Molecular Sieve

Zeolite

References
General introduction
J . Weitkamp, Solid State Ionics 131 (2000) 175.
M. Yates, J. Mat. Sci. 30 (1995) 4483-4491
,
65(4) (2007) 385-396
Rabo, Future opportunities in zeolite science and technology Appl.Catal.
A: Gen. 229 (2002) 710
Reference books
H. van Bekkum, E. M. Flanigen & J. C. Jansen (eds.) Introduction to
Zeolite Science & Practice, Elsevier, Amsterdam (1991)
D. W. Breck, Zeolite Molecular Sieves, J. Wiley, New York (1974)

(1987)

Number of Molecular Sieve Related Publications

Introduction

What is a Molecular Sieve Zeolite?

Its Brief History?
Natural and Synthetic Zeolites
Zeolite Nomenclature

What is a Molecular
Sieve Zeolite?

The WordZeoliteis Derived

from Greek ()

Cronstedtd Discovery
Cronstedt paper

Zeo - to boil
Lithos - a stone
Name was given to this class of
materials by Swedish minerologist
Baron Axel F. Cronstedt (17221765)
in 1756
Based on his experience with stilbite when heated, the material bubbled as if
it were boiling
9

250 Years after

cavity of Cronstedts zeolite

crystals (x20)

a cavity with stellerite crystals

(b) the former material was composed of spherulites

and wavy fragments consisting of radiating
pyramids whose apices apparently
terminate in a center, the latter was a mixture of a
massive opaque chalk-like material and
tangled concentric wedges ;

(e) when placed on charcoal the Swedish

specimen, but not the Icelandic specimen,
could be melted into a pure glass.
Because it came from a copper mine,
traces of copper impurity colored the
glass in opaque reddish-brown; the green
color of the flame also indicated copper.

(c) the hardness of both samples corresponded to that

of normal spar or massive limestone earth;
(d) in the blow-pipe flame both samples emitted gas
and puffed up almost like borax ; in the
Swedish specimen, in particular, the pyramids
were initially transformed into a white spongy
mass which subsequently fused with a
phosphorescent glow to a white glass;
Gualtieri, Micro. Meso. Mat. 105 (2007) 213221; Deventer, Chem. Mater. 17 (2005) 3075-308510

Glossary

aggregate with stellerite crystals

the first zeolite studied by Cronstedt was actually

a mixture of stellerite with minor (less than 10%
volume) stilbite
The re-discovery of Cronstedt zeolite has an
undoubted valence of historical
character, as this event is the first step of a long
and exciting story involving the discovery and
study of natural zeolites that still continues today.

(a) the Swedish specimen was light yellow, the

Iceland specimen was white;

Unit Cell - Smallest repeating

crystallographic unit of a zeolite framework
T-atom - Tetrahedrally coordinated atom
(normally Si or Al)
Framework Density - Number of T-atoms
per nm3, also expressed in g/cc
SBU - Secondary Building Unit

stilbite crystals which

accompany stellerite in some
11
zeolitized cavities

12

Broadest Definition

Broad Definition

Zeolites are porous solids consisting of

corner-sharing tetrahedra, representing
a three-dimensional, four-connected
net with T- atoms at the vertices of the
net and oxygen atoms near the
midpoints of the connecting lines.

Zeolites are crystalline inorganic

polymers based on a framework of
XO4 tetrahedra linked to each other
by the sharing of oxygen ions, where
X may be trivalent (e.g., Al, B,
Ga,...), tetravalent (e.g., Ge, Si, ...) or
pentavalent (e.g., P...)
13

14

Narrow Definition

Chemically

A zeolite is a member of a class of crystalline

aluminosilicates that has the following
properties:
Consists of a 3-dimensional structure
arising from a framework of [SiO4]4- and
[AlO4]5- coordination polyhedra linked by
all of their corners
Comprises a framework which is
generally open and contains channels and
cavities in which are located cations and
water molecules

M2/nO. Al2O3 . ySiO2 . wH2O

n = Cation valence
w = water contained in voids of the
zeolite
y = SiO2/A12O3 ratio

