JOURNAL OF COLLOID AND INTERFACE SCIENCE 189, 144–150 (1997)

ARTICLE NO. CS974798

Thermal Transformations of Chromium

Acetylacetonate on Silica Surface
IGOR V. BABICH,* ,1,2 YURI V. PLYUTO,* ,3 PASCAL VAN DER VOORT,† AND ETIENNE F. VANSANT†
*Laboratory for Inorganic Surface Chemistry, Institute of Surface Chemistry, National Academy of Sciences of Ukraine, Prospect Nauki 31,
252022 Kiev, Ukraine; and †University of Antwerp (U.I.A.), Department of Chemistry, Laboratory of Inorganic Chemistry,
Universiteitsplein 1, 2610 Wilrijk, Belgium

formation of metal acac surface species covalently bonded to

Chemical modification of a silica surface with chromium acetyl- the support surface (2, 6). Finally, chemical reaction of the
acetonate ( Cr( acac )3 , acac Å C5H7O2 ) was carried out from the
M n/ (acac)n molecule with coordinatively unsaturated ions
gas phase at 1907C. This results in the formation of chromium acac
on the support surface may take place (8, 9).
species which interact with the silica surface because of hydrogen
bonding between the surface hydroxyl groups and the quasi p-
The mechanism of the metal acetylacetonates interaction
electron system of two acac ligands of Cr( acac )3 . Ligand substitu- with the support surface depends on the properties of the
tion in the chromium acac species on the silica surface pretreated support used (8, 10) as well as on the shape and stability
at different temperatures was studied by IR spectroscopy, thermo- of M n/ (acac)n (1, 5). For example, Cu acetylacetonate,
gravimetry, temperature-programmed oxidation, and chemical which has square-planar symmetry, interacts with the silica
analysis. Water molecules and surface hydroxyl groups can replace surface due to hydrogen bonding between the surface hy-
acac ligands in the chromium acac surface species at 230 and droxyl groups and acetylacetonate ligands (5). In the case
2707C, respectively. The oxidation of the acac ligands in air occurs of the unstable octahedral Fe and Mn acetylacetonate mole-
at 3407C and is accompanied by conversion of Cr3/ to Cr6/ . q 1997 cules, acac ligands are replaced by the surface hydroxyl
Academic Press
groups under mild conditions (8, 10). In contrast, the highly
Key Words: silica; chemical modification; chromium acetylaceto-
stable and coordinatively saturated Cr(acac)3 molecule has a
nate; hydrogen bonding; ligands substitution.
low affinity toward the silica surface in the same conditions.
Kenvin et al. (5) showed that about 90% of the adsorbed
Cr(acac)3 was removed from the Cab-O-Sil surface by
INTRODUCTION
washing with pure acetonitrile.
In the last few years the application of metal b-diketonates Deposition of Cr(acac)3 from the gas phase onto the silica
in surface modification of dispersed solids has been exten- support was more successful. Thus, Haukka et al. (11) car-
sively studied (1–7). By this method supported catalysts ried out chemisorption of Cr(acac)3 in a flow-type reactor
with a highly dispersed active phase can be prepared (4, 6). at low pressure. They observed that chemical reaction of
The synthesis of the supported metal oxide catalysts includes Cr(acac)3 molecules with hydroxyl groups of the surface of
interaction of metal b-diketonates with the support surface silica gel resulted in elimination of one acac ligand and
followed by the transformation of metal b-diketonate surface formation of grafted chromium acetylacetonate surface spe-
species to the catalytically active oxide phase (1). cies. In contrast, Köhler et al. (12) concluded that Cr(acac)3
It has been found that the interaction of the metal acetyla- can be adsorbed on a silica surface without decomposition
cetonate molecules with the support surface may occur in when modification is carried out in a fluidized-bed reactor.
different ways. First, the quasi p-electron system of the acac The formation of hydrogen bonds between acetylacetonate
ligands may be involved in hydrogen bonding with the sur- ligands of Cr(acac)3 molecules and surface hydroxyl groups
was suggested without a detailed analysis of the structure
face hydroxyl groups (3, 5). Second, surface hydroxyl
of surface species which were formed.
groups can react with M n/ (acac)n molecules, resulting in the
The mechanism of acac ligand elimination from Cr(acac)3
molecules deposited on silica surface is not clear as yet.
1
To whom correspondence should be addressed. Very little is also known about the role of different active
2
Current address: University of Antwerp (U.I.A.) Department of Chemis- centers on the silica surface (i.e., isolated and H-bonded
try, Laboratory of Inorganic Chemistry, Universiteitsplein 1, 2610 Wilrijk,
surface hydroxyl groups, adsorbed water molecules, siloxane
Belgium.
3
Current address: Delft University of Technology, Faculty of Chemical bridges) in the chemisorption of Cr(acac)3 , whose reactivity
Technology and Materials Science, Laboratory of Organic Chemistry and and relative concentration depends on the thermal pretreat-
Catalysis, Julianalaan 136, 2628 BL Delft, The Netherlands. ment of the silica.

