 is carried o u t in a im in e, A rC H = N H , fo llo w ed by the h y d ro ly sis o f th e im in e to form benzalde-
w ater-h y d ro ca rb o n b ip h asic system at 50 °C w ith 89% yield o f m e n a d io n e at h y d e, an d , fin ally, the in tera ctio n betw een the benzyl am in e and b en za ld eh y d e
a 100% n a p h th o l c o n v ersio n . T h is is a p ro m isin g altern ative to the c o n v e n yield s a S ch iff-b ase.
tio n a l sy n th esis o f vitam in K 3 by o x id isin g 2 -m eth y ln a p h th a len e w ith C r 0 3.
2 -M e th y l-l-n a p h th o l can be p rod u ced in a high y ield b y a h e te ro g e n e o u sly A r C H 2O H + % 0 2 A r C H O + H 20 (5 .3 8 )
cata ly sed g a s-p h a se a lk y la tio n o f n ap h th a len e by m eth a n o l.
A r C H 2N H 2 + 0 2 — A r C H = N C H 2A r (5 .3 9 )
OH
Ja n sen t891 ap p lied H P A -n (n = 2, 3) su p p o rted o n a v ariety o f ch em ica lly
m o d ified ca rb o n su p p o rts a s ca ta ly sts fo r th e o x id a tio n o f T M P to T M B Q (eq.
m/4 + HPA-n + m/4 H20 m/4 + H m(H P A -n )
5.1 1 ) in p o la r m ed ia.
Ish ii et a / / 901 stu d ied the aero b ic o x id a tio n o f v a rio u s o rg a n ic c o m p o u n d s
ca ta ly sed by a ca rb o n -su p p o rted (1 0 % ) N H / salt o f H P A -n w ith an average
(5 .3 5 ) c o m p o sitio n o f ( N H ^ H ö f P M o ^ g C ^ o ] . T h is ca ta ly st sh o w s high ca ta ly tic
activ ity for th e o x id a tiv e d e h y d ro g e n a tio n o f b en zy lic and ally lic a lco h o ls to
H m(H P A -n ) + m / 4 0 2 -► H P A -n + m / 2 H 20 (5 .3 6 ) th e co rresp o n d in g a ld eh yd es a n d k e to n e s (4 6 -9 2 % y ield ) in to lu en e. T h e
ca ta ly st can be recycled w ith o u t lo ss o f its a ctiv ity . In co n tra st, the u n su p p o rted
K o zh ev n ik o v et a / / 851 h ave d ev elo p ed th e efficien t o n e -sta g e o x id a tio n o f ca ta ly st is in active fo r th ese o x id a tio n s. T h e en h a n cem en t o f ca ta ly tic a ctiv ity
T M P to T M B Q w ith 84% yield at a 100% T M P c o n v e rsio n in a tw o -p h a se b y su p p o rtin g th e h e te ro p o ly salt o n the a ctiv e ca rb o n is believed to be the
system at 50 °C and 1 atm 0 2 pressu re (eq. 5.11). T h e ca ta ly st (low er) p h a se is an resu lt o f an in crease in c o n c en tra tio n o f su b strate an d o x y g e n du e to their
H P A -4 so lu tio n in A cO H - H 20 . T h e u p p er p h ase is a T M P + T M B Q so lu tio n a d so rp tio n in th e vicin ity o f th e a ctiv e site. In a d d itio n , the a ctiv e ca rb o n co u ld
in a h y d ro ca rb o n so lv en t, e.g ., h ep tan e, b en zen e, etc. T h e o x id a tio n o f 2, be a g o o d m e d ia to r o f th e e lectro n transfer in red o x step s in v o lv ed in the
6 -d ia lk y lp h en o ls to 2 ,6 -d ia lk y l-1 ,4 -b en zo q u in o n es b y o x y g e n c a ta ly sed by c a ta ly tic p ro cess. It sh o u ld b e n o te d , th a t the su p p o rted ca ta ly st h a s a large
H P A -n in b ip h a sic w a ter-organ ic system s h as b een r e p o r te d /86’871 M o n flie r et su rface area co m p a red to th e b u lk h e te ro p o ly salt, w h ich m a y b e a reason for
a / / 801 reported the b ip h asic W ack er o x id a tio n o f 1-d ecen e to 2 -d e c a n o n e at 80 °C th e greater a ctiv ity o f th e su p p o rted sy stem . O ther aero b ic o x id a tio n s, su ch as
w ith ex cellen t yield (98% ) an d p ra ctically n o d o u b le b o n d m ig ra tio n (eq . 5.37). th e o x id a tio n o f p h en o ls an d a m in es, w ere a lso e x a m in e d /901 In the ca se o f
rea ctio n s in p o la r m ed ia a sig n ifica n t lea ch in g o f p o ly o x o m e ta la te from the
a c tiv e c a rb o n w as o b served . T h u s in the o x id a tio n o f T M P to T M B Q (eq. 5 .11)
in A c 0 H - H 20 , 7 % o f P O M su p p o rted o n a ctiv e ca rb o n d isso lv ed from the
+ k2^2
o
su p p o rt, w h ic h c o u ld g ive rise to h o m o g e n e o u s ly ca ta ly sed reaction . A lth o u g h
(5 .3 7 ) th e recycled ca ta ly st sh o w e d a lm o st th e sa m e p erfo rm a n ce as the origin al on e,
th e h o m o g e n e o u s reaction c o u ld n o t be ruled o u t. T h e b est w a y to exa m in e the
In th is ca se, the ca ta ly st (low er) p h a se is a th r e e-c o m p o n e n t system , c o n ta in in g role o f h o m o g e n e o u s ca ta ly sis w o u ld be to filter o f f the ca ta ly st at the reaction
P d (II), H P A -6 and C u (II) in an a q u eo u s so lu tio n , w h ere C u (II) is su g g ested to tem p eratu re an d test o u t the filtrate.
p ro m o te the P d (O ) reo x id a tio n . ß -C y clo d ex trin as a p h a se-tran sfer c a ta ly st is T h e h e te ro p o ly acid H 5[P M o i 0V 20 4 o] d ep o sited o n c o tto n clo th , p olyacrylic
u sed to transfer 1-decene to th e a q u eo u s p h ase b y a h o st-g u e st in tera ctio n . fibre, n y lo n fibre, or carb on p o w d er has b een used as a ca ta ly st for a erob ic
H o w ev er, n o ev id en ce o f th e in tegrity o f ß -cyclod extrin d u rin g the r ea ctio n liq u id -p h a se o x id a tio n o f a ceta ld eh y d e, 1 -p ro p a n eth io l, and tetrah yd ro-
co u rse is provid ed . t h io p h e n e /911
5.1.1.4 Heterogeneously Catalysed Oxidation 5.1.1.5 Mechanism

N eu m a n n et a / / 881 rep orted th e liq u id -p h a se o x id a tiv e d eh y d ro g e n a tio n o f D e sp ite th e im p o rta n ce a n d versa tility o f o x id a tio n s ca ta ly sed by H P A -n , there
b en zylic a lco h o ls a n d am in es ca talysed b y ca rb o n -su p p o rted H P A -n in to lu e n e is o n ly lim ited k n o w led g e a b o u t their m ech a n ism . T h e state o f H P A -n in
at 1 0 0 °C w ith ex cellen t yield s (9 4 -1 0 0 % ). T h e o x id a tio n o f b en z y lic a lc o h o ls to so lu tio n is extrem ely co m p lex , a n d the h igh er th e n valu e, the m o re c o m p lex
b en za ld eh y d es (eq. 5 .38) p roceed s w ith o u t o v e ro x id a tio n to c a rb o x y lic acid s. th e system . T h ese so lu tio n s co n ta in a great nu m b er o f p o ly a n io n s, their
p o s itio n a l iso m ers as w ell as m o n o m e r ic m e ta llo sp e c ie s.*2,10'2’ 1 F ig u re 5.1 sh o w s A s sta te d earlier, th e overa ll c a ta ly tic p ro cess ca n be rep resen ted sc h e m a tic
the 31P N M R sp ectru m for H P A -4 a q u e o u s s o lu tio n , w h ic h w a s u sed as th e a lly b y ste p s 5.1 a n d 5.2. T h e q u e s tio n is w h a t is th e m e ch a n ism o f th ese steps?
ca ta ly st fo r th e o x id a tio n o f T M P to T M B Q .[851 A s ca n b e seen , th is sy stem W h a t k in d o f a c tiv e sp ec ies is in v o lv ed ? In ste p 5 .1 , tw o ty p es o f a ctiv e sp ecies
c o n ta in s h e te ro p o ly a n io n s w ith o n e , tw o , th ree, a n d fo u r v a n a d iu m io n s. ca n b e c o n sid e r ed - th e m o n o m e r ic V 0 2^ c a tio n (a n d /o r c o m p le x e s th ereo f)
M o re o v er , each ty p e is rep resen ted b y an array o f p o s itio n a l iso m ers. S u ch a a n d h e te r o p o ly a n io n s .[2] T h e V 0 2 + c a tio n ca n b e fo rm ed b y d iss o c ia tio n o f
c o m p lex ity m a k e s m e ch a n istic stu d ies very d ifficu lt. M u ch w o r k o n th e c h a r p aren t H P A -n (eq . 5 .1 2 ). T h is is lik ely to o c cu r for H P A -n w ith h ig h er n and in
a cterisa tio n o f H P A -n so lu tio n s w a s d o n e in th e 1960—80s b y S o u c h a y ,[92'93] str o n g ly a c id ic m ed ia . T h ere is ev id en ce th a t V 0 2+ is th e a c tiv e sp ecies in the
P o p e ,1941 M a tv e e v t1-21 and co -w o rk er s. M o re recen tly P ette rsso n et al.[95] have o x id a tio n o f T M P to T M B Q (eq s 5 .1 2 -5 .1 7 ) .[56] R e ce n t c a lo r im e tr ic stu d y 1961
fu lly ch a ra cterised H P A -2 in a q u e o u s so lu tio n by c o m b in e d p o te n tio m e tr y an d sh o w s th a t in H P A -n s o lu tio n s, V 0 2+ in th e o u te r sp h ere red u ces first, fo llo w e d
31P a n d 31V N M R tech n iq u es. T h is sy stem , w h ich is relev a n t to th e C a ta ly tic a ’s b y r ed u c tio n o f V 5+ in sid e p o ly a n io n .
te c h n o lo g y fo r the W a ck er o x id a tio n o f o le fin s ,1211 c o n sists o f fiv e p o s itio n a l a - T h e p a ren t h e te r o p o ly a n io n s m a y a lso be th e a c tiv e sp ec ies in ste p 5 .1 .[2]
iso m ers a n d so m e ß -iso m e r s o f [P M 010V 2O 40]5“ . T h is is lik ely in th e ca se o f m o re sta b le p o ly a n io n s w ith few er V 5+ io n s su ch as
H P A -2 . S in ce th e h e te r o p o ly a n io n s are m u ltiele ctr o n o x id a n ts , th ey c o u ld , in
p rin cip le, react v ia a m u ltiele ctr o n -tr a n sfe r m e ch a n ism . In th is sen se, th e o x i
d a tio n o f a te st a lc o h o l 2 ,2 -d im e th y l-1 - p h e n y l-1 -p r o p a n o l is o f in terest1971 (eq.
PMou V
5 .4 0 ).
(5 .4 0 )
W ith tw o -e le c tr o n o x id a n ts , su ch a s P d (II), th is a lc o h o l g iv es k e to n e w ith th e

sa m e c a r b o n b a c k b o n e . W ith o n e -e le c tr o n o x id a n ts , e .g ., C e4+ o r p ersu lfa te,
th e C - C b o n d c le a v es to y ield b e n z a ld e h y d e a n d t-b u ty l ra d ica l a s th e p rim ary
p r o d u c ts (T a b le 5 .2 ). It ca n b e seen th a t V 0 2+ m a in ly rea cts as a o n e -e le ctr o n
o x id a n t, a s e x p e c te d , y ie ld in g 63 % b e n z a ld e h y d e. In c o n tr a st, H P A -6 p r e d o m
in a n tly r ea c ts as a tw o -e le c tr o n o x id a n t, g iv in g th e k e to n e in 6 7 % yield .
S im u lta n e o u sly so m e o n e -e le c tr o n o x id a tio n , p r o b a b ly b y V 0 2+ io n s, a lso
ta k e s p la c e to g iv e b e n z a ld e h y d e (3 3 %). T h e se resu lts in d ic a te a d irect in v o lv e
m e n t o f h e te r o p o ly a n io n s in rea c tio n 5 .4 0 .
E ffo r ts h a v e b een m a d e to cla rify th e m e ch a n ism o f o x id a tio n o f th e red u ced
fo r m o f H P A -n (h e te r o p o ly b lu e) b y 0 2 in so lu tio n (eq . 5 .2 ).[2,221 H o w ev er, th e
c o m p le x ity o f th e sy stem m a k e s c o n c lu s io n s rath er sp ec u la tiv e. T h e red o x
r e a c tio n s in v o lv e d in th e r ed u c tio n o f d io x y g e n in a n a c id ic a q u e o u s so lu tio n
Table 5.2 One-vs. two-electron oxidation of 2,2-dimethyl-1-phenyl-1-

propanol[97],a.
Oxidant PdCl2 Ce4+ s2o82- vo2+ HPA-6
Ketone, % 100 6 6 11 67
Figure 5.1 162MHz 31P NMR spectrum for 0.2mol l-1 Na5H2[PMo8V404o] aqueous PhCHO, % None 94 89 63 33
solution (pH 2.5, 1 % H3PO4 as external reference).1’01 Reprinted with permission from
a) Yields (mol%) on converted alcohol; a little PhCOOH is also formed
Chem. Rev. 1998, 98, 171. Copyright 1998 American Chemical Society.
Table 5.3 Reactions involved in the reduction of CL in o x id ise d fo r m H P A -n ; [H (H P A -n )]/{ [H (H P A -n )] + [H P A -n ]} < 1. U n d er such
acidic aqueous solution and the corresponding standard c o n d itio n s , th e rate o f o x id a tio n o f b lu es w a s fo u n d to be in th e order: H P A -2
reduction potentials (versus SHE, pH 0)[98].
< H P A -3 > H P A -4 > H P A -6 . In th e ca se o f th e H P A -3 b lu e, at a c o n sta n t pH
0 : + e" + H+ H 02* E = -0.05 V a n d io n ic stren g th , th e r ea c tio n is th ird -o rd er in H (H P A -n ), m in u s se c o n d -
0 ; + 2e~ + 2H+ -» H->02 E = 0.68 V ord er in H P A -n , a n d first-o rd er in 0 2.
0 2 + 4e“ + 4H+ -+ 2H20 E = 1.23 V
H 02* -f e + H+ —►H20 2 E = 1.44 V
H20 2 + e" + H+ -» HO* + H20 £ = 0.71 V Rate = ^ H ( H P A - n ) ] 3[0 2]
H20 2 + 2e~ + 2H+ 2H20 £ = 1.76 V [H P A -n ]2
HO* + e~ + H+ H20 £ = 2.81 V
T h e test w ith i-P rO H clea rly sh o w s th e fo r m a tio n o f free ra d ica ls. O n th ese
b a ses, a m e ch a n ism w a s p r o p o s e d , w h ic h is rep resen ted fo r th e H P A -3 b lu e by
to g e th er w ith th e c o r r e s p o n d in g sta n d a rd r ed o x p o te n tia ls 1981 are g iv en in T a b le eq s 5 .4 3 -5 .4 6 .
5.3. T h ese d a ta a llo w to m a k e th e r m o d y n a m ic a ssessm e n t as to h o w th e
o x id a tio n o f b lu es m a y p r o c ee d . T h e O 2 its e lf is a p o o r o n e -e le c tr o n o x id a n t. 2 { P M o 9V 25+V 4 + } { P M o 9V 5+V 24 + } + { P M o 9V 35+ } (5 .4 3 )
O n e -elec tr o n o x id a tio n o f th e red u ced H P A -n (E = 0 .7 V ) w ith 0 2 to fo r m H O j
radical is h ig h ly u n fa v o u r a b le th e r m o d y n a m ic a lly . H o w e v e r tw o -, th r e e-o r { P M o 9V 5+V 24+} + { P M o 9V 25+V 4 + } { P M o 9V 34 + } + { P M o 9V 35 +} (5 .4 4 )
fo u r-electro n o x id a tio n s are fea sib le. C o n se q u e n tly , th e H P A -1 b lu e,
(3e-)
[P M o h V 4+ 0 4 o]4~ , is p ra ctica lly n o t o x id ise d b y 0 2 u n d er m ild c o n d itio n s in
{ P M o g V s44-} + 0 2 + 3 H + { P M o 9V 35+ } + H 20 + H O * (5 .4 5 )
s o lu tio n . T h e a ll-m o ly b d en u m H P A -0 b lu e is n o t o x id ise d eith er fo r r ea so n s slo w
th a t are n o t clea r y et. B eca u se o f th is, o n ly th e H P A -n w ith n > 1 are u sed as
{ P M o 9V 25+V 4+ } + H O * + H + -»■ { P M o 9V 35+ } + H 20 (5 .4 6 )
ca ta ly sts fo r liq u id -p h a se a ero b ic o x id a tio n s . It sh o u ld b e n o te d , h o w e v e r , th a t
the reo x id a tio n o f H P A -0 an d H P A -1 b lu es b y 0 2 p r o c ee d s rea d ily at h ig h er
In step s 5.43 an d 5 .4 4 , a th r e e-e le ctr o n b lu e is fo r m e d b y th e fa st electro n
tem p era tu res ( > 2 00 °C ) w h ich a llo w s a p p ly in g th em fo r g a s-p h a s e o x id a tio n s ,
e x c h a n g e b e tw e e n o n e -e le c tr o n b lu es. T h e n th e th r e e-e le ctr o n b lu e is slo w ly
e .g ., fo r th e o x id a tio n o f m e th a cr o lein a n d o x id a tiv e d e h y d r o g e n a tio n o f iso -
o x id is e d b y 0 2 v ia a ste p w ise tra n sfer o f th ree e le ctr o n s fr o m th e b lu e to 0 2,
b u tyric a cid , w h ich w ill be d isc u sse d later in th is ch ap ter.
a c c o m p a n ie d b y th e p r o to n a tio n o f th e o x id a n t, to fo r m H O * rad ical w h ic h is
T h e m ech a n ism o f step 5.2 w a s sh o w n to d e p e n d o n th e d eg ree o f r ed u c tio n
fin a lly tra p p ed b y a n y V 4+ sp e c ie s .11001
o f the b lu e. T h e o x id a tio n o f a d eep ly red u ced b lu e (n > 4, all th e V p resen t
T h e slo w e r rate o f o x id a tio n o f th e H P A -2 b lu e m a y b e e x p la in ed a ssu m in g
red u ced to V 4+) fo llo w s a sim p le k in etics, b e in g first-o rd er in b o th th e b lu e an d
th a t th e p r o c ess o c cu rs v ia th e s lo w d isp r o p o r tio n a tio n 2 H P A -2 ^ H P A -3 +
0 2.[991 In th e p resen ce o f a rad ical sca v en g er, i-P r O H , n o a c e to n e is fo u n d . T h is
H P A -1 , le a d in g to th e m o r e a c tiv e H P A -3 b lu e .11001 T h e lo w e r rea ctiv ity o f the
in d ica tes th a t n o free ra d ica ls are fo r m e d d u rin g th e r ea c tio n . (H o w e v e r , th e
H P A -4 a n d H P A -6 b lu es m a y b e d u e to th eir lo w sta b ility in so lu tio n .
fo r m a tio n o f sh o rt-liv ed free ra d ica ls is n o t e x clu d ed .) H e n c e a fo u r -ele ctr o n -
F u rth er, it w a s fo u n d th a t th e free ra d ica ls g e n e ra te d in ste p 5 .2 ca n , to so m e
tran sfer m ech a n ism w a s p r o p o sed , in c lu d in g th e fo r m a tio n o f a c o m p le x b e
e x te n t, a ffec t th e se lec tiv ity o f th e o n e -sta g e c a ta ly tic p r o c e s s.11011 B ut. o b v i
tw een th e b lu e a n d 0 2 fo llo w e d b y a ste p w ise fo u r -ele ctr o n tra n sfer th erein (eq .
o u s ly , th e y w ill n o t a ffe c t th e tw o -s ta g e p ro cess.
5.41 ) .1991 E ach e lectro n -tra n sfer step is p r o b a b ly a c c o m p a n ie d b y th e p r o to n a
S ev eral ty p e s o f in te rm e d ia te c o m p le x e s b etw een h e te r o p o ly b lu es a n d 0 2
tio n o f th e o x id a n t.
h a v e b een s u g g e s te d .[42,100-1021 A s H P A -n is la b ile, e a sily e x ch a n g in g o x y g e n
a to m s in th e p o ly a n io n w ith a q u e o u s s o lu tio n ,1581 K o z h e v n ik o v et fl/.11001 p r o
(40
p o s e d th e fo r m a tio n o f an a d d u ct w ith th e d irect b o n d in g o f 0 2 to th e V 4+ io n
H m(H P A -n ) + 0 2 ( H m( H P A - n ) . . . 0 2} H m. 4(H P A -n ) + 2 H 20
slo w in th e H P A -n b lu e b y in c o rp o ra tin g 0 2 in to a c o o r d in a tio n v a c a n c y a t th e V 4+
(5 .4 1 ) io n . N e u m a n n an d L e v in 1421 su g g ested a p -p er o x o in term ed ia te in v o lv in g tw o
p o ly a n io n s a n d 0 2 in th e reo x id a tio n o f H P A -2 b lu e. F o r tu n g ste n b lu es, e.g.
In c o n tr a st, th e o x id a tio n o f a w e a k ly red u ced b lu e (b y less th a n o n e e le ctr o n [S iW i20 4 o]5 - , w h ich are inert to w a r d s o x y g e n e x ch a n g e, an a ss o c ia tio n o f 0 2
per K eg g in un it) sh o w s a m ore c o m p lex k in etics.11001 T h is sy stem is a d e q u a te to w ith p o ly a n io n th r o u g h the term in a l or b rid g in g o x y g e n a to m in th e K eg g in
a real o n e -sta g e c a ta ly tic p ro cess. F o r sim p licity , it ca n b e c o n sid e r ed a s a stru ctu re, fo r m in g a n o z o n id e -ty p e a d d u c t o r a se v e n -c o o r d in a te p e r o x o m o iety
sy stem c o n sistin g o f tw o sp ecies: o n e -e le ctr o n b lu e H (H P A -n ) a n d th e fu lly w a s su g g e s te d .11021
A m e ch a n ism in v o lv in g a c o v a le n tly -b o n d e d m e ta l- o x y g e n in te rm e d ia te o r g a n ic s u b s ta n c e s b y h y d ro g e n p e r o x id e , su ch a s e p o x id a tio n o f o lefin s,

w o u ld lead to O 2 in c o r p o r a tio n in to th e p o ly a n io n . D u n c a n a n d H ill[103] q u a n ti o x id a tio n o f a lc o h o ls , g ly c o ls, p h e n o ls , e tc ., in h o m o g e n e o u s o r tw o -p h a se
fied b y 170 N M R th e in c o r p o r a tio n o f !70 fro m 17C>2 in th e o x id a tio n o f r ed u ced s y s te m s .13,8,10,12,107 1121 T h e r e is su ffic ie n t e v id e n c e th a t th e K e g g in ty p e an d
[W 10O 32]4 , [P2 W ]gO()2]6~? a n d H P A -2 in C H 3C N s o lu tio n . In th e c a se o f t u n g r ela ted p o ly a n io n s are d e c o m p o s e d b y e x c e ss h y d r o g e n p e r o x id e in so lu tio n to
sten p o ly o x o m e ta la te s , n o l70 in c o r p o r a tio n in to p o ly a n io n w a s fo u n d ; n o r d id fo rm p e r o x o ( p o ly )o x o m e ta la te sp e c ie s . T h e s e m a y be th e a c tiv e in te rm e d ia tes
170 e x c h a n g e o c c u r b e tw e en th e p o ly o x o m e ta la te s a n d s o lv e n t. A ll th e 170 is in o x id a tio n s w ith H 20 2.
fo u n d in H 2O a n d H 2O 2 th a t fo rm in th e r ea c tio n . T h e s e d a ta rule o u t th e
fo r m a tio n o f c o v a le n tly -b o n d e d m e ta l- o x y g e n in te r m e d ia te s in th e c a se o f 5 .1 .2 .1 V e n tu r e llo -I sh ii S y s te m
tu n g ste n h e te r o p o ly b lu es a n d are c o n s is te n t w ith a n o u te r sp h e re e le c tr o n
tra n sfer b e tw e en O 2 a n d th e b l u e s t 1035 S u c h a m e c h a n is m is, in d e e d , lik ely V e n tu r e llo a n d Ish ii in d e p e n d e n tly d e v e lo p e d t w o h ig h ly e ffe c tiv e c a ta ly s t
fro m th e th e r m o d y n a m ic p o in t o f v ie w fo r th e a n io n s su ch a s [H 2W i 20 4 o]6~ , sy s te m s b a s e d o n p o ly o x o m e t a la t e s fo r h y d r o p e r o x id e o x id a tio n , e sp e c ia lly