15

16

Zeolites from T-Atoms

[Si-O-Si]0
> Si/Al > 10000

+4
Si

OH

OH

Si

Si

+3
Al

[Al-O-Si]- M+

OH

HO O H

OH

[Ti-O-Si]0

+4
Ti
OH

OH

Si/Ti > 1

HO

M+[Si-O-Al]- [Al-O-P]0
> Si/Al > 0
OH

Ti
HO

HO O H

HO OH

OH

HO

OH

Si/P > 1

OH

Al

HO

OH

Si
HO

HO

OH

OH

+4
Si

+3
Al

OH

OH

HO

OH

HO

+5
P

OH

OH

OH

Al
OH

HO

HO OH

OH

1+
OH

Si

1OH

OH

OH

Si

OH

HO

HO

17

Zeolite Frameworks

OH

OH

OH

+5
P

OH

OH

0
OH

OH

+3
Al

Al

Si

1+

1OH

OH

OH

HO

OH

Al/P = 1
HO

HO O H

OH

1OH

[Al-O-P]0

OH

OH

HO

OH

Si/Al > 1

Zeolites from T-Atoms

18

Primary Building Units

19

20

Structure of Zeolites

Structure of Zeolites

A defining feature of
Zeolites are the 4-connected
networks of atoms.
One way of thinking about
this is in terms of tetrahedral,
with a silicon atom in the
middle and oxygen atoms at
the corners.
These tetrahedra can then
link together by their corners
to form a variety of beautiful
21
structures.

Secondary Building Units (SBU)

23

Weitkamp, Solid State Ionics 131 (2000) 175188

25

These tetrahedra can then link together by their corners to

form a variety of beautiful structures.
The framework structure may contain linked cages,
cavities or channels, which are the right size to allow
small molecules to enter.
Zeolites have basically three different structural
variations.
Chain-like crystals
Sheet-like crystals
Equal in dimension
22

Some Cage Structures

24

X-Ray Diffraction Pattern vs. Crystal

Structure

26

The Incredible Pore System of Zeolites

SEM of ZSM-5 Crystals

Size measurement by SE Detector

27

28
Egeblad, K, Christensen, C. H., Kustova, M., Christensen, C. H.,(2007) (Eds.) Roth, W., Cejka, J., Perez-Pariente, P.

Structure - Property Relationships

MESOPOROUS MATERIALS

Implications
Structural Units
Ordered & Disordered Structures
Zoning
Acid Sites

MICROPOROUS MATERIALS
PILLARED LAYERED SOLIDS
ZEOTYPES
ZEOLITES

100

Pore Diameter (nm)

29

30

History of Molecular Sieves

31

32

Ordered Porous Silica

Evolution of Molecular Sieve Materials

1842
Discovery of Faujasite
1864
Discovery of Mordenite
1930-1934
First zeolite structure resolution
Late 40s to early 50s Low SiO2/Al2O3 ratio zeolites
Mid- to Late 60s
High SiO2/Al2O3 ratio zeolites
Early 70s
High siliceous zeolites
Late 70s
Metallosilicates and metalloaluminosilicates
Late 70s to early 80s
ALPO4, SAPO and MeAlPO molecular sieve
Mid 80s
VPI-5
Early 90s
MCM-41S materials

33

34

Natural Zeolites
Occur mainly in cavities of igneous rocks,

such as basaltic and volcanic

Some are known to be formed from
natural alteration of volcanic ash in
alkaline environments
Most common natural zeolites in use:
chabazite, erionite, mordenite and
clinoptiolite
K. Okada and K.J.D. MacKenzie, Nanoporous Materials from Mineral and Organic Templates, Elsevier (2006)

35

36

Natural Zeolites - Time Line

References

Date Mineral Described and named by

http://www.bza.org/zeolites.html
http://mineral.galleries.com/minerals/silicate/zeolites.htm

http://members.aol.com/vbetz/Zeolites.html
http://www.curriehj.freeserve.co.uk/skye6.htm