0021-9797/97 $25.00 144

Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.
 Cr(acac) ON SILICA SURFACE 145
with a flow of dry nitrogen at the same temperature for 0.5
h in order to ensure the removal of unbounded Cr(acac)3 .
Infrared spectra were collected using a Nicolet 510 FTIR
spectrometer in the range of 400–4000 cm01 with a resolu-
tion of 4 cm01 . For the registration of the diffuse reflectance
FTIR spectra, the samples were diluted with KBr (1:10),
finely ground and mounted in a microcup placed into a Spec-
tra Tech diffuse reflectance cell. The spectra were normal-
ized against the KBr background and presented in Kubelka–
Munk units. Transmittance FTIR spectra were registrated
using the pressed self-supporting thin silica pellet.
Thermogravimetric experiments were carried out in a
Mettler TG 50 thermobalance connected to a TG 10A pro-
cessor. The thermograms were recorded from 307C up to
5007C with a heating rate of 107C/min in an oxidizing (air
flow) and in an inert (nitrogen flow) atmosphere.
Temperature-programmed oxidation experiments were
carried out in the flow of 6% O2 in Ar (30 cm3 /min) with
a heating rate of 107C/min. The oxygen consumption was
measured with a thermal conductivity detector.
The chromium content in the modified samples was deter-
mined by the iodometric method (13).

RESULTS
FIG. 1. Schematic diagram of the experimental set-up.

The treatment of fumed silica with Cr(acac)3 in a nitrogen

The aim of this study is to examine in more detail the flow at 1907C leads to the deposition of the modifier on the
mechanism of Cr(acac)3 chemisorption on silica surface pre- silica surface since the presence of Cr 3/ ions was found in
treated at different temperatures and to discuss the structure the modified samples by chemical analysis. During modifi-
and reactivity of chromium acac surface species. cation the color of the initial silica changes from colourless
to greenish.
The chromium content in the synthesized samples is 0.83,
EXPERIMENTAL 0.69, and 0.56 atoms/nm2 for silica pretreated at 200, 400
and 8007C, respectively (Table 1). It is necessary to stress
Fumed silica (Degussa, SBET Å 200 m2 /g) was pressed, that an increase of the deposition time and the amount of
crushed, and sieved to a particle size of 0.25–0.50 mm. the modifier used does not result in a further increase of the
Cr(acac)3 was purchased from Fluka and was used without chromium content in the modified samples. This means that
additional purification. all active sites on silica surface which are accessible for
Silica modification was carried in a flow-type reactor at Cr(acac)3 are consumed under the conditions of the experi-
atmospheric pressure with a dry nitrogen as a carrier gas. ment. Also, the chromium loading depends only on the pre-
The schematic diagram of the experimental set-up is shown treatment temperature of the initial silica support.
in Fig. 1. Diffuse reflectance FTIR spectra of the synthesized sam-
The general procedure of the Cr(acac)3 deposition on
silica surface was the following. About 0.5 g of silica sample
was placed in the reactor and pretreated at the appropriate TABLE 1
temperature (200, 400, or 8007C) for 2 h under a flow of dry Surface Composition of Silica Samples Modified with Cr(acac)3
nitrogen (25 ml/min). Then the temperature was reduced to Tpre , Cr content, acac content,
1907C and Cr(acac)3 was introduced into the hot zone of Sample 7C atoms/nm2 u groups/nm2 acac/Cr
the reactor with a modifier holder. During the sample modi-
fication, the temperature was kept constant at 1907C. A con- SiO2-1 200 0.83 0.52 2.38 2.9
densation of Cr(acac)3 was observed near the outlet of the SiO2-2 400 0.69 0.43 2.05 3.0
SiO2-3 800 0.56 0.35 1.75 3.1
reactor indicating the end of the consumption of Cr(acac)3 .
Afterwards, the holder with the modifier was taken out from Note. Tpre : pretreatment temperature. u: surface coverage with chromium
the hot zone and the modified silica was additionally treated acac species.
146 BABICH ET AL.