fo r th e e p o x id a tio n o f a lk e n e s. L a ter o n , it w a s f o u n d th a t th e se sy s te m s w ere
[W 10O 32]4 - , [S iW i20 4o]4 _ , e tc ., h a v in g th e r e d o x p o te n tia l E ~ 0 V .[102] In c o n
c lo s e ly r ela ted m e c h a n is tic a lly a n d in c lu d e d th e sa m e p e r o x o p o ly o x o m e ta la te
tra st, th e m e c h a n ism fo r H P A -2 is n o t a s cle a r a s th a t fo r tu n g s te n p o ly a n io n s .
a s a c tiv e in te r m e d ia te .
F o r H P A -2 , th e 170 in c o r p o r a tio n w a s m e a su r e d in th e H P A - 2 - c a t a ly s e d o x id a
tio n o f 1 ,3 -c y c lo h e x a d ie n e w ith 170 2. In th is sy s te m , s o m e 170 d id in c o r p o r a te
in to th e P O M as w e ll as th e 170 e x c h a n g e b e tw e e n th e p o ly a n io n a n d s o lv e n t
E p o x id a tio n o f a lk e n e s V e n tu r e llo et al.}[109,113,114] p erfo rm ed th e e p o x id a tio n
o f a lk e n e s (eq . 5 .4 7 ) in a b ip h a s ic sy s te m , e .g ., C H C 13 - H 20 , a t 6 0 - 7 0 °C w ith
to o k p la c e. T h e to ta l e n r ic h m e n t o f p o ly a n io n r e p r e se n te d 6 % o f a ll 170 p r o d
th e u se o f d ilu te H 2O 2 ( 2 - 1 5 % ) a n d tu n g sta te a n d p h o s p h a te io n s a s c a ta ly s t
u cts. K in e tic m e a su r e m e n ts in d ic a te d th a t th e 170 e n r ic h m e n t m a in ly o c c u r r e d
p r e cu rso rs in th e p r e se n c e o f a p h a se -tr a n sfe r c a ta ly s t - q u a ter n a r y a m m o n iu m
b y th e 170 e x c h a n g e b e tw e e n th e p r o d u c t H ^ O a n d p o ly a n io n . T h e s e d a ta , t o o ,
c a tio n (Q + ) w ith C ö - Q 8 a lk y l g r o u p s .
m a y b e c o n sid e r e d as in c o n s is te n t w ith a c o v a le n t - b o n d e d m e t a l - o x y g e n in ter-
m e d ia te .[1031 H o w e v e r , i f th e o x id a t io n in q u e s tio n w e re a r a d ic a l c h a in p r o c e s s ,
R C H = C H 2 + H 20 2 --------------- RCH — ^C H , + H 20 ^
r e a c tio n s 5.1 a n d 5 .2 c o u ld p la y o n ly a m in o r r o le in th e o v e r a ll O 2 c o n s u m p t io n .
In th is c a se , in d e e d , th e 170 e x c h a n g e b e tw e e n th e p o ly a n io n a n d th e p r o d u c t
H 2 ,70 w o u ld c o n tr ib u te th e m o s t to th e 170 e n r ic h m e n t o f P O M r e g a r d le s s o f
th e m e c h a n is m o f r e a c tio n 5.2. In th is sy s te m , a p e r o x o p o ly o x o m e t a la t e , { P 0 4[ W 0 ( 0 2)2]4 } 3~ , a n a lo g o u s
K o z h e v n ik o v a n d K h o ld e e v a t,04] h a v e s tu d ie d th e k in e tic s o f a n u m b e r o f to th e m o ly b d e n u m p e r o x o p o ly a n io n first r e p o r te d b y B e ile s et ö /.,[115] w as
o n e -e le c tr o n r e a c tio n s b e tw e e n t u n g s te n h e te r o p o ly a n io n s a n d v a r io u s red u c - is o la te d a n d c h a r a c te r is e d .1109] T h is p e r o x o c o m p le x w a s f o u n d to b e rem a r k
ta n ts o r o x id a n ts , in c lu d in g th e o x id a t io n o f [S iW i2C>4o]5~ a n d [PW12O40]4- a b ly e ffe c tiv e in s to ic h io m e tr ic a s w e ll a s in c a ta ly tic b ip h a sic o x id a tio n o f
b lu es w ith O 2, b y a s t o p p e d - f lo w te c h n iq u e . T h e r e a c tio n r a tes w e r e f o u n d to b e a lk e n e s b y H 20 2 a n d w a s p o s t u la t e d to b e th e a c tiv e o x y g e n tr a n sfe r a g e n t in
in g o o d a g r e e m e n t w ith th e M a r c u s th e o r y fo r o u te r s p h e r e e le c tr o n tr a n sfe r r e a c tio n 5 .4 7 . F o r e x a m p le , th e e p o x id a t io n o f 1 - o c te n e w ith 1 5 % H 20 2 in th e
(C h a p te r 2 ), w h ic h s u p p o r ts th is m e c h a n is m fo r th e o x id a t io n o f { S iW i 20 4o} p r e se n c e o f { P 0 4[W 0 (0 2 )2]4 } 3_ in a C H 2C I C H 2C I-H 2O s y s te m a ffo r d s e p o x
a n d { P W 12O 40} b lu e s b y 0 2. H is k ia a n d P a p a c o n s t a n t in o u [102] s tu d ie d th e y o c t a n e in 8 9 % y ie ld (b a s e d o n th e in itia l H 20 2) a t 1 0 0 % H 20 2 c o n v e r s io n
k in e tic s a n d m e c h a n is m o f th e o x id a t io n o f r e d u c e d t u n g s te n p o l y o x o m e t a (7 0 °C , 1.5 h ). T h e r e a c tio n is s te r e o se le c tiv e : m - 2 - h e x e n e is c o n v e r te d s o le ly
la tes, su ch a s [S iW I20 4 o]4" , [ H 2W i 2 0 4 o]6~ , a n d [P 2W i 80 6 2 ]6 - , w ith d io x y g e n .

in to th e r ä - e p o x id e , w h ile trans-l-hexene g iv e s th e /r a « s -e p o x id e .ll09] L ik e w ise ,
In c o n c lu s io n , H P A - n is th e e ffic ie n t a n d v e r s a tile c a t a ly s t sy s te m f o r o x i d i s b u t in a s tr o n g e r a c id ic m e d iu m , th e b ip h a s ic o x id a t io n o f a lk e n e s p r o d u c e s
w a te r -s o lu b le v ic in a l t m « j - g ly c o ls in 7 1 - 8 8 % y ie ld ( 6 0 - 7 0 ° C , 1 - 4 h , 2 - 4 %
in g b y 0 2. S e v e ra l p r o m is in g liq u id -p h a s e o x id a t io n p r o c e s s e s b a s e d o n th e
H 20 2, p H 1.2 - 1 .5 ) (e q . 5 .4 8 ). T h e g ly c o ls fo r m e d a re p r e se n t a lm o s t e n tire ly
H P A - n c a ta ly s is h a v e b e e n d e v e lo p e d , fo r e x a m p le , th e W a c k e r o x i d a t io n o f
in th e a q u e o u s p h a s e a n d c a n b e r e a d ily is o la te d fr o m th e r e a c tio n m ix tu r e .1 1 141
o le fin s . H o w e v e r , m a n y m e c h a n is tic d e ta ils are y e t t o b e d is c lo s e d .
R2 R> ¥ ?H
5 .1 .2 O X ID A T IO N W IT H H Y D R O G E N P E R O X ID E + H ,o , -------► R| — I— (— r3 (5 .4 8 )
R3 R4 OH R4
It h a s lo n g b een know n th a t t u n g s te n a n d m o ly b d e n u m c o m p o u n d s are
e ffic ie n t c a ta ly s ts fo r o x id a t io n s by h yd rogen p e r o x id e .[105’106] T u n g s t e n The a n io n { P 0 4[ W 0 ( 0 2) 2]4 } 3_ w as c h a r a c te r ise d c r y s ta llo g r a p h ic a lly
and m o ly b d e n u m p o ly o x o m e t a la t e s a ls o c a t a ly s e v a r io u s o x i d a t io n s of (F ig u r e 5 .2 ).ll09] It h a s th e C 2 s y m m e tr y a n d c o n s is t s o f th e c e n tr a l P 0 4
T h is salt ca ta ly ses the e p o x id a tio n o f a lk en es[116] an d a lly lic a lc o h o ls[120] w ith

H 20 2 in a b ip h a sic system u sin g C H C 13 as a so lv e n t, w h ile a , ß -u n sa tu ra ted
c a rb o x y lic acid s are read ily e p o x id ise d in w ater a t p H 6 to 7 .[121]
A c c o r d in g to a sch em a tic m ech a n ism p r o p o sed b y Ishii et a/.,[lll] the tw o -
p h a se e p o x id a tio n o f alk en es b y h y d ro g en p ero x id e in the presen ce o f
[P W i 2O 40]3~ as the ca ta ly st p recu rso r p r o ceed s as fo llo w s (F ig u re 5 .3). A n
0
H3 PW12O40 lw ; 1
o
Figure 5.3 Schematic mechanism of the phase-transfer epoxidation of olefins catalysed

by peroxo polyoxometalate.11111
a ctiv e p e r o x o p o ly o x o m e ta la te is fo r m e d in th e a q u eo u s p h a se b y in tera ctin g

th e K eg g in h e te r o p o ly a n io n w ith h y d ro g e n p ero x id e. W ith th e p h a se-tra n sfer
ag en t, Q + , th e p e r o x o p o ly o x o m e ta la te is a lm o st fu lly transferred in to th e
o r g a n ic p h a se b eca u se its Q + salt is read ily so lu b le in o rg a n ic so lv e n ts. T h e
rea c tio n tak es p la ce p referen tia lly in the o rg a n ic p h a se via th e o x y g e n a to m
Figure 5.2 The structure of peroxo polyanion {PC^fWCKCh^L}3-:1-1091 (a) ball- tran sfer from the p e r o x o p o ly o x o m e ta la te to th e su b strate. T h e p e r o x o p o ly
and-stick and (b) polyhedral representation. Reprinted with permission from Chem. o x o m e ta la te is th en regen erated a t th e in terface b y th e in tera ctio n w ith H 20 2.
Rev. 1998, 98, 171. Copyright 1998 American Chemical Society. H o w e v er , th e n atu re o f p e r o x o p o ly o x o m e ta la te in term ed ia tes w a s n o t esta b
lish ed in th ese stu d ies.
tetra h ed ro n lin k ed th ro u g h its o x y g e n a to m s to tw o pairs o f e d g e-sh a rin g In recen t years, the V e n tu r e llo -I sh ii ch em istry h as b een in v estig a ted in detail
d isto rted p e n ta g o n a l b ip y ra m id s W (0 2 )20 3 . E a ch tu n g ste n a to m is lin k ed to b y several g r o u p s.[126_136] T h e se stu d ies sh o w e d th a t the e p o x id a tio n o f a lk en es
tw o p e r o x o g ro u p s - o n e n o n -b r id g in g ( p 2) a n d th e o th e r b rid g in g ( p 2, p ' ) - in th e V en tu rello sy stem a n d in th e Ishii sy stem d esp ite th e use o f different
lo ca te d in the eq u a to ria l p la n e o f th e p en ta g o n a l b ip yram id . c a ta ly sts p recu rsors in clu d es n early id en tica l p e r o x o p o ly o x o m e ta la te inter
Ishii et al.[111 ’116_1251 d em o n stra ted th a t o x id a tio n s o f a w id e va riety o f o rg a n ic m ed ia tes. C sa n y i a n d J a k y [126] d e m o n stra te d th a t H 3[P W i20 4o] and
su b stra tes w ith co m m e r cia lly a v a ila b le 35 % H 20 2 can b e e ffectiv ely p erform ed H 3[PM oi20 4o] by in tera ctin g w ith e x cess H 20 2 in a tw o -p h a se sy stem in the
in h o m o g e n e o u s p h a se o r even b etter in a b ip h a sic sy stem w ith th e u se o f a p resen ce o f a p h a se-tran sfer ag en t, d e c o m p o se to fo rm a variety o f p ero x o
ca ta ly st c o m p r isin g h e te r o p o ly a cid s H 3[P W i 2C>4o] or H 3[P M o i 2C>4o] an d c o m p lex e s in clu d in g { P 0 4 [W 0 (0 2)2]4 }3 - a n d { P 0 4 [M o O (0 2)2]4 } 3~ , resp ect
cety lp y rid in iu m ch lo rid e , th e la tter p r o v id in g p h a se-tra n sfer fu n c tio n . T h e iv ely , w h ich are tran sferred in to the o rg a n ic p h a se. T h ese a u th o rs su g g ested
H 3[P W i 2O 40] c a ta ly st is u su a lly su p erior to H 3[ P M o 120 4o]. T ris-cety lp y rid in iu m th a t th e p e r o x o a n io n s derived fro m H 3[P W i20 4o] o r H 3[P M o i 20 4 o] are the
sa lt o f H 3[P W 120 4oL [n -C 5H 5N + (C H 2) 15C H 3]3[P W i20 4 o]3“ (C P W ), is p rep ared ca ta ly tica lly a ctiv e sp ecies in the b ip h a sic e p o x id a tio n o f o lefin s. B reg ea u lt et
b y in tera ctin g H 3[P W i20 4 o] w ith three e q u iv a len ts o f c e ty lp y r id in iu m ch lo rid e. a /.[127] stu d ied th e e p o x id a tio n o f 1 -o cten e b y h y d ro g en p ero x id e in the
CHCI3 - H 20 sy s te m in th e p r e se n c e o f th e h e te r o p o ly a n io n s [ X M i 2C>4o]n a n a lo g u e , Q 3 { P 0 4[ M o O ( 0 2)2]4 }.*1281 A n o th e r m e c h a n istic a lly im p o r ta n t resu lt

a n d [X 2M i 80 62r an tl is o p o ly a n io n s [M xO y]z (M = M o 6+ o r W 6+ ; X = P 5+, is th a t th e M 0 ( 0 2)2 m o ie tie s in { P 0 4[ M 0 ( 0 2)2]4 }3' are rem a rk a b ly m o b ile
Si4+, o r B 3+) as p r e cu rso rs o f c a ta ly tic a lly a c tiv e p e r o x o p o ly o x o m e ta la te s . T h e in s o lu tio n . T h u s m ix in g s o lu tio n s o f { P 0 4[ W 0 ( 0 2)2]4 }3_ a n d ( P 0 4[M o O
a n io n s [B W 120 4o]5 - [ S i W ^ O ^ ] 4 , a n d [P 2W i S0 62]6 are in a c tiv e a n d , as ( 0 2)2]4 }3” a t r o o m te m p er a tu r e resu lts in th e fa st fo r m a tio n o f m ix ed -a d d e n d a
s h o w n b y a n u m b e r o f sp e c tr o s c o p ic m e th o d s , d o n o t c h a n g e th eir stru ctu re sp ec ies { P 0 4[M o 4_ xW x0 2o] }3 - .*1291 T h u s, th e w h o le array o f p e r o x o sp ec ies
d u r in g th e r ea c tio n . [P M 0 12 O 40]3 - e x h ib its a lo w a c tiv ity . O n th e o th e r h a n d , [P W xO y]z _ (x = 1 - 4) is lik ely to e x ist in a fa st a n d v ery c o m p le x eq u ilib riu m .
[P W 120 4 o]3 e x h ib its a h ig h a c tiv ity (7 9 % y ield o f e p o x id e b a s e d o n 1 -o c te n e ) T h is m a k e s it d iffic u lt to id e n tify th e a c tiv e sp ec ies k in etica lly .
w h e n th e c a ta ly tic sy stem is p r ep a red b e fo r e h a n d b y in te r a c tin g th e h e te r o p o ly B r eg e a u lt, G e lb a r d et alP 29A30] a n d G riffith et a/.*131 1341 h a v e iso la te d a
a n io n w ith H 20 2 in a q u e o u s s o lu tio n in th e a b s e n c e o f Q + a n d 1 -o c te n e . W h e n w id e v a r ie ty o f n e w m o n o - , d i-, tri-, a n d tetra n u clea r tu n g ste n a n d m o ly b d e -
all th e r ea g e n ts are m ix ed sim u lta n e o u s ly , n o a c tiv ity is o b s e r v e d . T u n g s tic m u m p e r o x o p o ly o x o m e ta la te s w ith q 2, q 1-p e r o x o m o ie tie s a n d v a r io u s cen tra l
a c id , ‘H 2W 0 4\ a n d [H 2W I2O 42] 10_ s h o w h ig h a c tiv itie s r eg a r d less o f th e g r o u p s su ch a s P 0 4, P h P 0 3, P h 2P 0 2, S 0 4, A s 0 4, H A s 0 4, C H 3A s 0 3, etc. T h e se
p r e p a r a tio n m e th o d u s e d , th e y ie ld s b e in g 76 a n d 6 7 % , r e s p e c tiv e ly . T h e h a v e b e e n c h a r a cte rise d b y X -r a y a n d te sted in o x id a tio n s w ith H 20 2.
K e g g in h e te r o p o ly a n io n s [P W ,2O 40]3~ are d e c o m p o s e d b y e x c e s s H 20 2 Schw en dt et al. r ep o rte d th e sy n th e sis a n d c h a r a c te r isa tio n o f v a n a d iu m (V )
{ [H 20 2] /[ M ] = 3 0 - 3 5 5 m o l / m o l } to fo r m th e peroxo p o ly o x o m e t a la t e s p e r o x o c o m p le x e s ( N H 4) 5[V 20 2( 0 2)4P 0 4][I371 a n d K 7[V 40 4( 0 2)8P 0 4].['381
{ P 0 4[ M 0 ( 0 2)2]4 } 3~ and [M 20 3( 0 2)4(H 20 ) 2]2~ . It is su g g e s te d th a t B a llistreri et fl/.*1351 a n d H ill et a/.*1361 h a v e sh o w n th a t th e V e n tu r e llo -I s h ii
{ P 0 4[ M 0 ( 0 2)2]4 } 3" is th e a c tiv e s p e c ie s r e s p o n s ib le fo r th e o le fin e p o x id a tio n e p o x id a tio n is first-o r d e r in b o th { P 0 4[ W 0 ( 0 2)2]4 }3_ a n d a lk e n e . H ill et u/.*136]
w ith th e K e g g in a n io n s [ P M ^ O ^ ] 3' in tw o -p h a s e sy s te m s .[l271 o b ta in e d k in e tic a n d s p e c tr o s c o p ic e v id e n c e th a t tw o p r o c e s se s d o m in a te
L a ter o n , 31P a n d 183W N M R s tu d y 11281 s h o w e d th a t se v e ra l p e r o x o p o ly d u r in g th e rea ctio n : (i) th e s lo w e p o x id a tio n b y o x y g e n a to m tra n sfer fr o m
o x o m e ta la te s o f th e c o m p o s it io n [P W xO y]z _ (x = 1 - 4 ) fo r m in th e a q u e o u s th e p e r o x o p o ly o x o m e t a la t e to a lk e n e (eq . 5 .4 9 )
H 3[P W i 20 4 o] / H 20 2 sy s te m , a n d th e se m a y w e ll b e th e a c tiv e sp e c ie s o r th eir
p recu rso rs in th e o le fin e p o x id a t io n b y p h a se -tr a n sfe r c a ta ly s is . T h e n o v e l
{ P 0 4[ W 0 ( 0 2)2]4 } 3- + a lk e n e — P W 4, P W 3, a n d P W 2 + e p o x id e (5 .4 9 )
{ H P 0 4[ W 0 ( 0 2)2]2 } 2 - a n io n w a s stu d ied in th e c r y s ta llin e sta te a n d in s o lu tio n .
T h e c ry sta l stru ctu re o f [ ( n - B u ) 4N ] 2 { H P 0 4[ W 0 ( 0 2)2]2 } (F ig u r e 5 .4 ) is c lo s e ly
fo llo w e d b y (ii) th e ra p id r eg e n e ra tio n o f { P 0 4[ W 0 ( 0 2)2]4 } 3~ w ith H 20 2.
r ela ted to th a t o f th e V e n tu r e llo c o m p le x [ ( n - B u ) 4N ] 3{ P 0 4[ W 0 ( 0 2)2]4} (F ig u r e
C a ta ly st d e a c tiv a tio n a s w e ll a s th e u se o f c h lo r in a te d h y d r o c a r b o n s a s so lv e n ts
5 .2 ). T h e tw o a n io n s, { H P 0 4[ W 0 ( 0 2)2]2 } 2“ a n d { P 0 4[ W 0 ( 0 2)2]4 } 3“ , in c lu d e
is n o te d a s th e m a jo r d r a w b a c k to th e V e n tu r e llo -I s h ii p ro cess.* 1361
th e [W 20 2( | i - 0 2)2( 0 2) 2] m o ie ty a s a p r in c ip a l b u ild in g b lo c k . In th e tw o -p h a s e
In a lk e n e e p o x id a tio n c a ta ly s e d b y tr a n sitio n m e ta l c o m p le x e s, th e m e c h a n
e p o x id a tio n o f lim o n e n e b y H 20 2, tu n g ste n sp e c ie s Q 3{ P 0 4[ W 0 ( 0 2)2]4 } a n d
ism o f th e o x y g e n a to m tra n sfer fro m a p e r o x o c o m p le x to a lk e n e is still
Q 2 { H P 0 4[ W 0 ( 0 2)2]4 } p r o v e d to b e 30 tim es m o r e a c tiv e th a n th e m o ly b d e n u m
a m a tte r o f d e b a te . A c c o r d in g to M im o u n ,* 1391 th e m e c h a n ism o f th e o x y g e n -
to -a lk e n e tra n sfer fr o m a s id e -b o n d e d q 2-p e r o x o g r o u p in v o lv e s a p r e co
o r d in a tio n o f th e a lk e n e to th e m e ta l c en tre. A lte r n a tiv e ly , Sh arp less*1401 p r o
p o s e d a c o o r d in a tio n o f th e a lk e n e to o n e o x y g e n a to m fr o m th e p e r o x o
g r o u p , fo r m in g a th r e e-c en tre tr a n sitio n sta te . A lth o u g h it is n o t e a sy to
m a k e a c h o ic e b e tw e e n th e tw o , e x p e rim en ta l resu lts o n m o n o n u c le a r p e r o x o
c o m p le x e s are in a b e tter a g r ee m en t w ith th e S h a rp less m ech a n ism .* 141,1421 T h is
m a y w ell b e th e c a se w ith p e r o x o p o ly o x o m e ta la te s , b u t n o d irect in fo r m a tio n
is a v a ila b le .
T h e p e r o x o tu n g s to p h o s p h a te Q 3 { P 0 4[ W 0 ( 0 2)2]4 } is a h ig h ly e ffic ie n t c a ta
ly st fo r th e p h a se -tra n sfe r e p o x id a tio n o f o le ic a c id (O A ) b y a q u e o u s 3 5 - 6 0 %
h y d r o g e n p eroxid e.*1431
o
/ \
CH3(CH2)7CH=CH(CH2)7COOH + H20 2 ----- ► CH3(CH2)7CH-CH(CH2)7C 0 0 H + h 2o
Figure 5.4 The structure of peroxo polyanion {HP0 4[W0 (0 2)2]2}2^ • Reprinted
with permission from Chem. Rev. 1998, 98, 171. Copyright 1998 American Chemical (5 .5 0 )
Society.
T he reaction is carried ou t in o leic acid m ed iu m w ith o u t solven t at 5 0 -8 0 °C T h ese b yp rod u cts m ay be o f interest as m o n o m ers for p o ly co n d en sa tio n . A s
and O A / H 2O 2 m o la r ratio o f 1:1.2, yield in g 84% e p o x id e (b ased on o leic acid) can be seen from T ab le 5.4, the yield o f H M W dep en d s m ain ly on the tem pera
at 9 5 % oleic acid con v ersio n and 8 0 0 -1 2 0 0 catalyst turnovers (T ab le 5.4). ture and the reaction len gth. A t 80 °C the H M W co n ten t is quite high, ca.
H igh m olecu la r w eigh t b yp rod u cts (H M W ) are a lso form ed p ro b a b ly by 26 wt%, but under op tim u m co n d itio n s at 5 0 -6 0 °C, it d rop s d o w n to 5 -6 wt%.
acid -ca ta ly sed reaction s 5 .5 1 -5 .5 2 . G iven the H M W a m o u n t o f 5 wt% present in the O A feed, practically n o H M W
is form ed under such con d itio n s.
OH T h e ep o x id a tio n o f sty ren e-b u ta d ien e and iso b u ten e-iso p re n e cop olym ers
A I
C H 3(C H 2) 7C H -C H (C H 2)7C OOH
by h yd rogen p eroxid e in the p resence o f C M P C ^ M C K C ^ ^ } has been
2 C H 3(C H 2)7C H -C H (C H ,)7COOH + h 2o
rep orted .[144]
0 A n in terestin g m o d ifica tio n o f the V e n tu re llo -Ish ii system for the e p o x id a
1 tion o f p rop en e has been d evelo p ed by X i et a /.[145] T h e ep o x id a tio n is carried
C H 3(C H 2)7C H -C H (C H 2)7C OOH
ou t h o m o g e n e o u sly by H 20 2 in the presence o f a p ero x o p o ly o x o m eta la te
I
OH [7I-C 5H 5N + (C H 2) 15C H 3]3 {P 0 4 [W (0 )2(0 2 )]4} (w h ich h as sligh tly different
p o ly a n io n th an the V en tu rello co m p lex ) in a m ixture o f to lu en e and tributyl-
(5.51)
p h o sp h a te at 35 °C . W h en the H 2O 2 is u sed up, the ca ta ly st p recip itates and can
be recycled (S ch em e 5.4).
O ?H
/\ I
2 C H 3(C H 2)7C H -C H (C H 2)7C OOH ----- -- C H 3(C H 2)7C H -C H (C H 2)7C OOH
h 2o 2
[tc-C 5H 5N C i 6H 33]3[P 0 4( W 0 3)4] --------------------------- [tc-C 5H 5N C 16H 33]3{ P 0 4[W (0 )2( 0 2)]4}
(5 .5 2 )
A
C H 3(C H 2)7C H -C H (C H 2)7C -0
? , ,,
(insoluble)
organic solvent
(soluble)
2 C H 3(C H 2)7C H = C H (C H 2)7C OOH C H 3(C H 2)7C H 2C H (C H 2)7C OOH
o
(5 .5 3 )
C H 3(C H 2)7C H = C H (CH2)7C -0
Scheme 5.4
o
T h e ep o x id a tio n is further co u p led w ith the 2-eth yla n th ra q u in o n e/2 -eth y la n -
Table 5.4 Epoxidation of oleic acid (OA) by H2O2 catalysed by Q3{P0 4[W0 (02)2]4}a [143]. th rah yd roq u in on e (E A Q /E A H Q ) p rocess fo r H 2O 2 p ro d u ctio n , so that O 2 and
Catalyst h 2o 2 T Time Conversion*3 Selectivity, %° HMW