37

1756:
1792:
1801:
1801:
1801:
1803:
1808:
1813:
1816:
1817:
1820:
1820:
1822:

ZEOLJTE GROUP
CHABAZITE
S11LBITE
ANALCIME
HARMOTOME
NATROLITE
LAUMONTITE
SCOLECITE
MESOLITE
GISMONDINE
THOMSONITE
HEULANDITE `
BREWSTERITE

CRONSTEDT
BOSC DANTIC
HAUEY
HAUEY
HAUEY
KLAPROTH
HAUEY
GEHLEN & FUCHS
FUCHS & GEHLEN
LEONHARD
BROOKE
BROOKE
BROOKE

38

Natural Zeolites - Time Line

Natural Zeolites - Time Line

Date Mineral Described and named by

Date Mineral Described and named by

1825
1825
1825
1825
1825
1826
1842
1846
1864
1890
1896
1897
1898

1906
1909
1918
1932
1952
1955
1957
1960
1962
1974
1975
1975
1977

EDINGTONITE
PHILLIPSITE
HERSCHELITE
GMELINITE
LEVYNE
EPISTILBITE
FAUJASITE
POLLUCITE
MORDENITE
OFFRETITE
GONNARDITE
WELLSITE
ERIONITE

HAIDINGER
LEVY
LEVY
BREWSTER
BREWSTER
ROSE
DAMOUR
BREITHAUPT
HOW
GONNARD
LACROIX
PRATT & FOOTE
EAKLE

DACHIARDITE
DACHIARDI
STELLERITE
MOROZEWICZ
FERRIERITE
GRAHAM
CLINOPTILOLITE
SCHALLER
YUGAWARALITE
SAKURAI & HAYASHI
WAIRAKITE
STEINER
BIKITAITE
HURLBUT
PAULINGITE
KAMB & OKE
GARRONITE
WALKER
MAZZITE
GALLI, PASSAGLIA, PONGILUPPI, RINALDI
BARRERITE
PASSAGLIA & PONGILUPPI
COWLESITE
WISE & TSCHERNICH
MERLINOITE
PASSAGLIA, PONGILUPPI, RINALDI

39

40

Natural Zeolites - Time Line

Structural Variations of Zeolites

Date Mineral Described and named by

1979
1980
1980
1980
1982
1984

AMICITE
ALBERTI, HENTSCHEL, VEZZALINI
PARANATROLITE
CHAO
TETRANATROLITE
CHEN & CHAO
GOOSECREEKITE DUNN, PEACOR, NEWBERRY, AND RAMIK
GOBBINSITE
NAWAZ & MALONE
WILLHENDERSONITE PEACOR, DUNN, SIMMOMS,

1984
1990
1991

PERLIALITE
BOGGSITE
MONTESOMMAITE

1992

TSCHERNICHITE

TILLMANNS, FISCHER
MENSHIKOV

There are chain-like

structures whose
minerals form needlelike prismatic crystals,
i.e. Natrolite.

HOWARD, TSCHERNICH, SMITH, KLEIN

ROUSE, DUNN, GRICE, SCHLENKER,
HIGGINS
B+OGGS, HOWARD, SMITH, KLEIN

Source: R. W. Tschemich, Zeolites of the World, Geoscience Press, Inc. (1992)

41

Structural Variations of Zeolites

42

Structural Variations of Zeolites

Sheet-like structures
where the crystals are
flattened or tubular,
i.e. Heulandite.

Framework structures
where the crystals are
more equal in
dimensions, i.e.
Chabazite.