groups with the quasi p-electron system of the acac ligands

of Cr(acac)3 molecules.
The details of the thermal transformations in the chro-
mium acac surface species were studied in the oxidizing and
the inert atmospheres by a thermogravimetric technique. The
weight changes in all samples in the 200–4007C temperature
range were observed (Figs. 4a and 4b). The influence of
the silica pretreatment temperature on the DTG profiles is
clearly seen. For modified samples pretreated at 800 and
4007C the weight loss occurs in two steps. The DTG profile
of the modified sample pretreated at 2007C contains an addi-
tional low temperature peak.
The position of the high temperature peak appears to be
dependent on the atmosphere used in the thermogravimetric
experiments. In the case of the oxidizing atmosphere, the
high temperature peak is observed at 3407C (Fig. 4a)
whereas it is seen at 3807C (Fig. 4b) if the inert atmosphere
is used.
In order to clarify the origin of the maxima in the DTG
FIG. 2. Diffuse reflectance FTIR spectra of modified silica pretreated profiles of the modified samples special attention was given
at 800 (1), 400 (2), and 2007C (3), and of bulk Cr(acac)3 (4). to the structure of the chromium surface species formed on
the silica surface at the corresponding temperatures. The
diffuse reflectance FTIR spectra of the modified sample (pre-
ples (Fig. 2) are shown in the region which is characteristic treatment temperature 2007C) after heating in air at 270,
for the vibrations of the acetylacetonate ligands (1600–1200 310, and 4007C are shown in Fig. 5.
cm01 ) (14). For comparison the spectrum of bulk Cr(acac)3 Thermal treatment at 2707C which corresponds to the
is also reported in Fig. 2. first weight loss does not change the IR spectrum of the
One can observe from the spectra of the modified samples modified silica in the acac ligands vibration region ( Fig.
that the relative intensities of the bands and their positions 5 ( 2 ) ) . The presence of the IR bands of the carbonyl and
are the same. All spectra show intensive bands at 1575, carbon – carbon double bonds indicates that the acac ligands
1524, 1378, and 1280 cm01 which are also present in the still possess ring structure and are coordinated to the Cr /3
spectrum of bulk Cr(acac)3 . These bands can be attributed ions ( 14 ) . However, the observed decrease in the intensity
to the vibrations of the carbonyl and carbon–carbon double of these IR bands suggests a partial acetylacetonate ligands
bonds in the conjugated chelate rings coordinated to the removal.
Cr 3/ ion (Table 2). The absolute IR band intensities of the When the treatment temperature corresponds to the sec-
modified samples, pretreated at different temperatures, are
correlated to the concentration of chromium acac surface
species, determined by the chemical analysis. TABLE 2
The appearance of the intensive IR bands corresponding Position of the IR Bands (cm01) of Chromium acac Species
to the acac vibrations is accompanied by changes in the on Silica Surface and of Bulk Cr(acac)3
01
intensity of the bands at 3800–3300 cm specific for surface
SiO2-1 SiO2-2 SiO2-3 Bulk
hydroxyl groups (15, 16). In order to show how the surface (2007C a) (4007C a) (8007C a) Cr(acac)3 Assignment
hydroxyl groups are perturbed by the chromium acac surface
species, the transmittance FTIR spectra of the fumed silica 1577 1572 1576 1575b
dehydrated at 8007C and silica modified by Cr(acac)3 are 1582 (14) n C rrr Os
1524 1525 1525 1522b
shown in Fig. 3. In the spectrum of the initial silica (Fig.
1535 (14) n C rrr C rrr Cas
3a) one can see the presence of the band at 3750 cm01 1431 — — 1426b
corresponding to isolated hydroxyl groups (15, 16). The 1429 (14) n CH3
modification of silica samples with Cr(acac)3 results in the 1378 1378 1378 1383b
01
decrease of the 3750 cm band intensity and the appearance 1389 (14) n C rrr Oas
01 1280 1280 shoulder at 1280 1278b
of the bands in the 3600–3300 cm region (Fig. 3b) which
1281 (14) n C rrr C rrr Cs
are specific for the surface hydroxyl groups involved in H-
bonding (15, 16). These changes can be attributed to a direct a
Pretreatment temperature.
interaction of the proton of the isolated surface hydroxyl b
This work.
 Cr(acac) ON SILICA SURFACE 147

