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A: GENERAL
ELSEVIER Applied Catalysis A: General 131 (1995) 323-334

Effect of sodium oxide on the morphology and

basicity of alumina
V . A . I v a n o v l,a, A. P i 6 p l u a, J.C. Lavalley a,*, p. N o r t i e r b
a Laboratoire Catalyse et Spectrochimie - - U R A CNRS 0414 - - 1SMRA Universite, 6, Boulevard du Mar6chal
Juin, 14050 Caen Cedex, France
b Centre de Recherche Rh6ne-Poulenc, 52, rue de la Haie Coq, 93308 Aubervilliers, France

Received 10 April 1995; revised 18 June 1995; accepted 20 June 1995

Abstract

Various samples of alumina were compared to study the effect of crystaUinity and sodium impurity
on alumina morphology and basicity. Carbon dioxide adsorption, followed by FT-IR and desorption
(TPD), and COS hydrolysis test reaction were used. The decrease of surface area observed on rather
amorphous samples after introduction of small amounts of sodium is ascribed to a better crystallinity
due to migration of a part of Na + into the bulk. The charge compensation phenomenon decreases the
number of defects in the anion subnetwork. It also provokes a decrease of the number of OH groups
which could explain the decrease of activity towards COS hydrolysis of the samples containing very
small amounts of Na20 ( < 1000 ppm). For larger amounts, COS conversion and carbon dioxide
experiments showed an increase in basicity.

Keywords." Alumina; Basicity; Sodium oxide; Temperature-programmed desorption

1. Introduction

The wide commercial use of aluminium oxide leads to a great interest for the
investigation of its properties. Industrial aluminas are never pure, neither from the
point of view of their crystallinity nor the presence of impurities like sodium.
Previous works were devoted to the study of both effects on acidity. It was found
that crystallinity increases the Lewis acidity [ 1 ]. This was related to the presence
of a higher number of AI 3 ÷ ions on tetrahedral coordination in the crystallised
samples. Generally, the effect of sodium was investigated for relatively large

* Corresponding author.
t Permanent address: Laboratory of Organic Catalysis, Chemistry Department, Moscow State University,
119899 Moscow, Russia.

0926-860X/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSD10926-860X ( 95 ) O 0 1 4 9 - 2
324 V.A. lvanov et al. /Applied Catalysis A: General 131 (1995) 323-334

amounts of Na20 ( 1% and more) [2-5]. It was shown that Na + addition decreases
the acidity of A1203. Smaller amounts of Na + (less than 2000 ppm) strongly
poison the acid centres of commercial alumina [6]. It was also found that the
presence of very small amounts (300 ppm Na20) in crystallized samples decreases
the number and the strength of the strongest acid sites [ 7]. This effect was similar
to that found for amorphisation.
The present paper is devoted to the study of both parameters - - crystallinity and
presence of small amounts of sodium - - o n alumina basicity. Basicity of metal
oxides is not well-known in our opinion [8] and it is difficult to find methods
sensitive enough to evidence the very small expected effects. Various methods are
generally used to study acidic or basic properties of heterogeneous systems [9,10].
Thermodesorption of acid molecules can give information about the total amount
and strength distribution of basic centres on the surface. Carbon dioxide is the most
used molecule [ 10]. Fourier transform infrared (FT-IR) spectroscopy of adsorbed
probe molecules is another method commonly used. However, while there are a
large variety of basic molecules to study the strength and number of acid sites, the
choice is very limited as far as acidic probe molecules are concerned. Deuterioch-
loroform has been proposed [ 11 ] and it gave a good correlation with CO2 temper-
ature-programmed desorption (TPD) for modified aluminas presenting great
differences in their basic properties [ 10]. Although carbon dioxide leads to various
adsorbed species, it was recently applied for the study of basicity on mixed oxides
[ 12]. In particular, carbon dioxide interaction with OH groups gives rise to hydro-
gencarbonate species well characterized by a 6(OH) absorption band near 1225
c m - i. These species are mainly observed on alumina.
The most sensitive method seems the measurement of catalytic activity in base
catalyzed reactions. Various reactions were proposed [9]. Among them, alcohol
decomposition is often used [ 9,10,12-14]. In particular, it is claimed that isopro-
panol dehydrogenation into acetone characterizes basicity [ 13]. However, it has
been shown that a typical basic oxide such as MgO is not very active towards
isopropanol dehydrogenation while ZnO is very active under the same conditions
[13]. Conversely, both oxides are active for methylbutynol conversion [ 13].
Recently COS hydrolysis was improved as a test for BrCnsted basicity [ 15,16].
Carbon dioxide and COS appear as two probe molecules convenient for the study
of the basicity of hydroxyls since the first step of the interaction is a nucleophilic
attack of the carbon dioxide [ 17,18] or COS [ 16] carbon atom by the basic OH
groups. In this work, the properties of sodium-impregnated aluminas are compared
using COS hydrolysis as test reaction and carbon dioxide for TPD and IR spec-
troscopy.

2. Experimental
2.1. Materials
Two series of sodium doped aluminium oxides were prepared. The samples of
the first series (C) were made by porous impregnation of commercially available
 V.A. Ivanov et al. / Applied Catalysis A: General 131 (1995) 323-334 325

Table 1
Sample characteristics

Sample Specific surface area (m 2 g-~)

C 207
C 300 207
C 700 203
C 1000 205
C 5000 206
F 300
F* 260
F 300 260
F 600 267
F 1000 228
F 2500 236
A 196
B 137

* The sample was obtained from sample F by addition of water and calcination 3 h at 773 K.