% epoxide diol wt% Pd catalyst
mmol% mol% °C min EAQ + H2 -------------------- EA H Q
0.038 0.050 80 50 99 57 5.7 25.8
0.038 0.050 60 30 98 80 3.1 9.3 EAHQ + 0 2 -----------► H 20 2 + EA Q
0.038 0.050 60 105 99 75 1.7 15.7 O
0.038 0.050 60 70 99 54 4.9 15.8 PO M / \
0.038 0.041 60 35 98 77 6.4 9.5 C H 3C H = C H 2 + h 2o 2 ------------ c h 3c h - c h 2+ h 2o
0.038 0.041 60 50 95 89 1.3 5.0
0.038 0.035 50 45 94 88 1.3 6.4
a) 10 g (0.03 mol) of the OA feed, containing 76 % OA, 7 % linoleic acid, 5 % palmitic acid, 6 % stearic acid, 1 % c h 3c h = ch 2+ o 2+ h 2 ---------- ►
A
c h 3c h - c h 2+ h 2o
erucic acid, and 5% HMW, was charged
b) Total conversion of oleic and linoleic acids
c) Total selectivity to epoxides and diols derived from oleic and linoleic acids Scheme 5.5
H 2 can be used instead of H20 2 for the epoxidation. This method is claimed to [P W i|0 39]7- shows the highest activity and selectivity for epoxidation.
give 85% yield of propene oxide based on 2-ethylanthrahydroquinone without [PW i20 4o]3~ is much less active. The complexes of Co(II), Cu(II), and Ru(IV)
any byproducts. The overall process is represented by Scheme 5.5. are inactive in the oxidation of cyclohexene but rapidly decompose H20 2. The
Ni(II), Ti(IV), and V( V) complexes are inert in both the oxidation of the substrate
Miscellaneous oxidations Ishii el al. reported many other hydroperoxide oxi and the decomposition of H20 2. The Fe(II) and Cr(III) complexes are moder
dations with the tris-cetylpyridinium salt of H3[PW i20 4o] (CPW). sec-Alcohols ately active in the oxidation, but the reaction is nonselective.11081
and diols are dehydrogenated by the CPW - H2O2 system in t-butyl alcohol to Polyoxometalates [WM3(H2 0 )2(XW90 34)2]12" (X = M = Zn2+ or Co2+,
give the corresponding ketones in good yields.11201 Primary alcohols are much which can be substituted by a variety of transition metal ions)11481 proved to
less reactive under such conditions. However, a,o)-diols give lactones in fair be promising oxidation catalysts. These anions contain two a-Keggin-type
yields.11111 The CPW - H2C>2 system is also efficient for the oxidative cleavage trivacant lacunary units B-{XW90 34} which are linked by four coplanar octa-
of carbon-carbon bonds of v/oglycols and alkenes to yield carboxylic acids.11201 hedrally coordinated and close-packed metal ions (Figure 2.13). In contrast to
Other reactions that can be readily carried out with this system include the Keggin anions, which are stable only in acidic solutions, these polyoxometa
conversion of internal alkynes to the corresponding a, ß-epoxy ketones,11231 lates are stable in the pH region from about 6 to about 10.1I48] The ions in M
allenes to a-alkoxy or a-hydroxy ketones,11241amines to oximes and nitrones,11221 positions can be substituted by Mn2+,M n3+,F e2+,F e 3+,N i2+,C u 2+,Z n 2+,
anilines to azoxy-nitroso- and nitrobenzenes[1191 and sulfides to sulfoxides and Pd2+,P t2+, V4+, etc., which provides interesting opportunities for catalyst
sulfones.11251 design. Unlike the Keggin anions, these polyoxometalates are fairly stable not
a- and ß-Naphthols (~ 10-3 mol l- ') are oxidised by H20 2 (2-15%) to 1, only to hydrolysis but also to degradation by H20 2. Thus Khenkin and Hill11491
2-naphthoquinone in 80-98% yield at 20 °C in the 1,2-dichloroethane-water reported that the [Fe4(PW90 34)2]10- anion is quite stable with respect to
biphasic system in the presence of peroxo heteropolytungstates and trioctyl- solvolysis by H2O2; it catalyses the selective homogeneous epoxidation of
benzylammonium chloride (TOBAC) (eqs 5.54-5.55). When the naphthol con alkenes by H20 2 in aqueous acetonitrile at 20 °C.
centration is increased, C-C coupling products are formed. The catalytic Neumann et a /.,1’50,1511 found that the solvolytically stable disubstituted
system is prepared by mixing PO43-, W 0 42-, and TOBAC in a molar ratio of manganese(II) polyanion, [WZnMn2(H20 ) 2(ZnW90 34)2]12% is a highly active
8:4:3. It is suggested that the active form of the catalyst is {P04[W 0 (0 2)2]4}3 -. catalyst for the epoxidation of alkenes and oxidation of alcohols by 30 % H20 2
The reaction proceeds via the semiquinone radical intermediates, which were in a biphasic system at ambient temperature with very high selectivities (>99%)
detected by ESR.[146] and hundreds to thousands of catalyst turnovers. Interestingly, the trisubsti-
tuted polyanion, [WMn3(H20 ) 2(ZnW90 34)2]12_, is significantly less efficient,
OH O followed by Zn2+ and Co2+ derivatives. The Rh3+ anion, [WZnRh2(H20 )2
(ZnW9O34)2]10~, is about as active as the disubstituted Mn2+ analogue.11521
(5.54) Other substrates, e.g. alkenols, diols, amines, etc., can be oxidised in such
systems.11531
Polyoxometalate-based solid catalysts for the epoxidation of alkenes have
been reported.11541 These contain polyanions {P04[W 0 (0 2)2]4}3- or [WZnMn2
(H20 ) 2(ZnW90 34)2]12_ immobilised on a silicate xerogel covalently modified
(5.55) with phenyl groups and quaternary ammonium groups. The catalysts epoxidise
alkenes by 30% H20 2 at room temperature in the absence of an organic solvent.
Another technique for immobilisation of polyoxometalates using polyethers has
Mechanistic aspects of the oxidation of N,N-benzylalkylamines to nitrones by been reported.11551 The Ti-substituted Keggin-type anions, [PW nTiO^]5-,
Q3{P04[M 0 (0 2)2]4} (where M = Mo or W) have been studied.11471 [PWioTi20 4o]7_, etc., have been studied as catalysts for the epoxidation of
alkenes with H 20 2. The kinetic data obtained imply the involvement of HO*
radicals generated by the decomposition of H20 2.1156] The kinetics of epoxida
5.1.2.2 Other Polyoxometalate Systems tion of cyclooctene with H20 2 catalysed by the peroxo polyoxometalate
Epoxidation of alkenes Heteropolytungstophosphates [PWi20 4o]3-, [PWn [PWioTi20 38( 0 2)2]7" has been studied.11571
0 39]7- , and {PWn 0 39M}, where M = Ni(II), Co(II), Cu(II), Fe(II), Cr(III), Triniobium (V) heteropolytungtophosphates have been structurally char
Ru(IV), Ti(IV), and V(V) have been studied as catalysts for the oxidation of acterised and tested as catalysts for alkene epoxidation by hydrogen perox
cyclohexene by hydrogen peroxide in acetonitrile at 35 °C. The lacunary anion ide.1' 581
P O L Y O X O M E T A L A T E S AS C A T A L Y S T S FOR SE L E C T IV E O X ID A T IO N 147
Cyclopentene is oxidised by hydrogen peroxide to glutaraldehyde in the Oxidation of aromatic compounds The HPA-n anions catalyse the oxidation
presence of mixed-addenda heteropoly acids H3[PMoi2- nWn0 4o](n = 1 - 9 ) of alkylaromatic compounds by 30% H2O2 in AcOH at 80 C to form the
in tributyl phosphate (TBP) solution in 60% yield based on H 2O2 (35 C, respective acetates or alcohols and aldehydes or ketones, HPA-2 being the most
3 h). Water is removed from the H2O2 —TBP system by vacuum distillation. effective catalyst.11651 There is spectroscopic evidence that HPA-2 is not de
Other heteropoly acids are also active; the yield of glutaraldehyde (%) decreases graded during the reaction. However, there is a significant decomposition of
in the order; H;?[PMoioW204o] (61) > H 3[PMoi204o](47) > H4[GeMoi204o] H 20 2 accompanying the oxidation of the alkylaromatic substrates. The mech
(21) > H 5[PMo10V204o](6) > H3[PW120 4o](5) > H4[SiMo12C>4o](l).ll59l anism proposed includes the homolytic cleavage of peroxo species at the
Reaction of alkenes with aqueous hydrogen peroxide and a catalytic quan vanadium atom of HPA-2 to form HO* and HO2* radicals, which react with
tity of Keggin heteropoly acid supported on MgO, AI2O3, or ZnO leads to the alkyl aromatic substrate to give the observed products, as represented by
complete cleavage of the alkenes to give carbonyl compounds.11601 equations 5.56-5.60.[16S1
Oxidation of alkanes Oxidation of alkanes, including methane, with hydrogen HPA-2 + H20 2 -> H(HPA-2) + H 0 2‘ (5.56)
peroxide in the presence of various polyoxometalates has been attem pted.1161"1641
Mizuno et a/.[162~1641 reported the selective oxidation of various alkanes from H(HPA-2) + H20 2 -> HPA-2 + HO* + H20 (5.57)
methane to n-hexane, cyclohexane, and adamantane with H 2O2 catalysed by the
ArH + HO*(or H 0 2’) -» Ar* + H20 (o r H20 2) (5.58)
Keggin type diiron(lII)-subsituted tungstosilicate [SiWio038Fe2]6- (Table 5.5).
The tetrabutylammonium salt is effective in acetonitrile solution and the water-
Ar* + HPA-2 + H + -► A r+ + H(HPA-2) (5.59)
soluble potassium salt is active in water. The efficiency of hydrogen peroxide
utilisation to oxygenated products is ca. 100% for the oxidation of cyclohexane Ar+ -I- AcOH (or H 2O) —►ArOAc + H + (or ArOH) (5.60)
and adamantane. It is suggested that the Keggin polyanions with two Fe(III) ions
occupying the neighbouring octahedra are the catalytically active species and
As shown by Shimizu et al.,[l66i the Keggin heteropoly acids catalyse the
their performance may be related to the catalysis by methane monooxygenase.
oxidation of 2,3,5- and 2,3,6-trimethylphenol (TMP) to 2,3,5-trimethyl-1,
4-benzoquinone (TMBQ) by hydrogen peroxide in acetic acid solution in 65-
Table 5.5 Oxidation of alkanes with hydrogen peroxide catalysed by 78% selectivity at 94-100% TM P conversion. The mechanism proposed in
[SiWi0O38Fe2]6_ in acetonitrile at 32 °C, 96h[l<Sl. volves the HPA-catalysed hydroxylation of the aromatic ring to form 2,3,5-
Substrate Conversion, % Product Selectivity, % trimethylhydroquinone, followed by its fast oxidation to TMBQ (eq. 5.61). In
this reaction, heteropoly acids apparently behave as Bronsted acid catalysts,
Methane 0.4 Methanol 73 enhancing the formation of peracetic acid; the latter is probably the true
co2 27 hydroxylating species.11661 v/c-Diols are oxidised with 30% aqueous H20 2 in
Ethane 1.2 Acetaldehyde 57
Acetic acid 40 the presence of heteropoly acids to yield carboxylic acid.[16?1
co2 3
Propane 4.0 Acetone 86 oh oh o
Acetaldehyde 12
co2 2
n-Butane 11 Methylethylketone 82
Acetaldehyde 17
co2 1 OH O
n-Pentane 9.0 Pentanols 33
Pentanones 67
n-Hexane 15 Hexanols 25 Tungsten and molybdenum polyoxometalates have been studied as catalysts
Hexanones 75 for the oxidation of benzene to phenol with 30 % aqueous H20 2 at 25 °C by
Cyclohexane 25 Cyclohexanol 32 Nomiya et <3/.[168" l7,] The Keggin anions, {PW10V2} and {PW9V3}, show
Cyclohexanone 68 92-98% selectivity to phenol (based on benzene) at < 8 % benzene conversion.
Adamantane 42 1-Adamantanol 20 The activity of {PW9V3} is initially high, but decreases after 48 h due to decom
2-Adamantanol 71
2-Adamantanone 9 position of the Keggin structure. The {PW10V2} anion remains intact and main
tains its activity even after 576 h.[1681 In the case of molybdovanadophosphates,
the oxidation of benzene is catalysed by the vanadium(V) species within the norbomene, and cyclooctene by iodosobenzene and pentafluoroiodosobenzene
Keggin anions or by the peroxo vanadium species V 0 (0 2)+ derived from in acetonitrile. The Mn(II) and Co(II) complexes exhibit the highest activity.*1811
polyanions.*1691 Kuznetsova et a/.*172,173] reported that the Fe3+-substituted A radical chain mechanism for the oxidation of cyclohexane and adamantane
polyoxometalate, [PW nC^Fe]4^, catalyses the oxidation of benzene to phenol by TBHP catalysed by {PWHO39M} has been suggested.*1811 [R4N]5
by H2O2 in CH3CN solution at 70 C, with the decomposition of H 20 2 being [SiWn0 39Ru(H20 )] catalyses the liquid-phase oxidation of alkanes and alkenes
the main reaction. A mechanism, including the oxidation of C öH ö by HO* by TBHP, potassium persulfite, sodium periodate, and iodosobenzene.*183’1841
radicals formed via the H20 2 decomposition, is suggested. Pd(II) and Pt(II) A number of polyoxometalates catalyse the selective oxidation of thioethers
complexes of [PWn0 39]7~ as well as sandwich type polyoxometalates catalyse to the corresponding sulfoxides by t-butyl hydroperoxide at 25 °C, HPA-2
the co-oxidative hydroxylation of benzene to phenol by a gas mixture of 0 2 and being particularly selective (>99.9%). A mechanism, including outer sphere
H2 in a two-phase system at 10-40 °C.[174,1751 Liquid-phase oxidation of ben electron transfer from thioether to polyanion, is suggested.*1851
zene to phenol by O2 (10atm, 25 C) in the presence of Fe2+ + {PW1204o} has The molybdovanadium isopoly acids {V|2_xMox03i } (x = 0 - 4 ) catalyse
been reported.*1761 This reaction is likely to be a free radical co-oxidation of an the oxidation of 1,2,4-trimethylbenzene to trimethylbenzoquinone by peracetic
Fe2+-POM and benzene by 0 2. acid in acetic acid solution (20 °C, 4h) with a 12-31 % selectivity at 15-22%
trimethylbenzene conversion.*1861
Oxidation of sulfur compounds Polyoxometalate-catalysed oxidation of sulfur
compounds with H20 2 may be promising for desulfurisation of oils. For
example, the oxidation of dibenzothiophene with H20 2 using {PW1204o} as 5.1.4 MISCELLANEOUS OXIDATIONS
a catalyst and (C8Hi7)4NBr as phase transfer agent in a two-phase water-
toluene system yields nearly 100% of dibenzothiophene sulfone. Treatment of Methane is converted to methyl trifluoroacetate in 95 % yield using vanadium
gas oils with this method shows that all the sulfur compounds present are containing Keggin heteropoly acids as catalysts and K2S20g as an oxidant in
oxidised by this catalyst system. Oxidised products can be separated from oil CF3C O O H /(C F3CO)20 solution (80 °C, 24 h, 20 atm).*1871
by adsorption on silica gel.*1771 Kinetics and mechanism of thioether oxidation p-Toluenesulfonic acid is electrocatalytically hydroxylated to the alcohol,
with H20 2 in the presence of Ti(IV) containing heteropoly tungstates has been p-H0 3 SC6H4CH20 H, by a system consisting of aqueous PtCl42~ as C-H
studied by Kholdeeva et a/.[178,1791 activation catalyst, 12-molybdophosphoric acid as redox mediator, in an elec
trochemical cell containing a carbon cloth anode.*1881
The manganese-substituted heteropolytungstates [SiW nC^Mn]6-, [SiW10
5.1.3 OXIDATION BY ORGANIC PEROXIDES 0 38Mn2]8~, [SiW9O37Mn3]10~, and [PW9037Mn3]9_ have been applied as cata
lysts for low-temperature bleaching of stained cotton cloth with sodium per-
The epoxidation of 1-hexene by cumene hydroperoxide (ROOH) in isopropa carbonate. These polyoxometalates are interesting alternatives to conventional
nol solution is catalysed by Keggin heteropoly salts at 110°C to give the complexes with organic ligands as catalysts in bleach processes. However, their
epoxide with 100% selectivity at 80% ROOH conversion. The reaction obeys instability under bleaching conditions and the fibre-damage induced to cotton
the kinetic equation r = /rJPOMf [ROOH][CeHi2], where p = 0.5-0.9 at cloths prevent their practical application.*1891
[POM] = (0.2 - 0.9) 10_5m oll_1. The catalytic activity of heteropoly salts
decreases in the order Na3[PMoi204o]> Al[PMoi204o] > N a4[PM onV04o]
> Na4[SiMoi204o] » Na3[PWi204o]. The heteropoly acids themselves are in 5.2 GAS-PHASE OXIDATION
effective as they catalyse the decomposition of cumene hydroperoxide to
phenol and acetone. There is evidence that the heteropolymolybdates decom 5.2.1 GENERAL OVERVIEW
pose in the reaction course. Monomeric molybdenum(VI) complexes are sug
gested as the catalytically active species.*1801 Polyoxometalate-catalysed selective oxidation of organic compounds (oxygen
Transition metal-substituted polyoxometalates (n-Bu4N)4H[PW ii039M], ation or oxidative dehydrogenation) in gas phase is carried out with use of 0 2
where M = Mn(II), Co(II), Cu(II), Fe(II), etc., catalyse the oxidation of cyclo- (air) or sometimes N20 as oxidants. These reactions are generally highly
hexanol and adamantane by t-butyl hydroperoxide (TBHP) in benzene. The exothermic, and the heat transfer from the reaction zone may be a serious
selectivity to the oxidation products (cyclohexanone or 1-adamantanol, 2-ada- issue. Usually, total oxidation (combustion) of an organic substrate is thermo
mantanol, and 2-adamantanone) reaches 90 % based on TBHP. These polyox dynamically more favourable than the partial oxidation; hence for partial
ometalates also catalyse the oxidation of olefins such as cyclohexene, 1-hexene, oxidation, the selectivity is a key issue, and care must be taken to avoid over-
oxidation of the desired products. For gas-phase oxidation by polyoxometa- efficient oxidation catalysts. The type of countercation is essential as well,
lates, the major concern is the relatively low thermal stability of heteropoly providing the catalyst with an optimal acidity, thermal stability and texture
compounds. Consequently, these reactions are usually carried out at moder (surface area, porosity, framework mobility, etc.).[9,161
ately high temperatures, below 350-400 °C. The Keggin heteropoly acids and The Keggin heteropoly acids and salts with the [PMoi2_n VnO40](3+nH
salts, both bulk and supported, are the most frequently used as the catalysts. In anions (HPA-n, n = 0-2) are the most frequently used as solid catalysts for
addition, polyoxometalates can be used as precursors to catalytically active selective oxidation with oxygen in the gas phase.19,161 The same polyoxometa
mixed oxide materials; in this case the reaction temperature is no longer lates, but with n = 2 - 6, are widely used as homogeneous catalysts for aerobic
restricted by the thermal stability of parent heteropoly compounds. Certain oxidation in solution (Section 5.1.1). In solution, the HPA-n-catalysed oxida
acidity/basicity in the catalyst as well as the presence of steam in the feed are tion follows the stepwise redox mechanism (eqs 5.1 and 5.2) that has already
essential for gas-phase oxidation. These may be required to enhance the forma been thoroughly discussed. A similar mechanism (M ars-van Krevelen type) is
tion or conversion of reaction intermediates as well as to facilitate desorption of suggested to operate in the case of gas-phase oxidation.
products from catalyst surface. There is sufficient evidence that such reactions
often involve bifunctional acid and redox catalysis.[9,13,16,171
Selective oxidation with mixed oxides and oxide-like catalysts such as poly 5.2.3 REACTIONS
oxometalates involves the activation of C —H or C —C bonds as well as of the
oxidant on the catalyst surface and frequently occurs by a M ars-van Krevelen Table 5.6 shows some typical examples of gas-phase selective oxidations of
redox mechanism,19,171 which may be represented by Scheme 5.6. organic compounds over polyoxometalate catalysts. These reactions are usually
carried out at temperatures of 150-400 °C. A number of bulk and supported
heteropoly compounds are used as the catalysts, frequently various promoters
(H20) Substrate
(e.g. As, Pb, Bi, Fe, Cu, etc.) added.
Ai[190] compared the catalytic properties of HPA-n with those of vanadyl
pyrophosphate, (V0)2P20 7 (VPO), and iron phosphate, F eP 04, for selective
gas-phase oxidations (Table 5.7). Generally, the catalytic activity of HPA-n is
about the same order of magnitude as that of VPO. HPA-n show higher
Oxidation selectivities than VPO for reactions such as the oxidative dehydrogenation of
catalyst product carboxylic acids and the oxidation of butadiene or crotonaldehyde to furan.
For the oxidation of methacrolein and allylic oxidation of isobutene or butadi
Scheme 5.6 ene the selectivities are similar.
Misono et a l? ’n] proposed two types of oxidation catalysis by solid hetero
The catalyst oxidises the substrate and then, in a separate step, is reoxidised by
poly compounds, namely (i) surface type and (ii) bulk type II. (The bulk type I
0 2. Either step can be rate-determining to control the overall reaction rate.
In this section, some basic features of the gas-phase selective oxidation with
Table 5.6 Heterogeneous gas-phase oxidation over heteropoly compounds191.
oxygen over polyoxometalate catalysts are reviewed. For more comprehensive
discussion, the reader should consult the recent books by Moffat1161 and by Reaction Catalyst T (°C)
Centi, Cavani, and Trifiro.1171
Methacrolein + 0 2 -» methacrylic acid CsH3[PMon V04o] 260
Isobutyric acid + 0 2 -+ methacrylic acid H5[PMoi0V20 4o] 300
CH3OH + 0 2 - HCHO, (CH3)20 H 3[P M o ,2C>4o] 200-290
5.2.2 OXIDATION CATALYSTS C2H5OH + 0 2 -►CH3CHO, (C2H5)20 H 3[P M o i 2O 40] (+ polysulfone) 170
C2H4 + 0 2 -►CH3COOH Pd + H4[SiW12040]/Si02 150
Selection of oxidation catalysts is largely based on the redox properties of Isobutene + 0 2 —>methacrolein PbFeBi[PMoi2Ox] 400
1-Butene + 0 2 —'• maleic anhydride Cs25H0jfPMoiaO^] + V02+ 290
polyoxometalates, which have been discussed in Chapter 2. A sufficiently CH4 + N20 - HCHO, CH3OH H3[PMoi204o]/Si02 570
high oxidation potential and fast, reversible redox transformations of polyox C2H6 + N20 (O2) - Q H 4, CH3CHO H3[PMo12O40]/SiO2 267
ometalates are key factors determining their efficiency as oxidation catalysts. C3H8 + 0 2 —<•acrylic acid H3[PMo)204o]( + As) 340
Also important is the ability of polyoxometalates to activate the substrate and/ n-Butane + 0 2 -*• maleic anhydride Bi[PMoj2Ox] + V02+ 360
or the oxidant, i.e. 0 2. On these bases, among various polyoxometalates, the Isobutane + 0 2 -»• methacrylic acid H3[PMoi204o]_______________ 350
Keggin compounds containing molybdenum and vanadium make the most
Table 5.7 Comparison of selectivities of different oxidations1'90*. a methacrolein conversion of 70-90%, the selectivity to methacrylic acid is
between 80-85%.
Reaction HPA-n VPO FeP04
The catalyst is an acidic caesium salt of HPA-n, H3+n- xCsx [PMon-n
Propane —►acrylic acid M G B Vn0 4o] (2 < x < 3; 0 < n < 2). These salts have advantage of the increased
n-Butane —* maleic anhydride M G B surface area and higher thermal stability compared to the parent heteropoly
Propene —>acrylic acid M G B acids. It has been shown that both acidity and oxidation ability of catalysts are
n-Butene —>maleic anhydride M G B
Isobutene —* methacrylic acid + methacrolein M M B necessary for the selective oxidation of methacrolein to occur. The preferred
Butadiene —►furan G M B acidic salts are nearly stoichiometric. But the stoichiometric caesium salts
Methanol —>formaldehyde M G B Cs3+n[PMoi2-nVn04o] are not catalytically active, probably due to the absence
Crotonaldehyde —►furan G M B of acidity. The vanadium substitution for part of the molybdenum increases the
Acrolein —►acrylic acid M G B oxidising ability. The effect of caesium-for-proton substitution in H4[PMon
Methacrolein —>methacrylic acid G G B
Propionic acid —>acrylic acid M M B VO40] on the catalytic activity and selectivity for the oxidation of methacrolein
Isobutyric acid —>methacrylic acid M M G is shown in Figure 5.5.
Substitution of one vanadium(V) for molybdenum!VI) in H 3[PMo]204o]
G = good. M = medium. B = bad
increases the thermal stability; the stability decreases, however, upon further
substitution. There is evidence that the Keggin structure is not intact during the
(pseudoliquid), discussed in Chapter 4, is relevant to the acid catalysis by bulk reaction. Upon heat treatment of solid H 4I P M 0 1 1 V O 40], vanadyl and molybde-
heteropoly acids.) The surface type is the conventional oxidation catalysis at a nyl species leave the Keggin unit. Substitution of Cs+ for proton in
gas-solid or liquid-solid interface; such processes can occur on the surface of H4[PM ou V O 40] stabilises the structure, while the presence of water vapour
both bulk and supported heteropoly compounds. The bulk type II is relevant to enhances its desintegration.[l92) The role of the vanadyl and molybdenyl species
reactions on bulk heteropoly compounds. This mechanism is suggested to oper is not yet clear. It is conceivable that, like in homogeneous catalysis
ate in the case of certain catalytic oxidations that largely occur on the catalyst
surface, with the bulk diffusion of electrons and protons assisting the redox
process. It is thought that this type does not normally involve the oxygenation of
organic compounds, which is more likely to proceed via the surface type cataly
sis. The surface type and the bulk type II catalysis over solid heteropoly com
pounds may be exemplified by the oxidation of CO and H2, respectively.[9,111
Two practically important oxidations - one oxygenation and the other
oxidative dehydrogenation - that have been studied in detail in the past two
decades may represent the surface type and bulk type II mechanisms. These are
the oxidation of methacrolein to methacrylic acid and the oxidative dehydro
genation of isobutyric acid to methacrylic acid, respectively.
5.2.3.1 Oxidation of Methacrolein to Methacrylic Acid19,11,1911