FIG. 3. Transmittance FTIR spectra of silica sample pretreated at 8007C (a) and modified by Cr(acac)3 at 1907C (b).

ond step of the weight loss at 3107C, the disappearance Additional information about the thermal transformations
of the IR bands at 1524, 1378, and 1280 cm01 of the of the chromium acac surface species was obtained from
coordinated acac ligands is observed ( Fig. 5 ( 3 ) ) . In con- the temperature-programmed oxidation (TPO) experiments.
trast, bands at 1550 and 1448 cm01 corresponding to the TPO patterns for all modified samples are similar and consist
intermediate oxycarbonate surface species ( 18 ) which are of one sharp peak at 3407C reflecting oxygen consumption
formed in the result of the partial destruction of the acac (Fig. 6). This can be attributed to an oxidative destruction
ligands are present. of the acac ligands in the chromium acac surface species.
A subsequent heating of the modified sample at 4007C This process is accompanied by the oxidation of Cr 3/ in the
results in the diffuse reflectance FTIR spectrum similar to chromium acac surface species to Cr 6/ ions which were
that of the initial silica (Fig. 5(4)) meaning a total removal detected by chemical analysis. The observed valence trans-
and/or destruction of the acetylacetonate ligands in the ini- formation occurs in the temperature range typical for the
tially observed chromium acac surface species. oxidation of silica-supported Cr /3 ions (17).

FIG. 4. DTG profiles in an oxidising (a) and in an inert atmosphere (b) for modified silica pretreated at 800 (1), 400 (2), and 2007C (3).
148 BABICH ET AL.