43

44

ZEOLITE GROUP

SERIES

Reference: Fleischers Glossary of Mineral Species

Series can be defined on the basis of dominant extra-framework cations

M.E. Back & J.A. Mandarino, Miner. Rec. Ed., Tuscon (AZ), 2008, 345 pp

MINERAL GROUPS
A mineral group, consisting of at least 3 species, involves members
having similar chemical formulae and, ideally, the same general
structure, thus belonging to the same crystal system
(not often respected)

BRE (Monoclinic): Ba, Sr Ex: Brewsterite-Ba

CHA (Trigonal): Na, K, Ca, Sr

Note: Herschellite (discredited) Chabasite-K

CLI (Monoclinic): Na, K, Ca

ZEOLITE GROUPS
(Alumino)silicates (and related?) with framework structures containing
open cavities in the form of channels and cages, usually occupied by
H2O and extra-framework (charge-compensating) cations.
Crystallography varies within the group.
90 officially recognized species (as for August 2008, including Direnzoite)
are partitioned between series species and non-series species

In the case of zeolites, series were established for 15 generic species, each
involving 2 or more species:

45

DAC (Monoclinic): Na, Ca

ERI (Hexagonal): Na, K, Ca
FAU (Cubic): Na, Ca, Mg

Note: Kaiserstuhl: presence of both FAU-Na & FAU-Mg

FAU-Ca exclusively found at Vogelsberg

46

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

SERIES
FER (Orth. & Mon.): Na, K, Mg
GME (Hexagonal): Na, K, Ca
HEU (Monoclinic): Na, K, Ba, Ca, Sr
LEV (Trigonal): Na, Ca
MAZ (Hexagonal): Na, Mg

Note: Mt Semiol = Mazzite-Mg; Mazzite-Ca = Boron (CA)

PAU (Cubic): K, Ca
PHI (Monoclinic): Na, K, Ca
STI (Monoclinic): Na, Ca
THO (Orthorhombic): Ca, Sr
Total: 41 valid species

47

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

48

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

49

50

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

51

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

52

RARE ZEOLITES, UNUSUAL COLORS,

UNEXPECTED COMPOSITIONS

53

NEW TOPOLOGIES ?

54

NEW TOPOLOGIES ?

55

56

NEW TOPOLOGIES ?

57

58

ZEOLITHE INFAILLIBLE : FIRST APPLICATION ?

59

60

Zeolite Nomenclature
There is no systematic nomenclature for zeolites
Natural zeolites are often named after
minerologists or locations where the crystal was
discovered:
goosecreekite, brewsterite, tschernichite, barrerite

Synthetic zeolites were systematically named by

companies who patented the materials:
Union Carbide: A, L, X, Y, LZ

61

Mobil: ZK-, Greek alphabet, ZSM-, MCMExxon: ECR

Chevron: SSZ
ICI: NU-, FU-, EU62

10

Zeolite Nomenclature
Formalized Procedure Administered by the
International Zeolite Association (IZA)
Three-letter codes given to unique zeolite
topologies
Examples: ZSM-5 - MFI
Y and X - FAU
ZSM-12 - MTW
Beta - BEA
ALPO4-5 - AFI

Other Nomenclatures
4 SAPO MAPO MEAPO
ALPO4
VPI CIT CF
Theta AMS AZ
EMC ECR CSZ TPZ TS TSZ
Silicalite

Source: W.M. Meier, D.H. Olson and Ch. Baerlocher, Atlas of Zeolite
Structure Types, Elsevier, 4th edition (1996)
63

Zeolite framework topologies by 3-letter

code and framework type
Silicates
ABW
AFG
BEA
BIK
BOG
BRE
CAS
CHI
DAC
DDR
DOH
EAB
EDI
EMT
EPI
EUO
FER
GME

GOO
HEU
KFI
JBW
LAU
LIO
LOS
LOV
LTL
LTN
MAZ
MEI
MEL
MEP
MER
MFI
MFS
MON

MOR
MTN
MTT
MTW
NAT
NES
NON
OFF
PAR
PAU
PHI
ROG
SGT
STI
THO
TON
WEN
YUG

Silicates and
phosphates
AFI
ANA
AST
BPH
CAN
CHA
SRI
FAU
GIS
LEV
LTA
RHO
SOD
ATT
ATV
AWW
CLO
VFI

Metalloaluminophosphates
Designation
Very Lg. Pore
VPI-5
Large Pore
5
36
37
40
46