Methacrylic acid is used for the production of methyl methacrylate which in
turn is used for manufacturing a crystal-clear plastic Plexiglas®. The oxidation
of methacrolein to methacrylic acid over a heteropoly compound catalyst has
been developed and commercialised in Japan (Chapter 7).
CH3 CHj
I . I (5.62)
c h 2= c -c h o + '/2 o 2 -------- CH2=C-COOH
Figure 5.5 Effect of caesium substitution in C sxH4^x(PM oii VO40] on catalytic activity
The reaction is carried out at 270-350 °C with a gas feed consisting of 2-5 % (solid circles) and selectivity (open squares) for the oxidation of methacrolein to
methacrolein, 10-20% steam and a methacrolein/oxygen molar ratio of 2-4. At methacrylic acid.*1911
154 CATALYSIS BY POLYOXOMETALA TES POLYOXOMETALATES AS CATALYSTS FOR SELECTIVE OXIDATION 155
(Section 5.1.1), these may he active species in oxidising the substrate, then re be an oxygen atom from the breakaway vanadyl or molybdyl species. Besides,
entering the polyanion to become reoxidised by dioxygen. as the oxidation occurs in the presence of steam, oxygen transfer from water
Mechanistic studies show that the oxidation of mcthacrolein is a surface type vapour is not excluded; if so, the mechanism would largely be the same as that
oxidation and involves a bifunctional, i.e. both acid base and redox cataly- for the homogeneous oxidation by HPA-n (eqs 5.1 and 5.2). This is still an open
sis P.n.i9i] p resence 0f water is essential for the reaction to occur; water may be question, though.
required for the formation of reaction intermediates, maintaining the stability Attempts have been made to discriminate the reactivity of terminal and
of catalyst active sites, as well as to enhance product desorption from the bridging oxygens in Keggin heteropolymolybdates by measuring the oxygen
catalyst surface. Apparently, one of the important acid-catalysed steps is the exchange between solid heteropoly compounds and water vapour using IR
conversion of methacrolein to methacrolein hydrate: spectroscopy1m i9 5 ^ and more recently I70 N M R J196' These studies show
that the oxygen exchange with H3[PMoi204o] occurs at temperatures above
RCHO + H20 -► RCH(OH)2 (5.63) 200 °C (Table 5.8) and is accompanied by fast mixing of terminal and bridging
oxygens in the Keggin unit, which makes it difficult to discriminate between the
Further oxidative dehydrogenation of RCH(OH)2, which is probably rate two types of oxygen atoms. On the basis of 170 NM R results, a mechanism of
determining, is suggested to proceed via a M ars-van Krevelen mechanism. oxygen exchange has been suggested (Scheme 5.7).[l961 It includes the breaking
This mechanism includes the oxidation of the intermediate by the catalyst,
followed by the reoxidation of the reduced catalyst with dioxygen.
O O
RCH(OH)2 + HPA-n RCOOH + H2[HPA-n] (5.64) -M -O H H P ’-M. -------- -M-0*-M-
O O .............. -h 2o
+H+ +HzO*
H 2[HPA-n] + V2 O 2 -* HPA-n + H 20 (5.65) -M-O-M- -M-OH M- or
-H+
O O-H
This mechanism is supported by the following experimental results. There is a
fairly good correlation between the oxidising ability of polyoxometalate and -M-OH 0=M -
the reaction rate. The selectivity remains the same for a prolonged period when
the supply of oxygen is stopped at the stationary state of catalytic reaction,
which supports the involvement of the polyoxometalate framework oxygen in
step 5.64. There is also rapid isotopic exchange of oxygen between the catalyst
and either RCHO or water. ?“ H
The following rate equation has been reported for the reaction catalysed by -M = 0 M-
H3[PM oi20 4o] at 300 °C, where in square brackets are the pressures of react n 9* O O*
ants:119^ -M-pHHÖ-iM------------ - -M-O-M-
.............. -h 2o
rate = k [RCHO]a 6- , [O2]0"0'2[H2O]0
Scheme 5.7
This equation indicates that step 5.64 is rate-limiting in the above mechanism.
The role of acidity is deemed manifold; it may enhance: Table 5.8 Oxygen exchange between n O-enriched heteropoly
acid and H2 160 vapour from 170 MAS NMRa,t1961.
• The formation of methacrolein hydrate (eq. 5.63) and its interaction with the Heteropoly acid T,°C Time, h Exchange, %b
polyoxometalate catalyst to form an ester intermediate. 200 1 <5
H3[PMoi2l704o]
• Oxygen transfer (water -» POM; POM -»• substrate; 0 2 —> POM, or water H3[PMoi217O40] 250 1 20
—* organic intermediate). H3[PMoi2l704o] 250 5 60
• Product desorption from catalyst surface. H3[PW,21704o] 300 2 0
a) H i i60 20 lorr, atmospheric pressure
Another question is which oxygen is transferred to the substrate? If from the b) Percentage of outer oxygens in the Keggin anion exchanged. Fast mixing of
polyoxometalate, is it the terminal or bridging oxygen? Alternatively, it could the terminal and bridging oxygens takes place
of an oxygen bridge initiated by protonation to form a pentacoordinate Mo(VI). vation is observed:1198,1991 the conversion of butene drops ten-fold from 60% to
The latter is attacked by an H20 molecule to give an octahedral Mo(VI), con 6 % after 1 h on stream, while the selectivity decreases less dramatically, only
taining the entering OH group in the equatorial or axial position with almost from 98% to 90%.
equal probabilities. Finally, the release of an H20 molecule restores the Keggin Nowinska et a/.f200 2031 reported a very stable activity in the oxidation of
structure, with either the terminal or the bridging oxygen atom exchanged. ethylene to acetaldehyde with a Mn2+-promoted catalyst, (PdCl2 + Mn2++
H PA -2)/Si02. After 50 h on stream at 70 °C, a constant 98% selectivity at
5.2.3.1 Oxidative Dehydrogenation of Isobutyric Acid 80% ethylene conversion is observed.
The oxidative dehydrogenation of isobutyric acid has attracted interest as 5.2.3.4 Oxidation of Ethylene to Acetic Acid
another route to methacrylic acid.19,11,16,1911
Another combination of palladium and polyoxometalate - Pd(0) and a non
cn3 ch 3 oxidising heteropoly acid H4[SiWi204o] - is effective for the gas-phase oxida
(5.66) tion of ethylene to acetic acid with oxygen.12051 This process has been developed
C H r C H -C O O H + l/2 0 2 ch 2= c -c o o h + h 2o
and commercialised by Showa Denko in Japan (Chapter 7).
Heteropoly compounds H 3+n-xCsx[PMoi2_nVn04o] (2 < x < 3; 0 < n < 2) CH2 = CH2 + 0 2 -» CH3COOH (5.68)
(HPA-n) have been found to be very efficient catalysts for this reaction. With
HPA-n, 78% selectivity to methacrylic acid at 97% conversion at 350 °C has Remarkably, even a simple combination of Pd metal and heteropoly acid
been reported.19,111 gives a relatively high yield of acetic acid (Table 5.9). In the absence of HP A,
Spectroscopic characterisations show that vanadium is removed from the when Pd metal is supported on silica, no partial oxidation is observed, only
Keggin heteropoly anion under reaction conditions.11971 The reaction follows complete oxidation to carbon dioxide. Without Pd, when only heteropoly acid
the Mars-van Krevelen mechanism. There is evidence that the oxidative de such as tungstosilicic acid on silica is used, no oxidation of ethylene occurs
hydrogenation of isobutyric acid over bulk HPA-n is a bulk type II reaction, i.e. either; only a small amount of ethanol is obtained. With the palladium(II) salt
bulk diffusion of electrons and protons assist the oxidation process.19,111 of HPA as a catalyst, almost equal amount of acetaldehyde and acetic acid are
obtained. In this case, the reaction may proceed through the equations:
5.2.3.3 Heterogeneous Wacker Reaction
C2H4 + V2O 2 —>CH3CHO (5.69)
Attempts have been made to apply the solid two-component Pd(II) + HPA-n
system for the gas-phase Wacker oxidation and related reactions.117,198-2041 CH3CHO + Y2O2 — CH3COOH (5.70)
These reactions are usually carried out at relatively low temperatures,
70-100 °C, in the presence of steam. Mechanistically, they may be considered Table 5.9 Oxidation of ethylene over Pd and HPA catalyst systems81,1205].
as pseudohomogeneous, i.e., occurring in the liquid catalyst phase entrapped in
a support. As a support, silica is often used, which is relatively inert towards Catalyst STYb Selectivity, %
polyoxometalates. The real mechanism, however, may be more complex, but g/lh HOAcc HAcd C02
little data is available so far. There are two main problems in applying this
system to the gas-phase oxidation: (i) the reoxidation of the catalyst by 0 2 Pd-H4[SiWi204o] 93.1 78.5 5.5 14.2
Pd-H3[PW1204o] 83.3 78.0 5.0 16.0
proceeds much slower than in solution and (ii) the catalyst is rapidly deacti 68.5 77.5
Pd-H3[PMo120 4o] 4.6 17.8
vated probably due to aggregation of palladium. Pd-Gao.o5H3.85[SiW12O40] 90.4 80.1 4.1 15.6
The heterogeneous oxidation of n-butene to methylethylketone is a challen Pd-Mgo o5H3.85[SiWi204o] 90.8 79.7 5.5 14.6
ging goal.1171 Pd-H5[PMoioV204o] 94.0 61.4 19.4 17.6
Pd 0 0 0 100
H3[PW12O40] 0 0 0 0
CH3CH2CH = CH2 + % 0 2 -> CH3CH2COCH3 (5.67)
a) Reaction conditions: 150°C; 5atm pressure; GHSV = 3 0 0 0 h 1; gas mixture Q IL t/O j/H aO
inert gas = 50/7/30/13
Stobbe-Kreemers et a/.1198,1" 1 and Nowinska et a/.12041 studied this reaction b) Space time yield (g/l-catalyst h)
with the solid Pd(II) + HPA-n catalyst system at 70 °C. Not only HPA-n but c) HOAc = acetic acid
also their Cu2+,N i2+,P d2+ and Cs+ salts were used. A strong catalyst deacti d) HAc = acetaldehyde
The same mechanism may be operating in the case of Pd - H 5[PM oioV204o], as propane to propene in a 10% yield. Ni-catalyst shows the best performance in
this heteropoly acid is capable of oxidising Pd° to Pd2+. the direct oxidation of isobutane to methacrylic acid (9% yield). The catalysts
In the case of the most efficient systems including Pd metal and strong, reportedly retain the Keggin structure during the oxidation.
nonoxidising tungsten heteropoly acids, such as H4[SiWi204o] or H 3PPW12O40], Albonetti et a /P 01] reported the efficient oxidative dehydrogenation of
the reaction is likely to proceed through the acid-catalysed hydration of ethyl ethane on a modified potassium salt of H3PPM012O40]. The addition of antim
ene to ethanol, followed by the oxidation of ethanol to acetaldehyde catalysed ony leads to a remarkable increase in the thermal stability of the catalyst. Fe,
by palladium: Ce and Cr additives were found to greatly improve the activity and selectivity
towards ethene formation. U nder the optimal conditions (fixed-bed reactor,
C2H4 + H20 -► CH 3CH2OH (5.71) 510 °C, 1 atm), this catalyst gives 74% selectivity for ethene at 26% conversion.
No acetic acid is formed, only COx as by-products. The catalyst shows a stable
CH3CH2OH + 0 2 -► CH 3COOH + H 20 (5.72) performance for at least 100 h and reportedly retains its structure after the
reaction.
It has been found that the higher the acid strength of heteropoly acid, the Li et al.[20S] reported that a Py salt of H 3IPM012O40], pre-activated at 420 °C
higher the catalytic efficiency. Heteropoly acids and salts with a weaker acidic under N 2, catalyses the direct oxidation of propane to acrylic acid and iso
strength showed a lower catalytic activity, but these catalysts displayed butane to methacrylic acid in the presence of steam. Methacrylic acid is
extended lifetime. obtained in 11 % yield, which is probably the highest yield reported so far.
The catalyst contains oxygen-deficient heteropoly anions with reduced Mo.
S.2.3.5 Oxidation of Alkanes Proton sites are also present, which is considered essential for the reaction.
Heteropoly compounds have attracted interest as catalysts for the partial The catalyst shows a stable performance for at least 10 h.
oxidation of alkanes in the gas phase.[9,u’16,171 Generally, heteropoly molyb Volkova et al.[209] reported that (PdCl2 + H PA -6)/Si02 catalyses the ox
dates, both bulk and supported, are used for such reactions. Other transition idation of methane and other alkanes by 0 2 at 300 °C. Methane is converted
metals are frequently added as promoters to improve the catalytic activity and to CH 3CI and C 0 2 with selectivities of 20 and 25%, respectively. No reac
selectivity. The mechanisms are yet unknown, but there is evidence that the tion occurs without PdCl2. HPA-6 is suggested to mediate the reoxidation of
proton acidity is important for these reactions. The reader can find a detailed reduced palladium by 0 2. The relative oxidation rate increases in the series of
account on alkane oxidation in the monograph by M offat.[16] alkanes: CH4(0.14) < C2H 6(1.0) < C3H 8(2.0) < i-C4H 10(2.2) < n-C4H 10(3.4)
Mizuno et al.[u,206] have studied Keggin-type molybdovanadophosphates < cyclopentane(6.8) = cyclohexane(6.8) < n-C5H i2(7.2).[210]
HPA-n as catalysts for the selective oxidation of light alkanes from methane
to isobutane (Table 5.10). Most of these catalysts are bulk Cs acidic salts of
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1996, 41, 153. This chapter presents an overview of the application of polyoxometalates in
197. (a) E. Blouet-Crusson, M. Rigole, M. Fournier, A. Aboukais, F. Daubrege, G. other fields of catalysis such as hydrogenation, carbonylation and related
Hecquet and M. Guelton, Appl. Catal. A 1999,178, 69. (b) C. Marchal-Roch, N. reactions. Also discussed are polyanion-stabilised metal clusters, the anchoring
Laronze, N. Guillou, A. Teze and G. Herve, Appl. Catal. A 2000, 203, 143. of homogeneous catalysts by polyoxometalates, and the use of polyoxometa
198. A.W. Stobbe-Kreemers, G. van der Lans, M. Makkee and J.J.F. Schölten, J. Catal. lates as catalyst precursors. For more information on these topics, the reader
1995, 154, 175. should consult the references provided.
199. A.W. Stobbe-Kreemers, R.B. Dielis, M. Makkee and J.J.F. Schölten, J. Catal.
1995, 154, 187.
200. K. Nowinska, D. Dudko and R. Golon, J. Chem. Soc. Chem. Commun. 1996, 277.
201. K. Nowinska, M. Sopa and D. Szuba, Catal. Lett. 1996, 39, 275. 6.1 HYDROGENATION, CARBONYLATION AND RELATED
202. K. Nowinska and D. Dudko, React. Kinet. Catal. Lett. 1997, 61, 187. REACTIONS
203. K. Nowinska and D. Dudko, Appl. Catal. A 1997, 159, 75.
204. K. Nowinska, M. Sopa, D. Dudko and M. Mocna, Catal. Lett. 1997, 49, 43. Polyoxometalates have attracted interest for catalysing the above reactions
205. K. Sano, H. Uchida and S. Wakabayashi, Catal. Surv. Japan 1999, 3, 55. recently. The reduction of aromatic and aliphatic aldehydes and ketones with
206. N. Mizuno and M. Misono, in Catalytic Activation and Functionalisation of Light dihydrogen is catalysed by potassium heteropoly salts supported on y-alumina
Alkanes. Advances and Challenges, Derouane, E.G., Haber, J., Lemos, F., Ribeiro, at 300 °C and H 2 pressure of 23-54 atm without solvent.'15The order of cataly
F.R., Guisnet, M. Eds, NATO ASI Series, Kluwer: Dordrecht, 1998, p. 311. tic activity correlates with the oxidation potentials of polyoxometalates:
207. L. Albonetti, F. Cavani, F. Trifiro and M. Koutyrev, Catal. Lett. 1995, 30, 253.
[SiW120 4o]4- < [PW,20 4o]3_ < [PM oi204 o]3- < [PM o^V sO ^]5". For [PMo,0
208. (a) W. Li and W. Ueda, Catal. Lett. 1997, 46, 261. (b) W. Li, K. Oshihara,
V204o]5- , the conversion of benzophenone into diphenylmethane (eq. 6.1) is
W. Ueda, Appl. Catal. A 1999,182, 357.
209. L.K. Volkova, E.S. Rudakov and V.P. Tretyakov, Kinet. Katal. 1996, 37, 540. quantitative (300 °C, 23 atm, 3.5 h).
210. L.K. Volkova, V.P. Tretyakov and E.S. Rudakov, Kinet. Katal. 1995, 36, 373.
O
( 6 . 1)
+ h 2o
168 CATALYSIS BY POLYOXOMETALATES MISCELLANEOUS CATALYTIC APPLICATIONS OF POLYOXOMETALATES 169
The 1R spectra and XRD pattern for the catalyst before and after the
reaction are identical, indicating that the structure o f polyoxometalate is un
changed.
12-Molybdophosphoric acid catalyses transfer hydrogenation of nitroben
zene to aniline by hydrazine in a homogeneous phase.[2] Protic solvents such as
water or methanol enhance the reduction. In methanol, the reaction occurs with
100% yield at room temperature. A redox mechanism (Scheme 6.1) involving
the reduction of Mo(VI) to Mo(V) in polyanion by hydrazine followed by Scheme 6.2
oxidation of Mo(V) with nitrobenzene is suggested.
6.2 POLYANION-STABILISED CLUSTERS
Transition metal nanoclusters and their catalytic properties are currently an