In accordance with this scheme, the chemisorption of

Cr(acac)3 is accompanied by a decrease in the concentration
of hydroxyl groups on the silica surface and by the substitu-
tion of at least one acac ligand in the initial Cr(acac)3 mole-
cule. Therefore, a decrease of the intensity of the IR band
corresponding to surface hydroxyl groups as well as a de-
crease of the acac ligands/chromium ratio have to be ex-
pected.
It is necessary to stress that acetylacetone (acacH) does
not interact with silica surface under the used reaction condi-
tions. Silica samples brought into a contact with acetylace-
tone did not show IR bands in the 1700–1200 cm01 region
characteristic to C|O or C|C vibrations in the acacH
molecule (19) and any weight loss in the treated silica sam-
ples was observed. Therefore, acetylacetone which is
evolved upon Cr(acac)3 chemisorption does not react with
surface hydroxyl groups and it cannot affect the experimen-
tally determined acac ligands/chromium ratio in the chro-
mium acac surface species.
FIG. 5. Diffuse reflectance FTIR spectra of modified silica (1) which (ii) Formation of the hydrogen bond between the silanol
was heated in air at 270 (2), 310 (3), and 4007C (4) (pretreatment tempera- group and the quasi p-electron system of the acac ligand.
ture 2007C). Since no ligands are lost by such interaction, the acac ligand/
chromium ratio in chromium acac surface species will be
equal to that of the initial Cr(acac)3 . Hydrogen bonding has
It is clear that the observed weight loss in the DTG profiles
to result in a decrease of the intensity of the 3750 cm01 band
of the modified samples has to be attributed to the complete
of the isolated surface hydroxyl groups accompanied by a
removal of the acac ligands in the oxidizing atmosphere
simultaneous appearance of the broad band at 3600–3400
(Fig. 4a). According to the results of chemical analysis this
cm01 corresponding to their hydrogen bonded form.
thermal treatment does not cause a decrease of chromium
(iii) Hydrolysis of Cr(acac)3 with water molecules or its
content in modified samples. Taking into account that pro-
reaction with siloxane bridges. These have to result either
cess of the acac ligands removal is accompanied by oxidation
in the formation of the hydroxylated chromium acac surface
of Cr 3/ ions to Cr 6/ , we suppose that the observed weight
species or (GSi-O)nCr(acac)30n , respectively. Both pro-
loss can be described by the following scheme:
cesses assume a decrease of the acac ligand/chromium ratio
below 3 in the initial Cr(acac)3 molecule. The appearance
Cr(acac)n CrO‹ 1 Volatile products. [1] of the IR bands corresponding to the vibrations of the acac

This makes it possible to determine the n value which reflects

the acac ligands/chromium ions ratio in the chromium acac
surface species. These data are presented in Table 1. As this
ratio is close to 3 for all modified samples, one can conclude
that interaction of Cr(acac)3 molecules with silica surface
occurs without a loss of the acac ligands.

DISCUSSION

As has already been discussed in the literature (1–12),

the interaction of Cr(acac)3 with a silica surface may involve
the following mechanisms:
(i) Anchoring of chromium acetylacetonate to the silica
surface due to the chemical reaction with the silanol groups