Phosphates
AEI
AEL
AET
AFO
AFR
AFS
AFT
AFY
APC
APD
ATN
ATO
ATS

Intermed Pore
11
31
41

65

Representative ALPO/SAPO/Zeolite
Code
CHA
AEL
AFO
MTT
ATO
MTW
ATS
IWV
AFR
SFO
AFT
FAU
AET

Name
ALPO/SAPO-34a
ALPO-11/SAPO-11b
ALPO-41/SAPO-41
ZSM-23
ALPO-31/SAPO-31
ZSM-12
ALPO-36/SAPO/MAPO-36
ITQ-27
ALPO-40/SAPO-40
SSZ-51
ALPO-5/SAPO-5
ALPO-37/SAPO-37
ALPO-8/SAPO-8

aIsodewaxing
bAmination;

MTO

MR
8
10
10
10
12
12
12
12
12
12
12
12
14

Channel
3D
1D
1D
1D
1D
1D
1D
2D
1D/2D
1D/2D
1D
3D
1D

64

Structure Type
Novel, determined
Novel, determined
Novel
Faujasite
Novel
Novel, determined

Novel, determined
Novel
Novel

Designation

Structure Type

Small Pore
14
17
18
26
33
34
35
39
42
43
44
47

Novel, determined
Erionite
Novel
Novel
Novel
Chabazite
Levynite
Novel
Linde Type A
Gismondine
Chabazite - like
Chabazite - like

Very Small Pore

16
Novel
20
Sodalite
25
Novel
28
Novel

66

Faujasite Structure

Pore size()
3.8 x 3.8
4.0 x 6.5
4.3 x 7.0
4.5 x 5.2
5.4 x 5.4
5.6 x 6.0
6.5 x 7.5
6.2 x 6.9
6.7 x 6.9
6.9 x 7.1
7.3 x 7.3
7.4 x 7.4
7.9 x 8.7

http://www.iza-structure.org/databases/

67

69

11

FAU (Cubic Faujasite) &

EMT (Hexagonal Faujasite)
Framework

Erionite & Offretite

Hexagonal
Volume(3) a
b
OFF 1159.95 13.29 13.29
ERI 2295.19 13.27 13.27

c() ()
7.58 90 90 120
15.05 90 90 120

70

71

TYPES OF STRUCTURE
1
1.00E-03
1.00E-06
1.00E-09
1.00E-10
1.00E-12
1.00E-15
1.00E-18

m
mm
m
nm
A

meter
millimeter
micron
nanometer
Angstrom

Gm
MG
g
NG

Gram
milligram
microgram
nanogram

PG picogram
FG
AG
72

Cage
Code
FAU
LTA
RHO
CHA
KFI
OFF
PHI
ERI
LTL
MOR
MEL
MFI

Full Name
Faujasite
Linde Type A
Rho
Chabazite
ZK-5
Offretite
Phillipsite
Erionite
Linde Type L
Mordenlte
ZSM-11
ZSM-5

Secondary Building Units

S4R S6R
D6R
S4R S6R S8R D4R
S4R S6R S8R
S4R S6R
D6R
S4R S6R S8R D6R
S4R S6R
D6R
S4R
S8R
S4R S6R
D6R
S6R
D6R
5-1
5-1
5-1

Units
B
A,B
A,B
A,C
D
D
D

Framework
Density
No. of T
3

Atoms/nm
12.70
12.90
14.30
14.60
14.70
15.50
15.80
15.60
16.40
17.20
17.70
17.90

73

C6ZSM-5

Framework Density (T-atoms/nm3)