im portant area of nanoscale chemistry. Finke et u/.[10_13] reported the prepar
ation of near monodisperse nanoclusters of lr(0) and Rh(0) stabilised by
heteropoly anions. For example, the 20±3 A Ir(0) clusters of an average com
position lr(0)^300 were synthesised by reduction of polyanion-supported Ir(I)
complex [(1,5-COD)Ir ■P2W 15N b3062]8 with H2. The process may be repre
sented as
300 [(1 ,5-COD)Ir • P2W 15N b30 62]8~ + 750 H2 — 300C8H 16+
Scheme 6.1
Ir(0)^3oo + 300 [P2W 15N b3062]9“ + 300 H + (6'3>
The two-component systems POM + Pd(II) and POM + Rh(l) have been
The lr(0) clusters show very high catalytic activity and stability in cyclohexene
used for carbonylation, hydroformylation and hydrogenation reactions.f3-8]
hydrogenation. Although the mechanism of self-assembly reaction 6.3 is not
The catalytic system
clear, it is conceivable that the presence o f polyanions is the key to the stabilisa
PdCl2-P O M is efficient for carbonylation of nitrobenzene to methyl phe-
tion of this system.
nylcarbamateJ8]
Augustine et u/.t14^have used polyoxometalates for immobilisation of homo
geneous metal-complex catalysts for enantioselective hydrogenation, which
A rN 0 2 + MeOH + 3 CO —►ArNHCOOM e + 2 C 0 2 (6.2)
may be viewed as an extension of the Finke’s approach. In this work, hetero
poly acids (e.g. H 3PPW12O40I) preadsorbed on a support material serve as
The catalytic activity is in line with the reducibility of polyanions. The
anchoring agents for a homogeneous catalytic complex. A Rh(DiPamp) com
[PM010VO40]4- anion shows the highest activity, whereas 12-molybdosilicate
plex supported on montmorillonite treated with H3[PWi204o] runs fifteen
and heteropolytungstates are much less active. Medium polarity solvents such as
successive hydrogenations of methyl 2-acetamidoacrylate with no loss of activ
acetone and other ketones give the best results. There is evidence that polyox-
ity or selectivity.
ometalates are reduced during the reaction but maintain their structure intact.
Maksimov et a/.[15,161 prepared highly stable colloidal systems containing
A multicomponent redox system consisting of Pd(OAc)2, a Keggin hetero
nanoclusters of precious metals by treating aqueous solutions of precursor
poly acid {XMoi2_nW n04o} (X = P or Si), and Mn(OAc)2 catalyses the oxida
metal complexes and polyoxometalates with reductants. The size of clusters
tive carbonylation of phenol to diphenyl carbonate at 80 °C and 8 atm pressure
so prepared, measured by transmission electron microscopy, depends on the
without solvent.[9] The efficiency of the catalysts depends on the composition of
type of polyoxometalate and the POM/metal ratio (Table 6.1). Supported metal
heteropoly anion. The best yield, 22%, is obtained for E^jPMoöWöCô]. The
catalysts were prepared by adsorption o f these colloids on AI2O3, MgO, or
heteroatom has little effect on catalyst performance. A stepwise redox mechan
carbon support. The metal dispersion in these catalysts was the same as that in
ism (Scheme 6.2), with M n(II)/M n(IlI) enhancing the reoxidation of palladium,
the colloid systems.
is suggested.
no CATALYSIS BY POLYOXOMETALATES MISCELLANEOUS CATALYTIC APPLICATIONS OF POLYOXOMETALATES 171
Table 6.1 Nanoclusters of precious metals stabilised by polyoxometalates1151. 200 C. The oxidation state of Mo in the materials sulfided at 300 C was found
to be 3.8 + for H3[PMoi204o], 4.8 + for Ni3/2[PMoi204o], 4.6 + for Co3/2
Metal (M) [M] [M]/[POM] POM Cluster size
nm [PM012O40], and 5 .4 + for K3[PMoi204o]. The results suggest that the
10~2mol 1_1 mol/mol
active catalyst in the HDS processes will not retain the Keggin structure
Pt 0.2 1.3 [V,0O28f - 2-3 and may consist of mixed thio/oxomolybdates and bulk metal sulfides, e.g.
Rh 0.3 1.8 [Mo70 24]6~ 2-3 M o S 2.
Ru 0.3 1.8 [M o 7024]6~ < 1.5
0.4 [SiWn 0 3|] 8- <2 Silica-supported tungstophosphoric heteropoly acid, H 3PW12O40, has
Ir 2
Au 0.2 3 [N b 6o ,9r 7.5-40 been found to be an efficient catalyst for the HDS of dibenzothiophene
Ag 1.0 5.5 [SiWn039]8- 1-150 (DBT).[26]
Pd 1.0 5 [ v 10o 28]6- 1-7
Pd 1.0 14 [Mo70 24]6~ 3-9
Pd 1.0 24 [H 2W 120 4 o]6- 3-10 h2
-------- ► H 2S + hydrocarbons ^ ^
Pd/Rh 10:1 0.3 3.9 [M o 7o 24r 3-4
PdPt 1:1 0.3 7 [M o 70 24]6_ 2-2.5 S
Pd/Pt 5:1 0.3 8.4 [M o 70 24]6_ 2-6
Pd/Au 1:1 0.3 7 [M o 70 24]6' 3-100
Pd/Ag 1:1 0.3 22 [ S iw n o 39]8- 3-150 Over 30wt% H P A /S i0 2 catalyst in a trickle bed flow reactor at industrially
relevant gas and liquid space velocities (GHSV 600 h-1 and LHSV 6 h-1 and an
H 2 pressure of 30 bar the HDS proceeds with a DBT conversion of 58 % at
290 °C and 80% at 350 °C. These values are comparable to the performance of
6.3 POLYOXOMETALATES AS CATALYST PRECURSORS the industrial Co—M o/A l2 0 3 catalyst (Figure 6.1). No loss of catalytic activity
was observed at 290 °C for a period of 56 h. 31P MAS NM R (Figure 6.2) and
Use of polyoxometalates as catalyst precursors for heterogeneous catalysis is TGA data show that the heteropoly acid was decomposed upon the interaction
attracting interest. Preparation of mixed oxide precatalysts by incorporating with H 2S /H 2 to yield an active HDS catalyst, whose composition is yet un
metal components into the polyoxometalate framework followed by a thermal known.
treatment may be more effective than traditional coprecipitation or successive
impregnation. In particular, this methodology has been explored for the prep
aration of catalysts for hydrodesulfurisation (HDS).[1726]
Griboval et a/.1231 have used two salts of 12-molybdophosphoric acid, non-
reduced C03/2IPM012O40] and reduced C o7/2[PM oi204 o], as precatalysts for the
HDS of thiophene. The salts were supported on y-alumina by impregnating
from aqueous solution. The nonreduced salt was decomposed on impregnation
and produced a well-dispersed surface polymolybdate phase. In contrast, the
reduced salt was stable on the alumina surface after impregnation and drying.
The use of the reduced salt is beneficial because it enhances the interaction of
the Co(II) with polyoxomolybdate in the impregnating solution and allows
avoiding the formation of the surface polymolybdate phase obtained with the
nonreduced salt.
Demirel et a/.1241 have studied conversion of 12-phosphomolybdates, the
heteropoly acid and its Ni(II), Co(II), and K(I) salts, under typical HDS
conditions. In the presence of H2 without H2S, these compounds are stable to
temperatures of ca. 350 °C, loosing only hydration water. When H 2S is present,
decomposition is observed at much lower temperatures. The initial reaction
with H2S occurs as water of hydration is being lost and is complete up to
Figure 6.1 Dibenzothiophene conversion for heteropoly acid and Co-Mo catalysts.1261
172 CATALYSIS BY POLYOXOMETALATES MISCELLANEOUS CATALYTIC APPLICATIONS OF POLYOXOMETALATES 173
4. K. Urabe, Y. Tanaka and Y. Izumi, Chem. Lett. 1985, 1595.

5. Z. Ainbinder and G.W. Parshall, U.S. Patent 4,386,217, 1983.
6. A.R. Siedle, C.G. Markell, P.A. Lyon, K.O. Hodson and A.L. Roe, Inorg. Chem.
1987, 26, 219.
7. Y. Izumi, Y. Satoh, H. Kondoh and K. Urabe, J. Mol. Catal. 1992, 72, 37.
8. F. Ragaini, M. Macchi and S. Cenini, J. Mol. Catal. A 1997, 127, 33.
9. G. Yin, C. Jia T. and Kitamura, T. Yamaji and T. Fujiwara, Catal. Lett. 2000,69, 89.
10. R.G. Finke, in Polyoxometalate Chemistry from Topology via Self-Assembly to
Applications; Pope, M.T., Müller, A. Eds; Kluwer: Dordrecht, 2001; p. 363.
11. J.D. Aiken, III; Y. Lin and R.G. Finke, J. Mol. Catal. A 1996, 114, 29.
12. Y. Lin and R.G. Finke, J. Am. Chem. Soc. 1994, 116, 8335.
13. J.D. Aiken, III and R.G. Finke, Chem. Mater. 1999, 11, 1035.
14. R. Augustine, S. Tanielyan, S. Anderson and H. Yang, Chem. Commun. 1999, 1257.
15. G.M. Maksimov, R.I. Maksimovskaya and K.I. Matveev, Zh. Neorg. Khim. 1997,
42, 990.
16. G.M. Maksimov, V.I. Zaikovskii, K.I. Matveev and V.A. Likholobov, Kinet. Katal.
2000, 41, 844.
17. S. Damyanova, A.A. Spojiakina and D.M. Shopov, Appl. Catal. 1989, 48, 177.
18. A.M. Maitra, N.W. Cant and D.L. Trimm, Appl. Catal. 1989, 48, 187.
19. A. Spojiakina, S. Damyanova, T. Shokhireva and T. Yurieva, React. Kinet. Catal.
Lett. 1985, 27, 333.
20. A. Spojiakina and S. Damyanova, React. Kinet. Catal. Lett. 1994, 53, 405.
21. S. Damyanova and J.L.G. Fierro, Appl. Catal. A 1996, 144, 59.
22. C.N. Siewe and F.T.T. Ng, Energy Fuels 1998, 12, 598.
23. A. Griboval, P. Blanchard, L. Gengembre, E. Payen, M. Fournier, J.L. Dubois and
J.R. Bernard, /. Catal. 1999,188, 102.
24. B. Demirel, S. Fang and E.N. Givens, Appl. Catal. A 2000, 201, 177.
25. B. Demirel and E.N. Givens, Catal. Today 1999, 50, 149.
26. R. Shafi, M.R.H. Siddiqui, G J. Hutchings, E.G. Derouane and I.V. Kozhevnikov,
Appl. Catal. A 2000, 204, 251.
27. F. Cavani, F. Trifirö and A. Vaccari, Catal. Today 1991, 11, 173.
28. I.V. Kozhevnikov, Chem. Rev. 1998, 98, 171.
Figure 6.2 31P MAS NMR spectra: (a) fresh 30% ^[PW Ô ^j/SiCh catalyst; (b) the
catalyst after use for HDS, spinning sidebands asterisked.[26J Reprinted with permission
from Appl. Catal. A 2000, 204, 251. Copyright 2000 Elsevier Science.
Pillaring hydrotalcite-type anionic clays (layered double hydroxides) by

polyanions to form expanded layered materials has attracted considerable
interest. These materials may be used as precursors to mixed oxide catalysts,
which possess basic and/or redox properties (see[27,281 and references therein).
REFERENCES
1. V. Kogan, Z. Aizenshtat and R. Neumann, Angew. Chem. Int. Ed. Engl. 1999, 38,
3331.
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3. Y. Izumi, Y. Tanaka and K. Urabe, Chem. Lett. 1982, 679.
7 C atalysis by Polyoxom etalates in
In d u stry
CONTENTS
7.1 A c id c a t a l y s i s ................................................................................................................................................................... 176
7.1.1 H yd ration o f o l e f i n s .................................................................................................................. 176
7.1.1.1 H yd ration o f p r o p e n e ......................................................................................... 176
7 .1 .1 .2 H yd ration o f is o b u te n e ......................................................................................... 176
7 .1 .2 S ynth esis o f ethyl acetate from ethylene and acetic a c i d ........................................ 178
7.2 S e l e c t i v e o x i d a t i o n ................................................................................................................................ 179
7.2.1 O x idation o f m ethacrolein in m ethacrylic a c i d ............................................................ 179
7 .2 .2 O x idation o f E thylene to A cetic A c id ................................................................................ 180
R e f e r e n c e s ............................................................................................................................................................. 182
In the last three decades, heteropoly compounds have found use as catalysts in
m any industrial processes, Japan being the world leader in their commercial
i s a t i o n . A f t e r first successful industrial application of heteropoly acid as a
homogeneous catalyst for the hydration of propene (Tokuyama process) in
1972,[1,31 several new large-scale processes have been commercialised. In these
processes, heteropoly acids or their salts are used as acid or oxidation catalysts
in homogeneous or heterogeneous systems (Table 7.1). Among them are the
liquid-phase hydration of butenes, the vapour-phase oxidation of methacrolein
to methacrylic acid and o f ethylene to acetic acid, and the gas-phase synthesis
T able 7.1 Industrial p rocesses catalysed by h eterop oly acids.
R ea ctio n C atalyst T yp e3 Start

(R ef.)
C H 2= C H C H 3 + H 20 -*• C H 3C H (O H )C H 3 H 4[SiW 120 4o] horn 1972 (4)

C H 2= C (C H 3)C H O + 0 2 - C H 2= C (C H 3)C O O H M o -V -P -H P A het 1982 C1)
C H 2= C ( C H 3)2 + H 20 - (C H 3)3C O H H 3[P M o i 20 4o] hom 1984 (')
n T H F + H 20 - * H O - [ - ( C H 2)4—O —]„- H H 3[PW 12O40] bip 1985 (2’5a)
C H 3C H = C H C H 3 + H 20 — C H 3C H (O H )C H 2C H 3 H^MoÔ,«] hom 1989 (3)
K e to n e a m in ation to im ine Supported H PA het 1996 (5b)
C H 2= C H 2 + 0 2 -» C H 3C O O H Pd-H4[SiW,2O40]/SiO2 het 1997 (6)
c h 2= c h 2 + c h 3c o o h c h 3c h 2o 2c c h 3 H4[SiW120 4o]/Si02 het 2001 (7)
a) hom = homogeneous, het = heterogeneous, and bip = biphasic

176 CATALYSIS BY POLYOXOMETALATES CATALYSIS BY POLYOXOMETALATES IN INDUSTRY 177
of ethyl acetate from ethanol and acetic acid. On a smaller scale, heteropoly A zeo colum n Light end column
acids are used as acid catalysts for the polymerisation of tetrahydrofuran in a
liquid'liquid biphasic system and synthesis of glycosides in a homogeneous
system.111 Armor151"1discussed, amongst others, recent industrial applications of
heteropoly acid catalysts in USA. which include the continuous animation of a
ketone to inline over a supported HPA in the synthesis of isophorone nitrileimine
by DuPont (1996 start) as well as pilot scale testing in several other processes.
This section briefly describes several industrial processes that use heteropoly
compounds as acid or oxidation catalysts, including the hydration of olefins,
the synthesis of ethyl acetate, the oxidation of methacrolein to methacrylic acid,
and the oxidation of ethylene to acetic acid.
7.1 ACID CATALYSIS
7.1.1 HYDRATION OF OLEFINS
Hydration of alkenes is catalysed by acid to yield a secondary or tertiary alcohol

through the addition of water to alkene that obeys the Markovnikov’s rule.
RCH=CHR' + H20 RCH(OH)CH2R'
Light C2—C4 alkene hydrations are all large-scale industrial processes carried
out with either homogeneous or heterogeneous acid catalysis.141 Alcohols thus Figure 7.1 Flow chart for the Tokuyama process of propene hydration.131Reprinted
obtained are mainly used as solvents. Heteropoly acids are the most active with permission from Catal. Today 1997, 33, 371. Copyright 1997 Elsevier Science.
catalysts for the hydration of alkenes, and they play an increasing role in
commercial production of alcohols by this route.11-31 n-butane and isobutane. Isobutene is the most reactive component in this
mixture, and this property can be utilised for a chemical separation. The selective
7.1.1.1 Hydration of Propene hydration of isobutene to t-butanol by reacting the C4 mixture with water in the
There are several conventional industrial processes that are currently used for presence of dilute mineral acid (e.g. H2S 0 4) or an acid ion-exchange resin is a
manufacturing isopropanol by liquid- or vapour-phase hydration of propene, common method of isobutene separation in industry. t-Butanol is then cataly-
H2S 04, H3P0 4/Si0 2 or sulfonic acid ion-exchange resin being used as cata tically dehydrated to yield pure isobutene.141
lysts. The selectivity to isopropanol is from 93 to 97 %.141 Asahi Chemical Industry in Japan developed a new process for highly selective
Tokuyama in Japan developed a new highly selective process for the pro hydration of isobutene using heteropoly acid as a homogeneous catalyst.11-3’81
duction of isopropanol that uses water-soluble 12-tungstosilicic acid or its acid This process was commercialised in 1984 on a scale o f50000 t/year.111The catalyst
salts to convert propene to isopropanol in the liquid phase at 270-280 °C and is H3[PM oi2C>4o] as a concentrated aqueous solution, 0.15-0.8 mol/1, which cor
200 bar.13,41The aqueous catalyst is recycled after distilling off the alcohol/water responds to 10-50wt%. The reaction is carried out in a counter-current multi
azeotrope. Propene conversion reaches 60-70 % with selectivity to isopropanol stage reactor at a relatively low temperature of 60-80 °C under pressure in a
of about 99 %. The first commercial plant with a production capacity of 30000 binary liquid system of water and butenes. t-Butanol is mainly dissolved in the
tonnes per year began operation in 1972. Figure 7.1 shows a flow chart for the aqueous phase and is easily separated from unreacted butene layer. The conver
Tokuyama process of hydration of propene. sion of isobutene can be increased to almost 100%, while the conversion of
n-butene is less than 0.1 %. After separation of t-butanol, the water phase con
7.1.1.2 Hydration of Isobutene taining the catalyst is recycled to the reactor. The catalyst lifetime is long enough;
phosphoric acid is added to the catalyst solution to stabilise ^ [P M o ^ O ^ ].
The C4 raffinate obtained from steam cracking of naphtha typically contains The process has the following advantages compared to the hydration of
44-49% isobutene, 24-28% 1-butene, 19-21% 2-butene, the rest being isobutene using conventional mineral acids:11,81
178 CATALYSIS BY POLYOXOMKTALATES
C A T A L Y S IS BY PO L Y O X O M E T A L A T E S IN IN D U S T R Y 179
1. High catalytic activity. The stronger acidity of heteropoly acid solution Pilot scale work showed that the following factors are important for efficient
compared to mineral acid at the same concentration and the differing operating this process with the highly active H4[SiWi204o]/Si0 2 catalyst at an
reaction mechanism, leading to the higher reaction order with respect to optimal temperature of 170 to 200 °C and elevated pressure:171
heteropoly acid in concentrated solutions (Section 4.2.2), arc the reasons for
higher reaction rate.
1. Operation with high ethylene/acetic acid feed molar ratio of 10/1 to 14/1.
2. High selectivity. Yields of byproducts, jw -butanol and diisobutene, are
2. Addition of 3-8m ol% steam to the reactor feed to minimise coke formation
significantly lower.
on the catalyst surface. This also leads to a reversible formation of ethanol
3. Low corrosion activity. It is claimed that heteropoly acid forms a passivated
and diethyl ether by-products.
layer on the surface of stainless steel, protecting the reactor from corrosion.
3. Recycle of ethanol and diethyl ether by-products to the reactor.
4. To limit the level of acetaldehyde by-product recycled to the reactor.
5. Protection of the catalyst from ingression of basic impurities (corrosion
7.1.2 SYNTHESIS OF ETHYL ACETATE FROM ETHYLENE A ND
metal ions, other metal salts, nitrogen containing compounds, etc.).
ACETIC ACID
Ethyl acetate is an industrially significant derivative of acetic acid, with the The reaction is only mildly exothermic and can be carried out in a series o f
present world manufacturing capacity about 1 million tonnes per year. It is adiabatic fixed beds of catalyst.
used as solvent in paints, inks and the pharmaceutical industry. Presently, two In 2001, BP Amoco started commercial production of ethyl acetate in their
processes are used for manufacturing ethyl acetate: the esterification of ethanol new plant at Hull, England.
and the Tischenko reaction of acetaldehyde. Both processes have their limita
tions, and there is a need for a cost effective and environmentally benign
process using ethylene feed.14,71 A number of patents have been published on 7.2 SELECTIVE OXIDATION
the production of ethyl acetate by direct reaction of ethylene with acetic acid in
vapour phase using solid acid catalysts. Among them, heteropoly acids have 7.2.1 OXIDATION O F M ETHACROLEIN TO M ETHACRYLIC ACID
shown a great promise.191
BP Amoco has developed a new process for manufacturing ethyl acetate Methacrylic acid has a limited use, but the methyl ester is the most frequently
by the direct reaction of ethylene with acetic acid in the gas phase using used derivative. In 1995, the world capacity for methyl methacrylate was 2.2
12-lungstosilicic acid on silica as the catalyst.17,101 million tonnes per annum. Most methyl methacrylate is used for the manufac
ture of a crystal-clear plastic Plexiglas®. Acetone cyanohydrin method is still
CH2= C H 2 + HO Ac -► CH 3CH2OA c (7.1) the main commercial route to methacrylic acid derivatives, although it suffers
from the overproduction of ammonium bisulfate, the coproduct of this routed41
Table 7.2 shows the excellent performance of the H4[SiWi204o]/Si0 2 cata In the 1980s alternative routes to methyl methacrylate were developed to
lyst in reaction 7.1 in comparison with other solid acid catalysts.[7] Such a avoid the overproduction of N H 4HSO4. One of these is the direct oxidation of
comparison, however, should be treated with caution because of differing isobutene to methacrylic acid, with heteropoly acid as a catalyst. This process
experimental parameters in literature reports. has been jointly developed by Nippon Shokubai-Sumitomo Chemical and
Mitsubishi Rayon and industrialised in 1982 on a scale of over 150000 ton/
Table 7.2 Solid acid catalysts for the reaction o f ethylene with acetic acid to ethyl acetate171. year of methacrylic acid.111
The process consists of two stages, both vapour-phase oxidations: (i) oxida
C atalyst C 2H4/A cO H Temp. Pressure C ontact H 20 in STY
m o l/m o l °C bar time feed g /lh
tion of isobutene to methacrolein over a Bi-Mo mixed oxide catalyst and (ii)
s % m ol methacrolein to methacrylic acid over heteropoly compounds based on molyb
denum, vanadium and phosphorus.
H -m ontm orillonite 5/1 200 50 4 0 144
The oxidation of methacrolein to methacrylic acid is carried out in a fixed-
X E 386 resin 5/1 155 50 4 0 120
N afion-H 5/1 170 50 4 0 102 bed flow reactor at 270-350 °C, contact time of 2-6 s, with a gas feed consisting
H-Zeolite Y 5/1 200 50 4 0 2 of 2-5% methacrolein, 10- 20% steam and a methacrolein/oxygen molar ratio
H 4[SiW ,20 4o]/S i0 2 12/1 180 10 2 6 380 of 2 -4 . At a methacrolein conversion of 70-90%, the selectivity to methacrylic
acid is between 80-85%.
180 CATALYSIS BY POLYOXOMHTALATES CATALYSIS BY POLYOXOMETALATES IN INDUSTRY 181
C a ta ly sts used in th e co m m e r cia l p r o c esses are rep o rted ly th e a cid ic c a esiu m Table 7.3 Catalysts for the direct oxidation of ethylene to acetic acid16*.
salts Hj+n- xC sx[ P M o i2..nV nC>4o] (2 < x < 3; 0 < n < 2). T h e a cid ic sa lts th a t are
Catalyst Temp. Pressure Selectivity STY“
n early sto ic h io m etr ic are p referred .111 C a esiu m and p o ta ssiu m a cid ic sa lts o f
°C atm % g/1 h
h e te ro p o ly a cid s m a y be co n sid e r ed as so lid s c o n sistin g o f an e p ita x ia l th in film
o f the h e te ro p o ly a cid fo rm ed on th e su rface o f th e s to ic h io m e tr ic c a esiu m or P d -C r/A l203 180 1 60 -
Pd—V20 5 248 1 74 2
p o ta ssiu m sa lt.1" 1?1
P d - V 20 5- S b 20 5/A l20 3 250 1 84 27
E x te n siv e m e ch a n istic stu d ies sh o w th at th e o x id a tio n o f m e th a cr o lein re P d - H 3P 0 4/ S i 0 2 150 1 90 56
q u ires a b ifu n ctio n a l c a ta ly sis, i.e. b o th a c id -b a se an d red o x c a ta ly s is (S e c tio n P d - A u - H 2S 0 4/active carbon 150 3.4 85 107
5 .2 .3 ).
a) Space time yield (g/l-catalyst h)
7 .2 .2 O X I D A T I O N O F E T H Y L E N E T O A C E T IC A C I D T h e c a ta ly s ts P d - H 3P 0 4/ S i 0 2 a n d P d - A u - H 2S 0 4/a ctiv e ca rb o n are su g g ested