n(GSiOH) / Cr(acac)3 r
(GSi{O)nCr(acac)30n / n acacH. [2] FIG. 6. TPO pattern of modified silica pretreated at 4007C.
 Cr(acac) ON SILICA SURFACE 149
ligands should be observed in the IR spectrum of the modi- for further calculations of the maximum loading of the silica
fied samples although the intensity of the band of the isolated surface with a closed-packed Cr(acac)3 monolayer. The
surface hydroxyl groups is not changed. maximum loading amax (molecules/nm2 ) of the silica surface
with Cr(acac)3 molecules was calculated in accordance with
Comparing the IR spectra of the initial and the modified the equation amax Å 1/ s and was found to be equal to 1.59
silica samples (Fig. 2 and 3) and taking into account the molecules/nm2 . The experimentally determined loading of
value of the acac ligand/chromium ratio in the chromium the silica surface with Cr(acac)3 molecules, a (molecules/
acac surface species (Table 1), we come to the conclusion nm2 ), makes it possible to calculate the surface coverage u
that Cr(acac)3 molecules interact with silica surface due to Å a / amax which shows the part of the silica surface occupied
the formation of hydrogen bonds with the surface hydroxyl by Cr(acac)3 . The surface coverage of silica surface with
groups. First, the diffuse reflectance FTIR spectra of the Cr(acac)3 molecules does not exceed 0.52–0.35 of the theo-
modified silica samples exhibit the IR bands of the acac retical monolayer value and depends on the pretreatment
ligands at 1575, 1524, 1378, and 1280 cm01 . Second, a broad temperature of the silica samples (see Table 1). One may
band in the region 3600–3400 cm01 caused by the hydrogen assume that the saturation of silica surface with the chro-
bonded surface hydroxyl groups appears. And finally, the mium acac surface species is not controlled by the sterical
acac ligand/chromium ratio in the chromium acac surface hindrance.
species determined from the weight loss and chemical analy- The proposed structure of the chromium acac surface spe-
sis (Table 1) appeared equal to that in the initial Cr(acac)3 . cies was confirmed by their thermal transformations.
Therefore the interaction of Cr(acac)3 with the silica surface From Scheme 1 it is clear that the acac ligands in the
can be given by Scheme 1. Cr(acac)3 molecule stabilised on silica surface are not equiv-
An appropriate orientation of the acac ligands in the Cr- alent. Thus, two acetylacetonate ligands in the Cr(acac)3
(acac)3 molecule toward surface hydroxyl groups is required molecule are hydrogen bonded with surface hydroxyl
for the formation of such complex. This may arise in the groups, while one acac ligand is oriented unfavorably to be
case when the Cr(acac)3 molecule is being adsorbed on the involved in such an interaction.
silica surface from the gas phase at high temperature. The Kenvin et al. (5) showed that the decomposition of the
proposed scheme represents essentially this situation. hydrogen-bonded acac ligands occurred at lower tempera-
It is important to know what part of silica surface is cov- tures than that of the nonbonded ligands. The possibility of
ered with the chromium acac surface species and how this a proton transfer from the surface hydroxyl group to the
depends on the pretreatment temperature of the initial silica. acac ligand assists its substitution, which results in the elimi-
In accordance with the scaled particle theory, the diameter nation of the acetylacetone molecule. Nonbonded acac li-
of Cr(acac)3 molecule is equal to 0.897 nm (20). The cross- gands are decomposed at higher temperatures because of
sectional area of a Cr(acac)3 molecule can be calculated their oxidation or pyrolysis in an oxidizing or an inert atmo-
using the equation s Å pD 2 /4 which connects the cross- sphere, respectively. Therefore, the position of the high tem-
sectional area s (nm2 ) with the diameter D (nm) of the perature peak appears to be dependent on the atmosphere
molecule. It appears to be equal to 0.63 nm2 and was used which is used in the thermogravimetric experiments. In the
case of the oxidizing atmosphere (Fig. 4a), the peak at
3407C reflects ligand oxidation while in the case of the inert
atmosphere (Fig. 4b) the peak at 3807C corresponds to li-
gands pyrolysis occurring at high temperature.
In the oxidizing atmosphere the weight loss with the max-
ima at 270 and 3407C (Fig. 4a) have a different nature. As
only the high temperature DTG peak at 3407C is accompa-
nied by an oxygen consumption, which is clearly seen from
the TPO pattern in Fig. 6, this peak is connected with the
oxidation of the acac ligands. The weight loss at 2707C does
not require the presence of oxygen and has to be attributed
to the elimination of acetylacetone molecules from the chro-
mium acac surface species.
Comparison of the integrated areas of the low and high
temperature DTG peaks obtained in an oxidizing atmosphere
for modified samples dehydrated at 400 and 8007C makes
it possible to determine what part of the acac ligands are
removed from the chromium acac surface species (Scheme
SCHEME 1 1) due to acetylacetone elimination and ligand oxidation. As
150 BABICH ET AL.

the integrated area of the first peak is two times higher than ACKNOWLEDGMENTS
that of the second peak, the former is connected with the
Igor Babich is indebted to the NFWO (Belgian National Science Founda-
elimination of two hydrogen-bonded acac ligands while the
tion) as a postdoctoral research fellow. Pascal Van Der Voort is indebted
latter reflects the oxidation of the residual nonbonded acac to the NFWO as a postdoctoral researcher.
ligand.
Both ligand substitution and oxidation are accompanied REFERENCES
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