ZSM-5

LTA
FAU
ERI
LTL
MAZ
MOR
MFI

Zeolite A
Zeolite Y
Erionite
Zeolite L
Mazzite (ZSM-4)
Mordenite
ZSM-5

12.7
12.5 12.9
15.1
16.1
16.5
17.2
17.9

5.1 x 5.5 ; 5.3 x 5.6

Hexane
Isomer
n-hexane
4.1 x 4.1 x 9.0

3.9 x 4.3 x 9.0

2-methylpentane
4.1 x 4.8 x 7.9
4.6 x 5.8 x 8.6

74

2,3-dimethylbutane
5.0 x 6.0 x 7.0
5.9 x 6.2 x 6.7

75
Chester, Stud. Suf. Sci. Catal. 28 (1986) p 547

12

Typical Pore Sizes

> 12-MR zeolite

12-MR zeolite

5.0 x 6.0 x 7.0

10-MR zeolite
Z S M -5

8-MR zeolite

4.1 x 4.8 x 7.9

4.1 x 4.1 x 9.0

Tsai, J. Chem. Edu. 2008

76

Pore Size and Shape

_______________________

14-Ring
7.5 to 9
ALPO-8

18-Ring
11.5 to 12.5
VPI-5

78

20-Ring
12.5 to 14
Cloverite
79

80

Zeolite Matrix-Pore System

81

82

13

Void Volume
Zeolite

Zeolite Matrix-Pore System

Window

Window Size

Void Vol

No. O atoms

cc H2O/cc

8
12
12
12
8
10

4.5
7.8
7.1
6.7 x 7.0
2.9 x 5.7
5.6 x 5.4

0.47
0.53
0.28
0.26

Zeolite A
Zeolite X, Y
Zeolite L
Mordenite
ZSM-5

0.32

83

84

Zeolites from T-Atoms

> Si/Al > 10000

+4
Si

OH

OH

Si

Si

+3
Al

[Al-O-Si]- M+

OH

+
OH

Al

Si
HO O H

OH

HO

OH

OH

No two aluminum atoms can share the same oxygen atom:

HO

HO O H

OH

1OH

OH

OH

HO

OH

Si/Al > 1

Lowensteins Rule

[Si-O-Si]0

HO

0
OH

[Ti-O-Si]0
Si/Ti > 1

+4
Ti
OH

OH

Ti

Si
HO

OH

OH

OH

HO

HO O H

85

86

Si/Al ratio
Low-silica (Si/Al <2): strong acidity, unstable at high temperature
Hydrated low-silica zeolites: ion-exchange applications
High cation content leads to high exchange capacities

Dehydrated form: adsorption and separation applications

Interactions between the under-coordinated cations and the sorbate molecules are
a crucial feature of this process

High-silica (Si/Al >2): more thermal stability

Shape-selective catalysis
Acid-catalyzed reaction: exchangeable cation is
replaced by a proton that provides Bronsted acidity
Shape and size of pores add the selectivity in the reaction

Isomerization catalysis in p-xylene production

Pure-silica (Si/Al = infinity)

Candidate of low-k material for integrated circuit

87

1: Cheetham A.K. et al., Angew.Chem.Int.Ed. 38 (1999), 3268-3292

2: Lai Z. et. Al., Science 300 (2003), 456

88

14

Thermal stability
Framework flexibility

Thermochemistry of Silica

0.16

The lattice vibrations at high temperature

make tetrahedra move or rotate about a
bridging oxygen

2.89

2.8

Framework

Structure Rigidity
Open frameworks are not the thermodynamically most stable
structures compared to their condensed analogues, but the difference
are quite small (15 kJ/mol, siliceous FAU/-quartz)
The strength of T-O bonds (e.g. 466 kJ/mol for Si-O bond)
render porous structures stable with respect to framework rearrangement
and determine their thermal stability
Most of possible structures cannot remove organic guests in the pores
without inducing the collapse of host structure
One family that approaches the stability of the silicates is the aluminum
phosphates (AlPO4)
1: van den Berg et al., J. Chem. Phys., 121(20) (2004), 10219-10216
2: van den Berg et al., J. Phys. Chem. B., 108 (2004), 5088-5094
3: Cheetham A.K. et al., Angew.Chem.Int.Ed. 38 (1999), 3268-3292

89

Thermal Stability

2.0
2.4
4.9
2.5-6.0
3
10
> 10

13.45
15.60
16.51
17.97
19.39
15.40
26.52

110.04
71.59
44.77
38.60
36.47
33.51
31.06
39.10
22.71

SBA-15
MCM-41
FAU
BEA
MWW
MFI/F
MTW
CHA
Quartz

Htrans
kJ/mol TO2

Strans
J/(K mol)