to fo llo w th is m ech a n ism .
A c etic a cid is m o st c o m m o n ly m a n u fa ctu re d from m e th a n o l a n d c a rb o n m o n In th e o th e r ro u te , e th y len e is first c o n v e rte d in to a c eta ld eh y d e by the W ack er
o x id e b y th e M o n sa n to p r o c e s s.141 A t p resen t, th is p r o c ess a c c o u n ts fo r 6 0 % o f ty p e r ea c tio n , a n d th e a c eta ld e h y d e is th en o x id ise d to a cetic a cid 161 (eq s 7 .2 an d
the w o r ld ’s p r o d u ctio n c a p a c ity . In th e M o n s a n to p r o c ess, th e se lec tiv ities 7 .3 ). T h is m e ch a n ism req uires th e reo x id a tio n o f pallad iu m : P d° —►P d 2+. T h e
b ased o n m e th a n o l an d c a rb o n m o n o x id e fo r th e a c etic a c id p r o d u c tio n are c a ta ly s t sy stem s, su ch a s P d - V 2O s a n d P d - V 20 5 - S b 20 5 / A l 20 3, are b elieved
9 9 and 9 0 % , resp ectiv ely. C o n v e n tio n a lly , rh o d iu m a s th e c a ta ly s t a n d an to fo llo w th is m e ch a n ism , as in th ese sy stem s th e red u ced p a lla d iu m can be
io d id e a s a n a c tiv a to r are u sed fo r th is p r o c ess. A n e w v e rsio n o f th is p ro cess o x id ise d b y v a n a d iu m (V ). O x y g en o r air th en r eo x id ises th e red u ced v a n a d iu m .
ca lled “C A T I V A ” w h ich is b a sed o n a p r o m o te d irid iu m /m eth y l io d id e c a ta ly st In sp ite o f e x ten siv e e ffo r ts o n th e se c o n d ro u te, n o in d u stria lly p r o m isin g results
h as b een d e v e lo p ed a n d co m m e r cia lised b y B P J71 h a v e b e e n o b ta in e d . T h e first ro u te, th ro u g h e th a n o l in term ed ia te, h a s p ro v ed to
A c etic acid is a lso m a n u fa ctu red b y th e o x id a tio n o f e th y le n e to a c e ta ld e be m o r e efficien t.
h yd e w ith the W a ck er c a ta ly st sy stem P d C l2- C u C l 2 (S e c tio n 5 .1 .1 ), w h ic h is S h o w a D e n k o d e v e lo p ed a o n e -sta g e p ro cess for th e p r o d u ctio n o f a cetic
su b seq u en tly o x id ise d to acetic acid w ith a m a n g a n ese a c eta te c a ta ly s t.141 A t a cid b y d irect o x id a tio n o f e th y len e w ith 0 2 o v er a ca ta ly st b ased o n a
p resen t th is a c co u n ts fo r 2 2 % o f th e w o r ld p r o d u ctio n o f a cetic acid . c o m b in a tio n o f p a lla d iu m a n d n o n o x id isin g h e te ro p o ly a cid H 4[S iW i2O 40].161
Illu stra tiv e e x a m p les o f th e p erfo rm a n ce o f th is sy stem are sh o w n in T a b le 5.9,
C 2H 4 + '/2 0 2 - v C H 3C H O (7 .2 ) S e c tio n 5 .2 .3 .4 . In th is p ro cess, a cetic a cid is m a n u fa ctu red w ith h ig h selectiv ity
fro m a m ixtu re o f eth y len e an d o x y g e n in th e v a p o u r p h a se at 1 6 0 -2 1 0 ° C . T h e
C H 3C H O + '/2 0 2 C H 3C O O H (7.3)
rea c tio n is lik ely to p ro ceed th ro u g h the a cid -ca ta ly sed h y d ra tio n o f e th y len e to
e th a n o l, fo llo w e d b y th e o x id a tio n o f e th a n o l to a ceta ld eh y d e c a ta ly sed by
A c etic a cid is a lso p ro d u ced in d u stria lly b y th e d irect liq u id -p h a se o x id a tio n o f
p a lla d iu m (eq s 7 .4 a n d 7.5).
h y d ro ca rb o n s lik e b u ta n e a n d n a p h th a .[41 T h is a c c o u n ts for 9 % o f th e w o r ld ’s
T h e flo w ch art o f th is p ro cess is sh o w n in F ig u re 7 .2. T h e p ro d u ct g a s fro m the
p r o d u ctio n ca p a city . C o b a lt and m a n g a n ese a ceta tes are u sed as c a ta ly sts in th is
reactor is c o o le d to a m b ien t tem p era tu re to sep a ra te acetic a cid a n d o th er o rg a n ic
p ro cess. T h is p ro cess is u su a lly e m p lo y ed w h en sim u lta n e o u s m a n u fa ctu rin g
b y -p ro d u c ts a n d w ater from th e u n co n d e n sed gas. T h e c o n d e n sa te is sep arated
v a rio u s a cid s is d esired or w h en the raw m aterial m a k e s it e c o n o m ic a lly feasib le.
from th e r ea ctio n se c tio n an d led to th e cru d e acetic acid ta n k , w h ich is co n n ected
Several c a ta ly sts h a v e b een rep o rted ^61 for th e d irect g a s-p h a se o x id a tio n o f
to th e p u rifica tio n sy stem . T h e u n co n d en sed g a s is recycled to th e reactor. T h e
e th y len e to a cetic acid (T a b le 7.3). A ll th ese c a ta ly sts are b a sed on p a lla d iu m ,
cru d e a c etic a cid , w h ic h is sto red in a ta n k , is sen t to th e lig h t-en d s co lu m n . T h is
and th e selectiv ity to a cetic acid is q u ite h igh . N o n e o f th ese c a ta ly sts are,
c o lu m n sep a ra tes th e lig h t-en d b y -p ro d u cts, su ch a s a c eta ld eh y d e, eth y l aceta te,
h o w ev er, su ita b le for th e in d u strial p r o d u ctio n o f a cetic acid .
e th a n o l a n d o th ers, from acetic a cid . T h en w a ter is sep a ra ted by ex tra ctio n . T h e
T h ere are tw o m a in rea ctio n m ech a n ism s th at h a v e b een p r o p o se d for the
a c etic acid is fu rth er p u rified to o b ta in a h ig h ly pure a cid as the p ro d u ct.
d irect o x id a tio n o f eth y len e to acetic a c id .[6] T h e first o n e in v o lv e s th e h y d ra
S h o w a D e n k o co n stru cted a co m m ercia l p la n t b ased o n th e n ew p rocess
tio n o f e th y len e to eth a n o l, w h ich is th en o x id ise d to acetic acid .
w ith a c a p a c ity o f 10Ö000 to n s/y e a r o f a cetic a cid in Japan . T h e p la n t is in
c 2h 4 + h 2o - » C H 3C H 2O H (7 .4 ) o p e r a tio n from 1997.161
C o m p a re d to m e th a n o l c a rb o n y la tio n , th e direct o x id a tio n o f eth y len e has
C H 3C H 2O H + 0 2 -► C H 3C O O H + h 2o (7 .5 ) several a d v a n ta g es. T h e m eth a n o l c a rb o n y la tio n requires ex p en siv e m aterials
8 Other Applications o f
Polyoxom etalates
water recycle
Figure 7.2 Flow chart for the Showa Denko process of oxidation of ethylene to acetic CONTENTS
acid.161 Reprinted with permission from Catal. Surv. Japan 1999, 3, 55. Copyright 1999 8.1 A nalytical chemistry ................................................................................................................... 184
Kluwer Academic/Plenum Publisher. 8.1.1 Elemental a n a l y s i s ............................................................................................................ 184
8.1.2 Analysis o f b iom aterials...................................................................................................... 186
lik e H a stello y , du e to the h igh ly co rro siv e cata ly st system . T h e p ro cess a lso 8.2 Se p a r a t io n ........................................................................................................................................ 186
requires pure carb on m o n o x id e p ro d u ction . A ll th is n ecessitates a h eavy in v e st 8.2.1 Processing o f radioactive w aste......................................................................................... 186
8.2.2 Sorption o f g a s e s .................................................................................................................. 187
m ent; hen ce the ca rb o n y la tio n p rocess o n ly b eco m es feasib le o n a large scale,
8.3 C orrosion-resistant c o a t i n g s ............................................................................................... 187
m ore than 2000 0 0 ton s/year. In co n trast, the direct o x id a tio n o f eth y len e is 8.4 P olyoxometalates as additives to inorganic and organic matrices . . . . 188
feasib le even for a p lan t w ith a h a lf th e cap acity, i.e. 100000 to n s/y e a r J 6^ 8.4.1 A dditives in so l-g el m a t r i c e s ......................................................................................... 188
8.4.2 A dditives in polym er m a tr ix e s ......................................................................................... 189
8.5 M e m b r a n e s ........................................................................................................................................ 190
8.5.1 Fuel c e l l s ................................................................................................................................ 190
REFERENCES
8.5.2 Selective e l e c t r o d e s ............................................................................................................ 192
8.5.3 G as s e n s o r s ......................................................................................................................... 192
1. M. Misono and N. Nojiri, Appl. Catal. 1990, 64, 1. 8.6 P olyoxometalates in medicine:antiviral and antitumoral activity . . . . 192
2. Y. Izumi, K. Urabe and M. Onaka, Zeolite, Clay and Heteropoly Acid in Organic R eferences ............................................................................................................................................ 193
Reactions; Kodansha/VCH: Tokyo, 1992; p. 99.
3. Y. Izumi, Catal. Today 1997,33, 371.
4. K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry; 3rd ed.; VCH; Wein- V a rio u s a p p lica tio n s o f p o ly o x o m e ta la te s are b ased o n their u n iq u e p h y sico
heim, 1997. ch em ica l p rop erties (T ab le 8.1). T h ese in clu d e large a n io n size a n d m ass,
5. (a) A. Aoshima, S. Tonomura and S. Yamamatsu, Polymersfor Advanced Technolo
gies 1990, 2, 127. (b) J.N. Armor, Appl. Catal. A. 2001, 222, 407. Table 8.1 Physicochemical properties of polyoxometalates utilised in
6. K. Sano, H. Uchida and S. Wakabayashi, Catal. Surv. Japan 1999, 3, 55. various applications111.
7. M.J. Howard, G.J. Sunley, A.D. Poole, R.J. W att and B.K. Sharma, Stud. Surf. Sei.
Catal. 1999, 121, 61. Mixed oxide like
8. (a) A. Aoshima, Shokubai 1987, 29, 378. (b) A. Aoshima, S. Yamamatsu and T. Discrete ionic structure
Nanosized anions (diameter, 0.6-4 nm)
Yamaguchi, Nippon Kagaku Kaishi 1987, 976; 1987, 984; 1990, 233.
Large anion charge (from —3 to greater than —14)
9. (a) Y. Murakami, T. Hattori and H. Uchida, Kogyo Kagaku Zasshi 1969, 70, 1945.
High molecular weight (103 - 104)
(b) K. Inoue, M. Iwasaki and K. Matsui, EP-A-538826, 1993. (c) K. Sano, M. Incorporate over 70 elements inside heteropoly anions
Nishiyama, T. Suzuki, S. Wakabayashi and K. Miyahara, EP-A-562139, 1993. High conductivity of solids
10. (a) M.J. Howard, Chemistry and Industry 1997, 19, 758. (b) M.P. Atkins and B. Strong Bronsted acidity
Sharma, EP-A-757027, 1997. Multielectron redox agents
11. K. Brückman, J. Haber, E. Lalik and E.M. Serwicka, Catal. Lett. 1998, 1, 35. Photoreducible/oxidisible
12. E.M. Serwicka, K. Brückman, J. Haber, E.A. Paukshtis and E.N. Yurchenko, Appl. Colour of oxidised forms different from colour of reduced forms
Catal. 1991,73, 153. High solubility of heteropoly acids in H2O and polar organic solvents
13. S. Tatematsu, T. Hibi, T. Ohukara and M. Misono, Chem. Lett. 1987, 865. Transferability of heteropoly anions into nonpolar solvents
184 CATALYSIS BY POLYOXOMETALATES OTHER APPLICATIONS OF POLYOXOMETALATES 185
Table 8.2 Main applications of polyoxometalates11,21. Table 8.3 Elemental analysis based on polyoxometalate chemistry1'1.
Catalysis Element Method
Analytical chemistry
Corrosion resistant coatings Si Voltammetry, SiM o^; polarography, SiM o^; photometry, SiMo^
Separations, processing radioactive waste, and sorbents o f gases blue
Membranes P Spectrophotometry, PM012 reduced by ascorbic acid
Sensors As Spectrophotometry, reduced M o-Sb-As complex
Cation exchangers
Dyes and pigments Ge Spectrophotometry, GeM oi2
Electrooptics Sn Spectrometry, after reduction of SiM o^ by Sn(II)
Electrochemistry, electrodes, fuel cells, and capacitors A1 Spectrophotometry, an ion-association complex of
Dopants in sol-gel and polymer matrices molybdoaluminium heteropoly acid with crystal violet
Flammability control
Medicine Ti Spectrophotometry, as ion-association complex of
molybdotitanophosphoric acid with Nile Blue
V Spectrophotometry, [PWn Viv04o]5-; photometry,
electron- and proton -tran sfer abilities, high B ronsted acid ity o f the co rresp on d vanadomolybdophosphate
ing acids, so lu b ility and extractability, etc. A m o n g the a p p lication s o f p o ly o x - Cu Spectrophotometry, based on Cu(II) catalytic effect on PM012/I
o m etalates, catalysis is by far the m ost im p ortan t (C h apter 7). A b o u t 8 0 -8 5 % redox reaction
o f the patent and app lied literature o n p o ly o x o m eta la tes is relevan t to their Mo Spectrophotometry, tungstomolybdophosphate blue
catalytic properties.[I] O ther uses inclu de m an y fields such as ch em ical and W Spectrophotometry, tungstomolybdovanadophosphate
b iochem ical analysis, n ew m aterials w ith ad van ced ch aracteristics, electro Nb Spectrophotometry, ion-associated complex of molybdoniobate with
chem istry and electrochem ical devices, p rotection from corro sio n , m edicine, crystal violet in PVA and arabic gum
etc. (T able 8.2). T he easier availab le and b etter-stu died K eggin type p o ly o x Hf Spectrophotometry, ion-associated complex of
o m etalates d o m in a te in the ap p lication s. O ther structural typ es attract an
molybdolanthanohafnic acid with Nile Blue in PVA
increasing interest as well. T h e variou s uses o f p o ly o x o m e ta la te s h ave been Zr Spectrophotometry, an ion-associated complex of zirconomolybdic
acid with Nile Blue in PVA
review ed by K a tso u lis^ and by P op e and M üller J2,31 S om e o f the ap p lication s,
other than catalysis, are briefly discussed in this chapter. Sc Spectrophotometry, an ion-associated complex of molybdoscandic
Th Spectrophotometry, an ion-associated complex of molybdothoric
8.1 ANALYTICAL CHEMISTRY
Y Spectrophotometry, using Nile Blue, M0O4', and PVA
Te Spectrophotometry, an ion-associated complex of molybdotelluric
P o ly o x o m eta la tes h ave lo n g been used for elem en tal analysis and determ in
acid with butylrhodamine B in PVA
ation o f biom aterials. T h is is m ain ly b ased on p roperties o f p o ly o x o m eta la tes
Ta Spectrophotometry, an ion-associated complex of molybdotantalic
such as their high m olecular w eight, red ucib ility to form co lou red species acid with Nile Blue in PVA
(h eterop oly blues), and the variety o f elem en ts th at can be in corp orated in
Hg Colorimetry, with dithizone in the presence of PW12
p o lya n io n s. O nly throu gh h eterop oly m oly b d a te fo rm ation can som e 26 elem
Bi Spectrophotometry, molybdobismuthophosphoric acid, reduction
ents be determ ined.
with ascorbic acid
Au Kinetic spectrometric method using the reduction of PM 012 by
formic acid
8.1.1 E L E M E N T A L A N A L Y S IS Tl Precipitation with PW12 and n-BojNBr, redissolution of precipitate
in alkaline solution and determination of Tl by spectrophotometry
T able 8.3 sh o w s so m e illustrative exam p les o f elem en tal an alyses u sin g p o ly Sb Spectrophotometry, ternary HPA Sb-As-Mo-ascorbic acid
ox o m eta la tes. T h e m o st w id ely used is the an alysis o f P and SiJ4' T h is is based S Spectrophotometry, after conversion to sulfide form; an HPA is used
on the inco rp o ra tio n o f the elem en t in a h eterop oly an io n fo llo w ed by its as reagent
determ in ation either gravim etrically or by sp ectroscop ic or electroch em ical
186 CATALYSIS BY POl YOXOMETALATES OTHER APPLICATIONS OF POLYOXOMETALATES 187
tech n iq u es after red u ctio n to h e te ro p o ly b lu es. S o m e o f th ese te ch n iq u e s a llo w o f a lu m in a or silica gel. T h ese ion ex ch a n g ers w ere cla im ed to rem o v e C s+ from
d eterm in a tio n o f n a n o m o la r co n c en tra tio n s o f P or Si in s o lu tio n s .11,21 w a ste so lu tio n s. C ro w n eth er/P O M a d d u cts w ere u sed to extract C s+ from
P o ly tu n g sta te s h ave lo n g b een e m p lo y ed a s im a g in g a g e n ts for e lectro n a q u e o u s so lu tio n in to n itro b en zen e or nitrom eth ane.*81 It w a s d em o n stra ted
m icroscopy.*51 th a t m o re than 9 9 % o f ca esiu m ca n be extracted in n itro b en zen e. A n o th e r
m e th o d cla im ed to sep arate C s+ fro m ra d io a ctiv e w a ste by p recip ita tio n w ith
H ? [P M i20 4 o] (M — M o or W ), fo llo w ed by a m m o n iu m h y d ro x id e treatm en t to
8 .1 .2 A N A L Y S IS O F B IO M A T E R IA L S
d iss o lv e the p recip ita te a n d su b jectin g it to an electric field. T h e c a th o d e
so lu tio n c o n ta in e d all th e C s as C sC l w ith less th a n 1 % o f P or M o .|9]
C lin ical ch em ists ro u tin ely use p o ly o x o m e ta la te s to a n a ly se v a r io u s b io m a te r
O th er se p a r a tio n s o f ra d io a ctiv e n u clei w ith th e use o f p o ly o x o m e ta la te s
ials su ch as p ro tein s, a lk a lo id s, d ru gs, etc.*2,61 T h e se a n a ly se s are b a sed o n the
in clu d e Sr,*10' " 1 U,*'2] N p and Pu.*'3]
w ell-k n o w n ab ility o f p o ly o x o m e ta la te s to c o a g u la te p ro tein s and p recip itate
m a n y b io a c tiv e o rg a n ic m olecu les. S o m e e x a m p les are sh o w n in T a b le 8.4. T h e
m e th o d s in v o lv e grav im etry, sp ec tro p h o to m e try after red u ctio n to b lu es, thin
8 .2 .2 S O R P T IO N O F G A S E S
layer c h r o m a to g ra p h y , etc. (for a review , see*61).
S o lid p o ly o x o m e ta la te s h ave b een cla im ed as so rb en ts o f g a ses fo r en v iro n