23.20
19.33
13.6
9.3
10.4
6.8
8.7
11.4
0.0

44.7
44.9
45.1

41.5
90

Navrotsky, Chem. Rev. 109 (2009) 3885

TempC
600
712
793
750
850
1000
>1050

900
DTA Thermal Peak (C)

SiO2/Al2O3

Molar volume,
cm3/mol

Thermal Stability of X- and Y- Zeolite in

Sodium Form

Decomposition Temperature
Type
Name
Pore Dia
LTA
NaA
4.5
FAU
NaX
7.8
FAU
NaY
7.8
MAZ ZSM-4
7.5
LTL
L
7.1
MOR Mordenite 6.7x7.0
MFI ZSM-5
5.4x5.6

Framework
density, Si/nm3

880
860
840
820
800
2

SiO 2 /Al 2 O 3
91

Acid Sites in Zeolites

92

Conversion to the H-Form

93

94
Frame
Modification

15

Acid Activity Per Aluminum

Zoning in ZSM-5 Crystal

95

Microporous Materials: Aluminum Phosphates

Greater Coordination for Aluminum

AlPO4-n

Extra-large pore structures

III-V analogues to aluminosilicates

Al and P are in alternating tetrahedral coordination
Al/P ratio = 1
electrostatically neutral frameworks
Modification is required regarding the chemical
properties for catalysis, ion-exchange, etc.

96

VPI-5

Partial incorporation of cations with different valences

Silicoaluminophosphates (SAPO-n), Metalaluminophosphates
(MAPO-n), Metalsilicoaluminophosphates (MAPSO-n)

AlPO4 family usually can have more

than 12-rings, while the pores in
aluminosilicates are limited up to 14ring at most
Poor thermal stability than
aluminosilicateswer framework
stability
Mixed metal ion coordination
Aluminum can adopt greater coordination numbers than 4, such as 6
coordination (octahedral)

General formula: (SixMwAlyPz)O2, 0 x 0.20, 0 w 0.25

Si substitutes at phosphorus sites preferentially
Metal (M=Mg2+, Mn2+, Fe2+, Co2+, Zn2+) at aluminum sites

Presence of non-tetrahedral framework species (H2O, OH-, F-)

Water groups or anionic species such as hydroxide complete the
coordination sphere of the aluminum

Negative framework charge-compensating cations required

When these cations are protons, acid catalytic properties
1: Cheetham A.K. et al., Angew.Chem.Int.Ed. 38 (1999), 3268-3292
2: Yu J., Xu R., Acc. Chem. Res., 36 (2003), 481-489

97

Molecular separations
Catalysis
Energy storage

Mobility of molecules
Porous materials
Intercalates

Immobility of molecules and ions

Dense phases

98

Nano Macro Scale

Mobility in Solids

Mobility of ions
Porous materials
Intercalates
Ionic conductors

1: Davis M. E., Nature 417 (2002), 813-821

2: Francis R.J., Ohare D., J. Chem. Soc., 1998, 3133-3148

Ion-exchange separations
Batteries
Gas sensors
Fuel cell electrolytes
Immobilisation

Reactions in confinement
Porous materials

Control synthesis
Control polymerization
99

100

16

Worldwide Zeolite Consumption

101

102

103

104

U. S. Zeolite Market

How Zeolites Work

How Zeolites Work

Zeolites have the ability to act as catalysts

for chemical reactions which take place
within the cavities.
Catalysis occurs by hydrogen-exchanged
Zeolites, whose framework-bound protons
give rise to very high acidity.

Catalysis is used in many organic reactions.

Crude oil cracking
Isomerization
Fuel synthesis

105

106

17

What is a Zeolite? How does it work?

Higher FCC Productivity by Zeolites

A variety of micropore sizes, shapes and connectivities:

1756
Discovery of Natural Zeolites by Cronstedt
1959
Catalytic Application in Gas Oil Cracking
(FCC)
107

108

ABB Lummus FCC Process

SCT Riser

DirectDirect-Coupled Cyclones

Efficient Stripping

Turbulent Regeneration

MicroMicro-Jet Nozzles
Square Bend Transfer
109

110

How Zeolites Work

How Zeolites Work

The shape-selective properties of Zeolites

are also the basis for their use in molecular
absorption.
This ability to absorb certain molecules,
while excluding others, has opened a wide
range of molecular sieving applications and
purification processes.