8.2 SEPARATION m e n ta l p r o te ctio n . M o st a p p lic a tio n s o f p o ly o x o m e ta la te s h a v e dea lt w ith the
rem o v a l o f flu e g a ses, trea tm en t o f to x ic o rg a n ic c o m p o u n d s , rem o v a l o f
8.2.1 P R O C E S S IN G O F R A D I O A C T I V E W A S T E a m in e s an d m erca p ta n s, etc.*'1 K eg g in h e te ro p o ly a cid s an d sa lts w ere used to
a d so rb flu e g a ses, su ch as N O x, S 0 2, an d C 0 2.*141 A c o m p lex ca ta ly st sy stem
T here is c o n sid era b le a n a ly tica l and p a ten t literatu re o n the use o f p o ly o x o m e in clu d in g H 3[P M I2C>4o] (M = M o o r W ) w a s u sed for th e d e c o m p o sitio n o f
ta la tes for the p r o cessin g o f rad io a ctiv e n u cle i.1111 M a c r o c y c lic c r o w n eth ers an d to x ic o r g a n ic c o m p o u n d s in g a se s fro m in cin era tio n o f m u n icip a l r efu se.1'51
h etero p o ly a cid s w ere claim ed to extract ca esiu m ions*71 from a q u e o u s so lu K eg g in h e te r o p o ly a cid s w ere a lso used as a b so rb en ts fo r H 2S, th e final
tio n s. 134C s an d 137C s are u su a lly p resen t in sm all q u a n tities in ra d io a ctiv e p r o d u cts b ein g su lfu r, h e te ro p o ly b lu e a n d w ater. T h e h e te ro p o ly blue w as
a q u eo u s w a ste. T h eir p resen ce m a k es so lid ific a tio n o f th is w a ste d ifficu lt b e reo x id ised w ith the use o f o x id a n ts su ch as N O ? , F e 3+, C l2, e tc .1'61 H 3[P M o6
c a u se th ey ev a p o ra te to a n o tic ea b le d egree a n d leach o u t o f th e so lid p r o d u cts W 6O 40] o n a p o r o u s su p p o rt w a s used for th e p u rifica tio n o f v en t air from
w h ich are in ten d ed for p erm an en t sto ra g e su ch as, e .g ., cem e n t o r b itu m en o d o r o u s c o m p o n e n ts , su ch as a m in es a n d m ercap tan s.*171 A c a ta ly tic co n v erter
b lo ck s. S o lid a d d u cts o f H n[X M j2 0 4 o] (X = Si, P; M = M o , W ) w ith cro w n for th e red u ctio n N 0 2 to N O in p o llu te d air or flu e g a ses w ith th e use o f
eth ers w ere prepared by m ix in g th e tw o c o m p o n e n ts in a c ro w n e th e r/P O M H 3[P M o |2O 40] w a s describ ed .*181 In so lu b le h e te r o p o ly sa lts a n d p o ly a lk y len e
m o la r ra tio o f 0 .5 :1 -2 :1 in a so lv e n t lik e a c eto n e. T h e preferred c r o w n eth ers g ly c o ls w ere cla im ed as so rb en ts fo r R a gas.*191
w ere b e n z o -1 5 -cr o w n -5 , d ib en zo -2 1 -c ro w n -7 , and d ib e n z o -3 0 -c r o w n -1 0 . Io n
ex ch a n g ers w ere p repared w h en th e so lid a d d u ct w a s fo rm ed in th e p resen ce
8.3 CORROSION-RESISTANT COATINGS
Table 8.4 Analysis of biomaterials using polyoxometalates*61.
M eta l su rfa ces are c o m m o n ly p ro tected fro m c o rr o sio n usin g c o rr o sio n in h ib i
Sample Substance Method to rs su ch as ch r o m a te s, p h o sp h a te s, or silica tes. T h e se c o m p o u n d s fo rm a
c o rr o sio n -r esista n t c o a tin g o n the m etal su rfa ce b y a d so rp tio n a n d /o r fo rm a
Whole blood Si spectrophotometry, SiM oi2 blue
tio n o f an o x id e layer. A lth o u g h to x ic, th e c h r o m a te s are e fficien t c o rro sio n
Blood serum Si spectrophotometry, SiM oi2 blue
in h ib ito r s, k n o w n as a n o d ic p a ssiv a tin g inh ib itors.*'1
Blood urine As spectrophotom etry or nephelometry, A sM oi2
M a n y rep orts o n th e use o f p o ly o x o m e ta la te s as c o rr o sio n in h ib ito rs h ave
blue
b een p u b lish e d (fo r a review , see*'1). P o ly o x o m e ta la te s are g en era lly less to x ic
Biosolutions uric acid spectrophotometry, SiM ot2 blue
uric acid gravimetry, PM oi2 th a n th e c h r o m a te s. T h eir ea sy red ox tra n sfo rm a tio n s w ith o u t m ajor structural
c h a n g e s an d th e fo r m a tio n o f in so lu b le sa lts w ith large c a tio n s m a k e th em
Cell nuclei histones spectrophotometry, PM o,2 blue
p r o m isin g o x id isin g a n d film -fo r m in g co rr o sio n in h ib ito rs.
Animal tissues cocaine thin layer chrom atography, PM oi2 in ethanol
amidopyrine gravimetry, SiM oi2 P o ly o x o m e ta la te s h ave b een stu d ied fo r co rr o sio n in h ib itio n o f a lu m in iu m
an d its a llo y s in a q u e o u s m ed ia at high tem peratures.*201 Such a llo y s are used in
a to m ic in d u str y , a n d th e r e fo r e a c o r r o s io n in h ib ito r s h o u ld h a v e h ig h r a d ia tio n a b r a s io n r e s is ta n c e are o f grea t im p o r ta n c e . C o m m o n in o r g a n ic m a tric es are
sta b ility . In th e p r e se n c e of is o p o ly or h e te r o p o ly tu n g s ta te s , su c h as u s u a lly d e r iv a tiv e s o f A l, S i, G e , T i, or Z r a lk o x id e s a n d , to a lesser e x ten t, o f
( N H 4) u-t[H2W i 20 42] o r ( N H 4) 6[P 2W 180 6 2 ] (1 0 0 g/1), th e r a te o f c o r r o s io n S n , P b , o r N b a l k o x i d e s / 27,281
d e c r e a se d s ig n ific a n tly , fa c to r o f te n c o m p a r e d to th a t in p u re w a te r at U s in g s o l - g e l te c h n iq u e s, p o ly a n io n s su ch as [ P W ^ O ^ ] 3 - , [S iW i20 4o]4% or
2 5 0 C . H o w e v e r , th e [ P M o ^ O ^ ] 3' a n io n in c r e a se d th e rate o f c o r r o s io n [ W i o 0 32]4 - w e re in c lu d e d in to gel m a tr ic e s .1291 T h is led to io n ic c o n d u c to r s , a lso
w h ic h w a s a ttr ib u te d to th e in s ta b ility o f th is p o ly a n io n in d ilu te s o lu tio n s . p o s s e s s in g e le c tr o c h r o m ic a n d p h o to c h r o m ic p r o p erties.
X P S stu d ie s s h o w e d th e p r e se n c e o f W 6+ a n d W 5+ in th e film . A p p a r e n tly , th e S ilo x a n e c o a tin g s o n steel w ere m a d e b y th e h y d r o ly s is /c o n d e n s a tio n o f
r e d u c tio n o f W 64" to W 5+ w a s c a u s e d b y A l° . S im ila r ly , w h e n m o ly b d o p h o - a lk o x y s ila n e s a n d /o r sila n o ls in th e p r e se n c e o f a h e te r o p o ly a c id , e .g .
s p h a te s w e re u s e d , m o ly b d a te w a s in c o r p o r a te d in th e film , w ith M o 6+ r ed u c ed H 4[ S iM o i20 4o ] / 301 T h e se silo x a n e c o a tin g s sh o w e d g o o d a d h e s io n a n d w a ter-
to M o5+. T h e n a tu re o f th e p o ly tu n g s ta te film r em a in s u n k n o w n . A lu m in iu m - r e p e lle n t p r o p e r tie s a s w e ll a s se lf-c le a n in g c h a r a cte ristic s. S ilo x a n e -P O M c o a t
c o n ta in in g h e te r o p o ly tu n g s ta te s m ig h t h a v e fo r m e d in th e film . in g s w e r e r e p o r te d to e x h ib it a n tista tic p r o p e r tie s.1311
P o ly o x o m e t a la t e s w e re r e p o r te d a s c o r r o s io n in h ib ito r s fo r o th e r m e ta ls S ta b le in s o lu b le H 3[P W i20 4o ]/tita n ia g e ls w e re c la im e d to h a v e e le c tr o c h r o
su ch a s z in c a n d g a lv a n is e d steel. T h e c o m m o n K e g g in ty p e h e te r o p o ly a c id s, m ic p r o p e r tie s a n d io n ic c o n d u c t iv it y /321 T h e ir e le c tr o c h r o m ic p r o p e r tie s w ere
H n[ X M i2 0 4 o] (X = P , Si; M = M o , W ), w ere te s te d a s p a s s iv a to r s fo r z in c a ttr ib u te d t o th e tita n ia g e ls a n d th e ir c o n d u c tiv ity to th e p r e se n c e o f p o ly o x
p la tin g , th e m o s t e ffic ie n t a c id b e in g H 3[ P M o i20 4o ] /211 o m e ta la te s . P r o to n c o n d u c tiv e s o lid m a te r ia ls w e re o b ta in e d b y d o p in g h e te r o
A s a h i C h e m ic a l In d u str y c la im e d [221 th a t s ta in le ss ste e l s h o w e d h ig h c o r r o p o ly a c id s in to th e a m o r p h o u s o x id e m a tr ix e s o f e le m e n ts su ch a s B, A l, S i, G e ,
sio n r esista n c e a fter tr ea tm e n t w ith a 10% su lfu r ic a c id s o lu t io n c o n t a in in g S n , P , T i, o r Z r .[33] S o m e d o p e d o x id e s w e re c la im e d a s s o lid e le c tr o ly te s fo r fu el
100 p p m H 3[ P M o 12O 40] fo r a sh o r t tim e a t 100 °C . A s d is c u s s e d in C h a p te r 7, c e l l s / 341
H 3[ P M o i2 0 4 o] is u s e d a s th e c a ta ly s t fo r th e A s a h i C h e m ic a l I n d u str y p r o c e s s T h e P O M - d o p e d g e ls m a y fin d a p p lic a tio n s in so lid -s ta te e le c tr o c h r o m ic
o f liq u id -p h a s e h y d r a tio n o f is o b u te n e . T h e lo w e r c o r r o s io n a c tiv ity o f th e d is p la y s a n d w in d o w s fo r r elia b le lig h t c o n tr o l fo r b u ild in g s a n d a u t o m o b il e s / 11
h e te r o p o ly a c id as c o m p a r e d to c o n v e n t io n a l m in e r a l a c id s is th e im p o r ta n t
a d v a n ta g e o f th is p r o c e s s / 231
In ter estin g ly , m o ly b d o v a n a d o p h o s p h a t e s w e re r e p o r te d to in h ib it c o r r o s io n
8 .4 .2 A D D IT IV E S IN P O L Y M E R M A T R IC E S
o f ste e l S t3 (m ild ste el) in a s o lu t io n c o n ta in in g 150 m g/1 C l~ a n d 5 4 0 m g/1 S O ^ at
4 0 °C d u rin g 1 0 0 h / 24,251 S in ce th e se p o ly o x o m e t a la t e s are w id e ly u s e d a s c a ta
T h e in c o r p o r a tio n o f p o ly o x o m e t a la t e s in to o r g a n ic m a tric es o f c o n d u c tiv e
ly s ts fo r se le c tiv e o x id a tio n in liq u id p h a se (C h a p te r 5), th e ir p a s s iv a tin g a b ility
p o ly m e r s h a s a ttr a c te d c o n sid e r a b le in te re st. T h e m a ter ia ls th u s o b ta in e d are
w o u ld b e a n im p o r ta n t v a lu e -a d d in g c o n tr ib u tio n to th e ir c a ta ly tic p r o p e r tie s.
u s e fu l a s s o lid c a ta ly s ts fo r c h e m ic a l a n d e le c tr o c h e m ic a l r ed o x p r o c e s se s in
S a lts o f p o ly o x o m e t a la t e s w ith o r g a n ic c a tio n s , e .g . q u a te r n a r y a m m o n iu m liq u id p h a se , a s w e ll a s e le c tr o d e s, se n so r s, etc. T h e o r g a n ic m a trices in clu d e
c a tio n s , w h ic h th e m se lv e s are k n o w n a s a c la s s o f c o r r o s io n in h ib ito r s , w e re c o n d u c tiv e p o ly m e r s su ch a s p o ly p y r r o le , p o ly th io p h e n e , p o ly a n ilin e , p o l y ( l -
c la im e d to e x h ib it g o o d a n tic o r r o s iv e p r o p e r t ie s /261 n a p h th o l), o r p o ly (p -p h e n y le n e ). T h e in c o r p o r a tio n o f p o ly o x o m e ta la te s ty p ic
L ittle is k n o w n s o fa r a b o u t th e m e c h a n is m s o f c o r r o s io n in h ib itio n b y a lly in v o lv e s th e c h e m ic a l o r e le c tr o c h e m ic a l o x id a tio n o f p o ly m e r isa b le m o n o
p o ly o x o m e t a la t e s . S ig n ific a n t o n g o in g r esea r ch s h o u ld in c r e a se th e u n d e r m er in th e p r e se n c e o f a p o ly o x o m e t a la t e s o lu tio n . T h e P O M -d o p e d p o ly m e r
s ta n d in g o f th e s e e ffe c ts a n d h e lp t o d e v e lo p a n d im p r o v e th e in h ib ito r s c a n b e d e p o s ite d o n e le c tr o d e s (e .g . c a r b o n o r g r a p h ite ) a n d u sed in e le c tr o
b a s e d o n p o ly o x o m e ta la te s . c h e m ic a l c a t a l y s i s / 11 T a b le 8.5 lis ts s o m e e x a m p le s o f P O M -d o p e d c o n d u c tiv e
p o ly m e r s a n d th e ir a p p lic a tio n s.
P o ly o x o m e t a la t e s are a ls o in c o r p o r a te d in o r g a n ic n o n c o n d u c tiv e p o ly m e r
8 .4 P O L Y O X O M E T A L A T E S A S A D D IT IV E S T O IN O R G A N IC A N D m a tr ic e s to fo r m c o m p o s ite m a teria ls. S u ch c o m p o s ite s are c la im ed to h a v e
O R G A N IC M A T R IC E S a d v a n c e d o p to e le c tr o n ic p r o p e r tie s d u e to th e p resen ce o f p o ly o x o m e ta la te s .
T h e p o ly m e r s in c lu d e p o ly v in y l a lc o h o l, b u ta d ie n e -s ty r e n e ru b b er, e p o x id e
8 .4 .1 A D D IT IV E S IN S O L -G E L M A T R IC E S r esin s, e t c / 11 F o r e x a m p le , a p h o to c h r o m ic r ec o rd in g m a ter ia l c o n s is tin g o f
(y -g ly c id o x y p r o p y l)tr im e th o x y s ila n e /H 4[S iW i20 4o] o n a p o ly a c r y la te p la te w a s
P o ly o x o m e t a la t e a d d itiv e s c a n b e in tr o d u c e d in in o r g a n ic m a tr ic e s b y s o l - g e l p a te n te d . In fo r m a tio n w a s r ec o rd ed b y irr a d ia tio n w ith lig h t a n d era sed b y
m e th o d s th a t are n o w w id e ly u sed fo r th e p r e p a r a tio n o f in o r g a n ic d e sig n e r e x p o s in g th e c o a t e d su rfa c e to air o r o x y g e n / 421
m a te r ia ls .127,281 T h e p r im a ry a p p lic a tio n o f th e se c o m p o s it e sy s te m s is in c o a t
in g s w h er e c h a r a c te r istic s su ch a s o p tic a l p r o p e r tie s, a d h e s io n , h a r d n e s s a n d
Table 8.5 Polyoxometalate-doped conductive polymers. Table 8.6 Spec‘ific resistance of polyoxometalate plates at room
tem perature3 '
POM Polymer Application Ref.
[35] Compound Specific resistance, fl • cm
[H2W ,204 o]6' Polypyrrole Proton permeability
Electrocatalytic reduction of 0 2
[36] H3[PM oi204oJ ■30H2O single crystal 5
[PMo,204o f ' Polypyrrole
and CIO, H3[PM o 1204 o] • 30H2O 11
Detection of catecholamines, [37-39] H 3[PW,204 o] • 30H2O single crystal 7
[PM012O40]3' Poly (5-amino-1- 12
H 3[PW,2O40] • 30H2O
naphthol) chemical polymerisation,
(N H 4)3[PM oi204 o] • 3H20 21
electrocatalysis
[40] K3[PM oi204 o] • 6H20 22
[Si\V1204o]4 ' Polyaniline Electrocatalytic reduction of N a3[PM oi2O40] • 21H20 17
C103 , B r0 3 (N H 4)3[PW,204 o]-3 H 20 20
Polypyrrole Catalysis of 0 2 reduction [41] K3[PM oi204 o] ■6H20 20
[P2W18062]6‘ [35]
[Dy(SiM o,i0 39)2]13 Polypyrrole Electrocatalytic reduction o f N aafPW Ô ^] • 21H20 19
C103-, BrO, H4[SiMoi2O40] • 26H20 12
H4[SiMoi204o] • 22H20 24
Na4[SiW|20 4o] ■30H2O 13
Na4[SiW1204o] • 22H20 22
H 5[BW1204 o] ■30H2O 13
8 .5 M EM BRANES
K 6[P2W ,80 62] • 14H20 123
N a5[W60 24] • 8H20 235
M u ch o n g o in g research co n cen tra tes o n th e d e v e lo p m en t o f n e w m em b ran es Z r0 2 - CaO (solid solution) 10000 (600 °C); 40 (1000 °C)
th a t in clu d e p o ly o x o m e ta la te s as c o n d u ctiv e c o m p o n e n ts. T h ese stu d ies e x p lo it ß-Al20 3 700 (RT); 14 (300 C)
the high io n ic co n d u ctiv ity o f p o ly o x o m e ta la te s, e sp ecia lly th eir acid form s, in
a) The plates, 15mm x 15mm x 2mm, prepared under pressure o f 1000atm; specific
the so lid state. T h ese m em b ran es are c o m m o n ly u sed in v a rio u s electro ch em ica l resistance measured at an AC frequency o f I kHz
d evices su ch as electro ly tic (fu el) cells, selective electro d es, g a s sen so rs, etc.
8.5.1 F U E L CELLS
S o lid h y d rated h etero p o ly acid s an d their salts exh ib it extrem ely h ig h p r o to n ic