Cation-containing Zeolites are extensively

used as desiccants due to their high affinity
for water, and also find application in gas
separation.
Organic solvents can be absorbed using
silica Zeolites.
Zeolites can separate molecules based on
differences of size, shape and polarity.

111

112

18

How Zeolites are used Today

How Zeolites are used Today

Zeolites have many useful purposes

The most well known use for Zeolites is in water

softeners.
Calcium in water can cause it to be hard and
capable of forming scum and other problems.
Zeolites charged with much less damaging sodium
ions can allow hard water to pass through its
structure and exchange the calcium for the sodium
ions.

Ion-exchange
Filtering
Odor removal
Chemical sieve
Gas absorption tasks

113

114

Commercial catalytic uses of molecular sieves

(refining and petrochemicals)

How Zeolites are used Today

Since Zeolites can absorb ions and
molecules they can act as a filter for odor
control, toxin removal and chemical sieve.
Most municipal water supplies are
processed through Zeolites before public
consumption.

115

Rabo, Appl. Catal. A Gen. 222 (2001) 261-275

116

Application of Molecular Sieves in Industrial Adsorption Processes

Ion Exchange: Fine-Tuning Pore Size

Progressive exchange of 2Na+ for
Ca2+ in Zeolite-A (LTA) leads to
an increase in the pore aperture.
Na12[Al12Si12O48].{guests}
Ca2+ ( Na+
Ca6[Al12Si12O48].{more guests}

Ca-A is used for O2 / N2 separation:

O2 diameter = 3.46
N2 diameter = 3.64
117

118

19

Microporous Catalysis

119

Reactant Shape Selective Catalysis

120

Product Shape Selective Catalysis

121

Transition-State Shape Selective Catalysis

122

Encasement of Polymers in M41S

Adsorb Aniline Monomer in Vapor Phase
Conduct Polymerization (Oxidative)
Allows Control of Polymer Morphology and Physical
Properties

123

124

20

XRD patterns of zeolite Y and Carbons

(a) zeolite Y; (b) the carbon prepared by the
previous procedure; (c) the carbon from the
present method

2
125

Zhao, Angew. Chem. Int. Ed. 2005, 44, 7053 7059

126

Kyotani, Chem. Mater. 2001, 13, 4413-4415

Pores Can Be Functionalized by Direct

Synthesis or by Post Treatment Methods
Functionalized groups can be a component of the synthesis
mixture and subsequently part of the pore wall or anchored to
the pore walls using the silanol groups

MCM-41: A New Class of Nanomaterials

Vary the Pore Size
1.5nm to >10nm
Clad the Surface
Vary the Chemical
Composition

127

Functionalized MCM-41 Is Used To Remove

Heavy Metals From Aqueous Waste Streams
OCH 3
CH3O

Si

O
H

O
H

MCM-41

Functionalized
MCM-41
O

SH

SH

Hydrogen storage in Chabazite

zeolite frameworks

H
O

Tris (Methoxy)
Mercaptopropane Silane
(TMMPS)

SH

128

OCH3

O
C3H6SH

Waste
Stream

Anchor Metals
and Catalysts

SH

SH

SH

SH

SH

SH

SH

Hg

Hg

Hg

Hg

Hg

Hg

Hg

Hg

Hg

Hg

+
HO Si O Si O Si O Si O Si O Si O Si O Si O Si O Si OH
O
O
O
O
O
O
O
O
O
O

Functionalized Surface

HO Si O Si O Si O Si O Si O Si O Si O Si O Si O Si OH
O
O
O
O
O
O
O
O
O
O

Heavy Metal Removed

from Stream
129

Regli, Phys. Chem. Chem. Phys., 2005, 7, 3197 - 3203

130

21