co n d u ctiv ity .^431 T heir co n d u ctiv ity is com p a ra b le to th a t o f c o n v e n tio n a l liq u id
electro ly tes (T ab le 8.6), w ith m u ch easier h a n d lin g co m p a red to th e liq u id
system s. T h is property h as b een used for d esig n in g electro ch em ica l c e lls.144,451
T h e h etero p o ly acid p lates were d em o n stra ted to fu n ctio n effectiv ely as so lid
sep arators b etw een the a n o d e and c a th o d e ch am b ers o f H 2/ O 2 fu el c ells, w ith P t
or Pd as a ca ta ly st (F igu re 8 .1 ).[44,45] T h ey a llow ed the selective p er m ea tio n o f
p r o to n s fro m the a n o d e to the c a th o d e ch am b er, p r o b a b ly th ro u g h h y d ro g en
b o n d ed n etw o rk s facilitated by so lv en t m o lecu les. T h e electro n s gen erated b y the
o x id a tio n w ere su p p lied in to th e a n o d e b y an extern al circu it. T h e O 2 - p rod u ced
by red u ctio n o f 0 2 co m b in ed w ith the arriving p r o to n s to fo rm H 20 . T h is d evice
c o u ld be u sed for m ea su rin g p artial pressu re o f H 2 or 0 2. T h e electro ly tic
gen era tio n o f H 2 fro m steam u sin g a sh eet o f p o ly cry sta llin e H 3IP M 0 12 O 40].
3 OH2O as a so lid sep arator w as p a te n te d .[46] L im ita tio n s o f th ese cells are the
stro n g in flu en ce o f h u m id ity o n their p r o to n ic c o n d u ctiv ity , d iffu sio n a l p r o b
lem s, and the high io n ic resistan ce a sso cia ted w ith ex cessiv e e lectro ly te th ick n ess.
Figure 8.1 Schematic representation of an electrochemical cell utilising a polycrystal
O ther types o f liq u id and so lid fu el cells based on h e te ro p o ly acid s h a v e been line heteropoly acid as a solid separator.[1] Reprinted with permission from Chem. Rev.
describ ed in the litera tu re.[11 1998, 98, 359. Copyright 1998 American Chemical Society.
192 CATALYSIS BY POL.YOXOMETALATES OTHER APPLICATIONS OF POLYOXOMETALATES 193
8 .5 .2 S E L E C T IV E E L E C T R O D E S T h e m ech a n ism o f an tiviral a ctiv ity o f p o ly o x o m e ta la te s rem ain s u n k n o w n .
T h ere is str o n g e v id en ce that p o ly o x o m e ta la te s can p en etra te cell m em b ra n es
M a n y io n -selectiv e e lectro d es b ased on p o ly o x o m e ta la te s and p o ly v in y l c h lo r and lo ca lise in tracellu larly.'521 R e a so n s for b io lo g ic a l a ctiv ity o f p o ly o x o m e ta
ide (P V C ) h a v e been d e v e lo p e d .'1' T h e e lectro d es b ased on H ^ P W ^ O ^ ] an d la tes m ay in clu d e io n ic size an d ch a rg e, electro n -tra n sfer pro p erties, b eh a v io u r
cro w n eth ers (e.g. 1 8-crow n -6) p recip itated on a P V C m em b ra n e sh o w e d g o o d o f p o ly a n io n s in ex trem ely d ilu te so lu tio n s at p h y sio lo g ic a l p H . etc.
selectiv ity for o rg a n ic a m m o n iu m io n s su ch as B u N H | , C 6H 5C H 2N H J ,
E t; N I U , and E u N H + w ith in the c o n c en tra tio n ran ge o f 10 1 - 10“ 5 m J471
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m ed icin a l ch em istry o f p o ly o x o m e ta la te s to d a te (for a recen t review , see'521). Patent 04,035,716, 1992 (Chem. Abstr. 1992, 117, 117592).
T h e an tiviral a ctiv ity o f p o ly o x o m e ta la te s w a s rep orted as early as 1971 18. J. Myai and Y. Yanase, Japanese Patent 08,304,377, 1996 (Chem. Abstr. 1996, 126,
w h en R a y n a u d et a /.'531 fo u n d that h e te ro p o ly tu n g sto silic a te s in h ib ite d m u rin e 108083).
leu k em ia sa rco m a virus in vitro. F u rth er stu d ies o f v a rio u s g r o u p s sh o w e d the 19. F. Sebesta, Chech Patent 180,789, 1979 (Chem. Abstr. 1979, 93, 53243).
20. S.V. Lomakina, T.S. Shatova and L.P. Kazansky, Corros. Sei. 1994, 36, 1645.
e ffectiv en ess o f th ese p o ly o x o m e ta la te s a g a in st several viru ses su ch as vesicu la r
21. N. Wu, S. Wang, Z. Wang, H. Xu and J. Fang, Yingyong Huaxue 1993, 10, 5 (Chem.
sto m a titis, p o lio , ru b ella, R a u sch er leu k em ia , rabies, e tc.'521 O n e p articu lar
Abstr. 1993, 119, 186166).
h ete ro p o ly tu n g sta te , H P A -2 3 o f fo rm u la (N F D ^ N a fN a S b g W iiO g e ]. th a t e x 22. Asahi Chemical Industry Co. Ltd., Japanese Patent 59,200,769, 1984 (Chem. Abstr.
h ib ited p r o m isin g resu lts in vitro}54*w a s u sed for trea tm en t o f A I D S p a tie n ts in 1984, 102, 82691).
F ra n ce an d th e U S A . L a ter o n , th e d ru g w a s fo u n d u n a cc e p ta b le b e c a u se o f its 23. M. Misono and N. Nojiri, Appl. Catal. 1990, 64, 1.
m arked to x icity a n d in su fficien t an tiviral a c tiv ity .'55,561 T h e se resu lts e n c o u r 24. A.Ya. Pikel’nyi, G.G. Reznikova, A.P. Brynza, S.A. Khmelovskaya and O.A.
a ged sev era l g r o u p s to d e v e lo p less to x ic a n d m o re e ffic ie n t se c o n d -g e n e ra tio n Pikel’naya, Russ. J. Electrochem. 1995, 31, 484.
P O M an tiv ira l a g en ts th a t c o u ld b e effe c tiv e aga in st H IV . 25. A.Ya. Pikel’nyi, G.G. Reznikova, A.P. Brynza and S.A. Khmelovskaya, Zashch.
Met. 1994, 30, 443.
194 CATAL YSIS BY POLYOXOMIiTALATHS
26. (a) G.L. Roberts Jr. and R.G. Fcssler, U. S. Patent 3,346,604, 1967 (b) U.S. Patent
3,365,313. 1968.
27. C..1. Brinker and G.W. Scherrer, “ Sol-Gel Science: The Physics and Chemistry of
Sol-Gel Process, Academic Press, New York, 1990.
In d e x
28. J. Livage, Catal. Today, 1998, 41, 3.
29. P. Judeinstein and H. Schmidt, J. Sol-Gel Sei. Techno!. 1994, 3, 189.
30. M. Minami. M. Hiraoka, K. Izumi and Y. Uchida, Japanese Patent 08,141,493,
1996 {Chem. Abstr. 1996. 125, 171066).
31. M. Asuka, M. Myazaki, Y„ N akatani and K. M yamoto, Japanese Patent
07,333,401, 1995 {Chem. Abstr. 1996. 124, 215718).
32. B. Orel, U. Lavrencic-Stangar, M.G. Hutchings and K. Kalcher, J. Non-Cryst. acetaldehyde 128 temperature-programmed desorption
Solids 1994, 175, 251. acetalisation, steroids 97 (TPD) 33
33. T. Satake and T. Yoneda, Japanese Patent 01,192,742, 1989 {Chem. Abstr. 1989, acetic acid 30,157-8,178-82 thermal desorption 83
112, 163860).
esterification 101 ammonium 12-molybdophosphate 2
acetonation, L-sorbose 74 Anderson-Evans anion 10
34. S. Ayusawa and S. Kondo, Japanese Patent 60,220,503, 1985 {Chem. Abstr. 1985,
acetone 30, 31, 76 Anderson-Evans structure 13
104, 132910). acetonitrile solution 31 anion charge vs. one-electron reduction
35. T. Ohtsuka, T. W akabayashi and H. Einaga, J. Electroanal. Chem. 1994, 377, 107. l -acetoxy-4-hydroxy-2- potential 39
36. M.S. Freund. C. Karp and N.S. Lewis, Inorg. Chim. Acta 1995, 240, 447. methylnaphthalene 74 antimony-substituted Keggin
37. G. Bidan. B. Fabre and M. Lapkowski, World Patent 9,423,291, 1994 {Chem. Abstr. acid-catalysed reactions polyoxomolybdate 122
1994, 122, 122121). biphasic liquid-liquid systems 76-9 antitumoral activity 192-3
38. J. Ding and S.-J. Dong, Huaxue Xuebao 1996, 54, 193 {Chem. Abstr. 1996, 124, by heteropoly acids 62 antiviral activity 192-3
233838). Hammett plots for 64, 69 aromatic compounds, oxidation 147-8
39. T.V. Vernitskaya, O.N. Efimov and A.B. Gavrilov, Electrokhimiya 1994, 30, 1123. homogeneous acid catalysis 68-76 Asahi Chemical Industry 177,188
40. T. Ohtsuka, T. Wakabayashi and H. Einaga, Synth. Met. 1996, 79, 235.
acid catalysis 61-116,176-9
applications 62 benzene
41. B. Fabre, G. Bidan and M. Lapkowski, J. Chem. Soc. Chem. Commun. 1994, 1509. heterogeneous systems 65-6 alkylation 102
42. M. Nakajima, E. Okanoe and T. Magami, Japanese Patent 62,061,048,1987 {Chem. homogeneous systems 63-5 nitration 106-7
Abstr. 1987, 107, 124676). mechanistic principles 63-6 N,N-benzylalkylamines, oxidation 144
43. A.V. Yaroslavtsev, Usp. Khim. 1994, 63, 449. overview 62-6 bimolecular rate constant 40
44. O. Nakamura, T. Kodama, I. Ogino and Y. Miyake, Japanese Patent 51,106,694 acid properties 25-36 biomaterials, analysis 186
1976 {Chem. Abstr. 1976, 86, 19085). acid sites 80-9 biphasic liquid-liquid systems,
45. O. Nakamura, T. Kodama, I. Ogino and Y. Miyake, US Patent 4,024,036, 1977. acidification 48 acid-catalysed reactions 76-9
46. O. Nakam ura, T. Kodama, I. Ogino and Y. Miyake, Japanese Patent 76,106,683 addenda biphasic oxidation 129-30
1976 {Chem. Abstr. 1976, 86, 35749). oxidation potentials 38 biphasic reactions 77-9
substitution in heteropoly anions BP Amoco 178,179
47. H.-C. Sheu and J.-S. Shih, Anal. Chim. Acta 1996, 324, 125. 23 bridging oxygen atoms 25-6
48. V.L. Volkov, G.S. Zakharova and L.I. M anakova, Soviet Patent 1,567,958, 1990 addenda atoms 1, 2 Bronsted acids 25,31,32,71
{Chem. Abstr. 1990, 113, 144488). additives bulk heteropoly acids 80-1
49. S.R. Sheen and J.S. Shih, Analyst (Cambridge, U.K.) 1992, 117, 1691. inorganic matrices 188-9 bulk type I catalysis 65-6
50. (a) A. Polak and A.J. Beuhler, US Patent 4,710,278, 1987. (b) S. Petty-Weeks, US organic matrices 188-9 bulk type II catalysis 65-6
Patent 4,661,211, 1987. polymer matrices 189 n-butane, isomerisation 103, 104
51. K. Goswami, D.P.S. Saini, S.M. Klainer and C.H. Ejiofor, US Patent 5,405,583, sol-gel matrices 188-9 t-butanol 177
1995. adipic acid 123 t-butyl fluoride, hydrolysis 63
52. J.T. Rhule, C.L. Hill and D.A. Judd, Chem. Rev. 1998, 98, 327. aerobic oxidation 118 p-/m-butylphenol (TBP),
alcohols, dehydration 100-1 alkylation 92-4
53. M. Raynaud, J.C. Chermann, F. Plata, C. Jasmin and G. Mathe, C. R. Acad. Sei.,
alkanes
Ser. £>1971, 272, 347. isomerisation 103-5 caesium salts 106, 153
54. W. Rozenbaum, D. Dormont, B. Spire, E. Vilmer, M. Gentilini, C. Griscelli, L. oxidation 120, 146, 158-9 camphene, hydration 69
Montagnier, F. Barre-Sinoussi and J.C. Chermann, Lancet 1985, 450. alkenes, epoxidation 137-46 carbon, heteropoly acids on 84
55. B.L. Moskovitz, A AC 1988, 32, 1300. alkylation, benzene 102 carbonylation 167-8
56. M. Burgard, P. Sansonetti, D. Vittecoq, P. Descamps, D. Guetard, S., Herson, W., ammonia catalyst precursors 170-2
Rozenbaum and C. Rouzioux, AIDS 1989, 3, 665.
1% INDEX INDEX 197
cationic reaction intermediates 65 2.2- dimethyl-1-phenyl-1-propanol, gas sensors 192 concentrated solutions 31
C ATI VA process 180 one-electron vs. two-electron gas-solid systems, heterogeneous catalysis deprotonation 31
central atoms 1 oxidation 133 in 99-107 dissociation constants 29-30
CH2C1CH2C1-H20 137 1.2- diols 76 gases, sorption of 187 homogeneous acid catalysis 67-76
coatings, corrosion-resistant 187-8 1.4- diols 76 glycosides, synthesis 72 in solution 29-32
condensation 73 -5 1.5- diols 76 industrial processes catalysed by 175
conductive polymers 189-90 dioxygen, oxidation with 118-36 'H magic-angle spinning (MAS) on carbon 84
corner-bridging oxygen atoms 26 diphenoquinones 125 N M R 81 on silica 81-4
corrosion inhibitors 187-8 dipicolinic acid (DA) diester 97 H 3[PM ol2O40] 18, 29, 30, 39, 48, 51-2, solid 32-6
corrosion-resistant coatings 187-8 dissociation, poly-protonic acids 29-30 79, 138,139, 159, 168 surface proton sites in 27-9
Coulombic interaction 40 dissociation constants 63 H 3P 0 4-6M o03 59 synthesis 48-50
CPW H20 2 system 144 heteropoly acids 29-30 H3[PW12O40] 16, 25-7, 29, 33,48, 49, 51, thermal decomposition 17
p-cresol, alkylation 93 D 3[PW120 4o] 36 63, 64, 71, 75, 79, 138, 139, 144 heteropoly anions 1,31
crystal structure l70-enriched 28 addenda substitution in 23
heteropoly compounds 14-15 edge-bridging oxygen atoms 26 anhydrous 29 heteropoly compounds
12-tungstophosphoric acid electric potential 49 derivative thermogravimetry 17 acid catalysis by see acid catalysis
hydrates 14 electrodialysis 49 pseudoliquid 66 advantages 4
Cs,.9D u [PWl204o] 36 electromembrane synthesis 49 sorption of polar and nonpolar applications 4
C s25H o5[PW,204 o] 18, 34-5, 57, 96, 105 electron-transfer reactions 41 substances onto 66 crystal structure 14-15
Csi[PW 12C>4o] 26 elemental analysis 184-6 titania 84, 98, 189 model systems for fundamental
Cu(ll) 130 epichlorohydrin 75 H3[PWi2O40] hydrates, crystal research 4
cumene hydroperoxide (ROOH) 63, 76, epoxidation structure 14 multifunctionality 4
148 alkenes 137-46 H 3[PW i2O40]/M CM -41 86 properties 4
cyclic voltammograms of type I 1-hexene 148 H 3[PW i2O40]/SiO2 172 solubility 19
polyoxometalates 37-8 isobutene-isoprene copolymer 143 H 3[PWi20 4o]-6H20 14, 16 structural mobility 4
cycloalkenes, hydration 69 olefins, phase-transfer 139 EUfGeW^CXto] 52 thermal stability 15-19
cyclohexanone 123 oleic acid 142 H4[PMon VO40] 19, 53 heteropoly salts 18, 87
cyclopentene 146 styrene-butadiene copolymer 143 H4[SiMoi2O40] 50 physiochemical properties 87
p-cymene 121 ESR spectroscopy 36, 37 H4[SiMo]2O40]-8H2O 19 proton generation in 88
esterification 63, 71-3, 95-8 EUfSiW^Ckto] 26, 29, 30, 48, 51, 64, 75, heteropolytungstates,
dehydration of alcohols 100-1 acetic acid 101 79, 103 manganese-substituted 149
dehydrogenation 118 p-nitrobenzoic acid 78 H4[Si W i2O40]/SiO2 178-9 2,2',3,3',6,6'-hexamethyl-4,4'-bisphenol
deprotonation of heteropoly acid 31 steroids 97 H 5[P M o io V 20 40] 53, 123, 131 (HMBP) 124, 125
Dexter-Silverton structure 10, 13 ethanol 101 H6[P2W 18062] 54-5 hexamethy ldiphenoq uinone
diacetone-L-sorbose (DAS) 74 etherate method 48-9 H6[PMo9V3O40] 53-4 (HMDQ) 124, 125
2.6- dialkyl-1,4-benzoquinones 130 ethyl acetate, synthesis 178-9 Hammett acidity function 29, 31, 35, 63 n-hexane, isomerisation 104
2.6- dialkylphenols 125, 130 2-ethylanthraquinone/ Hammett plot for acid-catalysed 1-hexene, epoxidation 148
dialkylphthalates 72 2-ethylanthrahydroq uinone reactions 64,69 Hg(II) 129
dibenzothiophene (DBT) 171 (EAQ/EAHQ) process 143^1 heteroatoms 38-9 H(HPA-n) 125, 134
2.6- di-n?r/-butylphenols, heteropoly ethylene 102, 128, 178-9 heterogeneous acid catalysis 80-107 high molecular weight byproducts
acid-catalysed transdealkylation 94 oxidation 157—8, 180-2 by heteropoly compounds 65-6 (HMW) 142-3
2.6- dicyclohexylphenol 93 Eyring equation 40 heterogeneous catalysis homogeneous acid catalysis 58-9
Diels-Alder reaction 62, 98 gas-solid systems 99-107 acid-catalysed reactions 68-76
diethyl sulfide, HPA-n-catalysed formaldehyde 75 liquid-solid systems 89-98 by heteropoly acids 67-76
oxidation 125 vapour-phase trimerisation 79 oxidation 130-1 homogeneous oxidation 120-9
differential scanning calorimetry Friedel-Crafts reactions 90-5, 101-3 heterogeneous gas-phase oxidation over homogeneous systems, acid catalysis by
(DSC) 16 fuel cells 190 heteropoly compounds 151 heteropoly compounds 63-5
differential thermal analysis (DTA) 16 heteropoly acid catalysts 80-9 HPA solvates 66
dihydromyrcene (DHM) 96 gas-phase oxidation 149-59 deactivation and regeneration 107-9 HPA-0 134
acetoxylation and hydration 78 comparison of selectivities 152 heteropoly acid hydrates 32 HPA-1 134, 135
dihydromyrcenol (DH M -OH ) 78 general overview 149-50 heteropoly acid plates 190 HPA-2 121, 126, 135, 136, 147
dihydromyrcenyl acetate reactions 151-9 heteropoly acids HPA-3 135
(DHM-OAc) 78 selection of catalysts 150-1 acid-catalysed reactions by 62 HPA-4 123, 135
N,N-dimethylformamide 75 see also specific reactions acidity 32-6 HPA-6 124, 130, 135
198 INDEX INDEX 199
HPA-n 118. 119, 123-6, 130, 131, 133, Keggin polyoxometalates 50-4 12-molybdosilicic acid see H4[SiMoi20 4o] oxidation potentials 38
136, 151, 153 Keggin polyoxomolybdate, antimony- molybdovanadophosphates see oxidative bromination 121
mechanism 131-6 substituted 122 [PMo12_nVn0 4oF+n)- oxidative coupling 125
one-component system 120-7 Keggin structure 10-12,147-8 9- molybdo-3-vanadophosphoric acid oxygen exchange between 170-enriched
HPA-n (contd.) kinetics 23-4 see H6[PMo9V304o] heteropoly acid and H2 160
two-component system 127-9 redox reactions 40 10- molybdo-2-vanadophosphoric acid vapour 155
HPA-n + Pd(Il), two-component K,o[WZnRh(//(H20)(ZnW90M)2] 56 see H5[PMoioV20 4o] oxygenation 117-18
system 127-9 K i, [W ZnRu5/ / (0 H )(H 20 )(ZnW 90 34)2] 11- molybdo-l-vanadophosphoric acid
{HP04[WO(02)2]2}2- 140 56 see H4[PMoh V04o] 31PMASNMR 81,171-2
hydration monomolecular reaction 64 paraffin alkylation 89-90
camphene 69 lactam 75 Monsanto process 180 Pd(II) 119,127,128,130
cycloalkenes 69 lacunary anions 22-3, 49 MTBE 73, 103, 106 Pd-Au-H2S04/active carbon 181
isobutene 63, 65, 68, 176-8 Langmuir Hinshelwood type process 65 multicomponent systems 119,129 PdCl2-POM 168
olefins 68-71, 100, 176-8 ligands 22-3 Pd-H3P 04/Si02 181
propene 68, 176 lignin 126 Na5H2[PMo8V404o] 132 peroxo polyoxometalates 56-7, 137-9
hydrocarbons limonene, liquid-phase hydration and N afM o 0 4 24 pH range 20-2
conversion of methanol to 105-6 acetoxylation 70 nanoclusters of precious metals 170 phase-transfer epoxidation, olefins
oxidations 121 liquid-phase oxidation 118-48 nanoscale chemistry 169 139
hydrogen peroxide, oxidation with general principles 119-20 [NaP5W3oOU0]14- 126 phenols 76
136-48 liquid-solid systems, heterogeneous a-naphthols 144 alkylation 93
hydrogenation 167-8 catalysis in 89-98 ß-naphthols 144 trans-de-/<?r/-butylation 94
hydrolysis 95-8 lowest unoccupied molecular orbital N a 12[W C o»(H 20 )2(C o//W 90 34)2] phthalic anhydride 72
isobutyl propionate 71-2 (LUMO) 37 55-6 a-pinene, liquid-phase hydration and
t-butyl fluoride 63 N a ,2[WZn3(H20 ) 2(ZnW90 34)2] 55 acetoxylation 70
hydroquinone (HQ) 129 manganese-substituted (NH4)5H6[PMo4V8O40] 131 ß-pinene, liquid-phase hydration and
hydroxyacetophenones 103 heteropolytungstates 149 nitration of benzene 106-7 acetoxylation 70
HZSM-5 36, 96, 106 Marcus equation 40 nitrobenzene 168 [PMonOjoSb111]4“ 122
Marcus theory 40, 41 p-nitrobenzoic acid, esterification 78 {PMo12_nVn04o} 39
iminium salt 75 Markinovnikov’s rule 176 [PMo12_„Vn04o]<3+n)- 58, 188
industrial processes 175-82 Mars-van Krevelen mechanism 154 olefins {PMo12_nWn04o} 39
inorganic matrices, additives 188-9 MCM-41 123 hydration 68-71, 100, 176-8 a-[PMoi20 4o]3_, cyclic
intrazeolite heteropoly acids 85-7 membranes 190-2 oligomerisation 103 voltammogram 38
ion exchange 49 menadione 130 oleic acid, epoxidation 142 {P04[MoO(02)2]4) 3“ 139
Ir(O) clusters 169 methacrolein, oxidation 152-6, 179-80 oligomerisation {P04[W0(02)2]4} 56-7, 137-9
isobutane 36, 103 methacrylic acid 152—6, 179—80 olefins 103 polar nonaqueous solvents 31
isobutene 93 methane 149 propane 104 polar solvents 30
hydration 63, 65, 68, 176-8 methanol, conversion to one-component systems 119-27 polyanion-stabilised clusters 169
separation 68 hydrocarbons 105-6 one-electron oxidation 134 polymer matrices, additives in 189
solubility 68 methyl formate 75 one-electron redox reactions 41 polyoxometalates 57-9
isobutene-isoprene copolymer, methyl glucolate 75 one-electron reduction potential vs. anion analytical chemistry 184-6
epoxidation 143 2-methyl-1-naphthol 130 charge 39 applications 3, 4, 167-73, 183-94
isobutyl propionate, hydrolysis 71-2 methyl phenylcarbamate 168 organic matrices, additives 188-9 chemistry 3
isobutyric acid, oxidative methyl t-butyl ether see MTBE organic peroxides, oxidation by cis-dioxo (type II) 37
dehydrogenation 156 methyl trifluoroacetate 149 148-9 formation 19-25,48
isomerisation methylmethoxy acetate 75 oxidation historical background 2-3
alkanes 103-5 2-methylnaphthalene, oxidation 121 alkanes 146, 158-9 industrial applications 175-82
n-butane 103, 104 2-methylpropanal 122 aromatic compounds 147-8 industrial chemical processes 4
n-hexane 104 molybdenum(VI) heteropoly anions, N,N-benzylalkylamines 144 main applications 184
isophytol, condensation 73-4 stability 21 by organic peroxides 148-9 mono-oxo (type I) 37
isopoly anions 1 12-molybdophosphate 21 ethylene 157-8, 180-2 nomenclature 2
isopropanol 176 molybdophosphoric acid see methacrolein 152-6, 179-80 physicochemical properties 183
isotope exchange 23-4 H3PO4- 6M0O3 sulfur compounds 125, 148 properties 9-45
12-molybdophosphoric acid see with dioxygen 118-36 see also specific properties
Keggin acids 31 H3[PMo12O40] with hydrogen peroxide 136-48 reviews 3, 5
200 INDEX INDEX 201
polyoxometalates {cant.) solubility of heteropoly compounds 19 TOBAC 144 12-tungstogermanic acid see
sandwich-type 55-6 L-sorbose, acetonation 74 a-tocopherol 73 H4[GeW,2O40]
scope and definitions 1-2 sorption of gases 187 Tokuyama process of propene 12-tungstophosphoric acid see
state in solution 19-25 stability in solution 19-22 hydration 176-7 H3[PW|2O40]
types 1 standard hydrogen electrode (SHE) 120 p-toluenesulfonic acid 149 12-tungstosilicic acid see H4[SiW]20 4o]
polyoxomolybdate-diphosphate standard reduction potentials 134 transition metal nanoclusters 169 two-component systems 119,127-9
complexes 76 stepwise redox mechanism 127 transition metal-substituted
polyoxytetramethyleneglycol steroids polyoxometalates 50,118,148-9 Venturello complex 140
(PTMG) 77 acetalisation 97 transition metal-substituted Venturello-Ishii system 137-44
poly-protonic acids, dissociation 29-30 esterification 97 tungstophosphates see PWj | M 039 vitamin C 73
polytungstates 186 structures 10-13 tributyl phosphate (TBP) 146 vitamin E 73
POM-based catalyst systems 126 Anderson-Evans structure 13 triethylphosphine oxide (TEPO) 34 vitamin K| 73
precious metals, nanoclusters of 170 crystal structure of heteropoly triflic acid 31 vitamin K3 121
Prins reaction 75 compounds 14-15 1.3.5- trihydroxybenzene 76
propene hydration 68,176 Dexter-Silverton structure 13 1.3.5- triisopropylbenzene Wacker oxidation 127-9
proton conductivities 32 general principles 10 hydroperoxide 76 Wacker process 127
proton generation in heteropoly salts 88 Keggin structure 10-12 trimethylbenzoquinone see TMBQ Wacker reaction 156-7
proton structure 25-9 Wells-Dawson structure 12 2.3.5- trimethylhydroquinone Wells-Dawson anion 119
purification 50 styrene 94 (TMHQ) 73 Wells-Dawson polyoxometalates
PW„MOm 54, 122 styrene-butadiene copolymer, 2.3.5- trimethylphenol see TMP 54-5
[PWu 039Co]5- 122 epoxidation 143 trioxane 79 Wells-Dawson structure 12
[PW nO ^M p- 122 substitution mechanism 23-4 tris-cetylpyridinium salts 144 [WZnMn2(H20)2(ZnW90 34)2]12~ 145
[PWn039Zn]5- 126 sucrose 76 TsOH 72
pyrophosphate, molybdate-catalysed sulfur compounds, oxidation 125, 148 tungsten acids 31 zeolite 85-7, 96
hydrolysis 76 superacids 35 18-tungstodiphosphoric acid see zirconia, 12-tungstophosphoric acid
supported heteropoly acids 81-5 H 6[P 2W i 8 0 6 2] supported on 84
Q3{P04[W0(02)2]4} 141-2 surface proton sites in heteropoly
quinone 121 acids 27-9
surface type catalysis 65-6
radioactive waste processing 186-7 synthesis 47-60
RCHO 154 general methods 48-50
redox properties 37-42
mixed-addenda anions 39 12-tungstophosphoric acid
redox reactions 41 supported on titania 84, 98, 189
kinetics 40 supported on zirconia 84
redox systems TBHP 148-9
multicomponent 168 temperature-programmed desorption
reversible 119 (TPD) of ammonia 33
three-component 129 temperature-programmed reduction 41
regeneration 49 a-terpinene 121
tert-butylphenol derivatives,
sandwich-type polyoxometalates 55-6 dealkylation 94
selective electrodes 192 tetrahydrofuran (THF),
selective oxidation 117-66,179-82 polymerisation 77
separation 186-7 thermal gravimetric analysis (TGA) 16
Showa Denko process 181-2 thermal stability of heteropoly
silica, heteropoly acids on 81-4 compounds 15-19
silica-supported H^PWnO^] 57 three-component redox sytem 129
siloxane coatings on steel 189 Tischenko reaction 178
[SiW„039]8- 126 titania, 12-tungstophosphoric acid
[SiWn 0 39Zn]6- 126 on 84, 98, 189
sol-gel catalysts 58, 89, 96, 98 TMBQ 124, 125, 130-2, 147
sol-gel matrices, additives 188-9 TMHQ 73
solid acid catalysts 57 TMP 124, 130-2, 147
Catalysts for Fine Chemical Synthesis
Series Editors:
J| Sta n le y M . Roberts, Iv a n V. K o zh e v n ik o v and E ric Derouane
(University o f Liverpool, U K)
Catalysts are increasingly used by chemists engaged in fine chemical synthesis

within both industry and academia. Today, there exists a huge choice of high-
tech catalysts, which add enormously to the repertoire of synthetic possibilities, m
However, catalysts are occasionally capricious, sometimes difficult to use and ™
alm ost always require both skill and experience in order to achieve optimal
results. J|
This series aims to be a practical help for advanced undergraduate, graduate
and postgraduate students, as well as experienced chemists in industry and
academia working in organic and organometallic synthesis.
The series features:

I Tested and validated procedures
I Authoritative reviews on classes of catalysts
I Assessments of all types o f catalysts
I Expertise from the Leverhulme Centre for Innovative Catalysis, Liverpool, UK ^
CATALYSTS FOR FINE CHEMICAL SYNTHESIS

Volume 2
C atalysis b y Polyoxom etalates
Ivan V. Kozhevnikov
(University o f Liverpool. UK)
Arguably, catalysis by polyoxometalates has been one of the most successful

areas in fundamental and applied catalysis in the last few decades. Industry is
using these catalysts for a number of large-scale chemical processes. On the
other hand, the enormous versatility of polyoxometalates offers significant
opportunities for clean synthesis of fine and speciality chemicals. M uch
research is focussed on the use of these catalysts in laboratory scale synthesis.
The second volume in the series presents a survey o f recent developments in

catalysis by polyoxometalates for fine chemicals synthesis One chapter
concentrates on the practical preparation of specific acid and oxidation
catalysts Other chapters describe in detail the use in homogeneous and
heterogeneous synthesis

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CATALYSTS FOR

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ISBN 0 471 62381 4

Preface to Volume 2 ............................................................................................ xiii

3 Synthesis of Polyoxom etalates............................................................. 47

8.5 M em branes................................................................................... 190

During the early-to-mid 1990s we published a wide range of protocols, detailing

background information better to delineate the optimum strategy to try to

The chemistry of polyoxometalates (heteropoly acids and heteropoly salts),

some new approaches to catalysis by polyoxometalates are described in Chap­

[XxMmOy]q_(x < m) Heteropoly anions

Properties of many polyoxometalates have been studied in detail and thor­

Dozens of structural types and stoichiometries of polyoxometalates are known

1. Addenda atoms occupy a metal-oxygen polyhedron MOx that is most

2.1.2 THE KEGGIN STRUCTURE

Figure 2.4 The Wells-Dawson structure of the [X2Mig062]2x 16 anion (a isomer).

2.1.4 THE ANDERSON-EVANS STRUCTURE

This example represents a different structural type with an octahedron as a

2.1.3 THE W ELLS-DAWSON STRUCTURE

Figure 2.6 The Dexter-Silverton structure of the PCM12O42F 12 anion.111

Figure 2.7 Crystal packing of H3[PWi204o]-6H20 .ll4a]

Primary structure Secondary structure Tertiary structure

Figure 2.8 Structural hierarchy of heteropoly compounds.[2c]

2.5.1 STABILITY OF POLYOXOMETALATES IN SOLUTION

In solution of a polyoxometalate, several species frequently exist in equilibrium,

W(VI) > Mo(VI) > V(V).

The stability of the molybdenum(VI) heteropoly anions decreases in the series

12-Molybdophosphate exists in aqueous solution at pH < 1.5 (Figure 2.10).

OH“ OH- OH~

2 {PM011VO40} {PM012O40} + {P M oio V20 4o}

Similar disproportionation of {PW11VO40} was found to be second order with

[PW1204 o]3- t± [PW90 39f - + W(VI)

Kinetics and mechanism of addenda substitution in heteropoly anions have

2.6.2 HETEROPOLY ACIDS IN SOLUTION

In solutions, the acid properties o f heteropoly acids have been characterised in

Table 2.3 Dissociation constants of heteropoly acids in water at 20 °C*535.

Acid pK, pK2 pK3 pKi

(1) Sol-gel S i02

Figure 2.19 Correlation between AS (31P NMR) and AH (calorimetry of pyridine

[XM i26+O40]x- 8 + p e" + q H + H qpCM12_p6+Mp5+0 4o]x+q- p_8 (2.1)

where q < p . [1’28] On reduction in acidic aqueous solution at pH < 1, the

of Keggin polyoxometalates (Table 2.8) using both conventional and stopped-

one can obtain the equation

Table 2.8 Kinetics of redox reactions of Keggin anions in water at 25 °C1921.

Entry R eaction A:(lmol 's " 1)3 ln * o b

1 [SiW 12f - + [C oniW I2]5- - [SiW I2]4" -H C o H W d 6" 7 x 106 3.8

General methods of synthesis of heteropoly- and isopolyoxometalates are well

some new approaches to catalysis by polyoxometalates are described in Chap

Properties of many polyoxometalates have been studied in detail and thor

It is suggested that heteropoly anions can stabilise cationic reaction inter

The major problem, limiting the utility of homogeneously catalysed pro

Generally, prevention of catalyst deactivation is preferable to catalyst regen

(C h a p te r 2 ), w h ic h s u p p o r ts th is m e c h a n is m fo r th e o x id a t io n o f { S iW i 20 4o} p r e se n c e o f { P 0 4[W 0 (0 2 )2]4 } 3_ in a C H 2C I C H 2C I-H 2O s y s te m a ffo r d s e p o x

k in e tic s a n d m e c h a n is m o f th e o x id a t io n o f r e d u c e d t u n g s te n p o l y o x o m e t a (7 0 °C , 1.5 h ). T h e r e a c tio n is s te r e o se le c tiv e : m - 2 - h e x e n e is c o n v e r te d s o le ly

S o lid p o ly o x o m e ta la te s h ave b een cla im ed as so rb en ts o f g a ses fo r en v iro n