"y-Al203GFS with aqueous solutions of sodium nitrate of the concentration needed,

followed by drying at 403 K and calcination for 3 h at 773 K.
The precursor aluminium oxide for the samples of the second series (F) was
prepared from aluminium isopropylate (Fluka) by hydrolysis. Sodium-containing
samples were obtained by impregnation of A1203 with sodium nitrate following the
procedure described for the first series.
The amount of sodium oxide in samples after calcination was controlled by
chemical analysis, using emission spectrometry. The samples were labelled taking
into account their Na20 amount. For instance C-300 means that sample C contains
300 ppm of Na20. The structural properties of the alumina samples, measured by
nitrogen adsorption at 77 K, are given in Table 1. Comparison has been made with
amorphous (A) and well crystallized (B) aluminas, which contain 40 and 400
ppm of Na20, respectively, as already described [ 1 ].

2.2. Temperature-programmed desorption of carbon dioxide

Thermodesorption of carbon dioxide was carried out in a flow of helium with a

constant heating rate of 5 K m i n - 1. The quantity of desorbed carbon dioxide was
measured by a gas chromatograph equipped with a catharometer. Samples were
pretreated under a flow of helium (2 h, 673 K), then cooled to 323 K and saturated
for 1 h in a flow of dry carbon dioxide. After saturation alumina samples were
heated at 323 K in a flow of helium. TPD spectra were then recorded in the
temperature range 323-673 K.

2.3. IR study

IR spectra were recorded at beam temperature using a Nicolet 740 FT-IR spec-
trometer with a resolution of 2 cm-~. Samples were used in the form of self
326 V.A. Ivanov et al. /Applied Catalysis A: General 131 (1995) 323-334

supported wafers of ca. l0 mg cm -2, activated in situ under vacuum at 673 K or

as wafers of samples pressed in KBr (2 mg of sample in 200 mg of KBr). Carbon
dioxide was introduced in measured amounts on the activated samples at room
temperature. The spectra of adsorbed carbon dioxide were recorded after evacuation
at different temperatures.

2.4. Catalytic test

The reaction of COS hydrolysis was investigated in a flow reactor containing 25

mg of catalyst with a grain size of 0.5-1.0 mm. The mixture of vapours of water
and COS was carried by helium (2.3% H20; 1% COS) with a constant rate 2.7
mmol h - 1.of COS. The samples were pretreated 2 h at 523 K in the helium flow.
The catalytic activity was studied at 373 K. The initial compounds and reaction
products were analyzed in a gas chromatograph equipped with a column of Porapak
Q and a thermal catharometer detector.

3. Results

3.1. IR study in the region 400-1000 cm -1

IR study in KBr was shown as a sensitive method of phase investigation of

transition aluminas [ 19]. Generally two broad bands are observed near 800--850
and 600 c m - 1. The former was assigned to a stretching mode of tetrahedral groups.
It clearly appears in Fig. 1 that the relative intensity of the ca. 800 c m - t band is
higher in the spectrum of the well crystallized sample (B) than in that of the more
amorphous one (A). This is in agreement with the nuclear magnetic resonance
(NMR) results reported in [ 1 ] indicating that the amount ofAl ~v cations increased
with crystallization.
The spectra of sodium modified alumina samples are presented in Fig. 1. Based
on the IR spectra the proportion of AIIV/A1 vI cations for samples C is close to that

;-
J
~6oo ~oo ~oo 400 tOoo ~oo ~oo ~oo
NI~VENUMBER NI°tVENUMBER
Fig. 1. Infrared spectra of samples in KBr.
 V.A. Ivanov et al. /Applied Catalysis A: General I31 (1995) 323-334 327

~ F

7 2e 70
Fig.2. X-raydiffractionpatternsofsamplesF. Allanglesarein° (20) witha CuKa source.

of the well crystallized sample. Moreover, it does not change after Na + addition.
By contrast, the spectrum of sample F is close to that of the more amorphous
alumina. However, addition of 1000 ppm of Na20 increases the relative intensity
of the 800 c m - 1 band, and so the relative amount of A1TMcations. A larger Na +
amount (2500 ppm) does not modify the spectrum.

3.2. X-ray diffraction (XRD) measurements

The XRD patterns of samples A, B, C have already been reported in [ 1 ]. Those

of modified samples F are shown in Fig. 2. Comparison of peak intensities and
widths confirms the IR results reported above. In particular, it appears that treatment
by water followed by recalcination ( sample F* ) slightly increases the crystallinity
state of the starting compound F. Impregnation by sodium nitrate followed by
recalcination makes this effect more evident, principally when the sodium amount
reaches 1000 ppm.

3.3. OH vibrations

The spectra of the A, B and C samples have already been described in the u(OH)
vibration region [7 ]. Those of the F series are presented in Fig. 3. Initial aluminium
oxide F presents three peaks at 3770, 3730 and 3680 c m - 1 which are assigned to
types I, II and III OH groups, respectively. Addition of sodium oxide gives rise to
328 V.A. lvanov et al. /Applied Catalysis A." General 131 (1995) 323-334

] ~F2500

3~oo 3~so
NRVENUMBER
31oo 3~so 3~oo

Fig. 3. IR spectra of samples F after evacuation at 673 K in the 1,(OH) absorption range.

a decrease in intensity of the band at 3770 c m - J, which completely disappears for

the sample with 2500 ppm of Na20. A new band at 3755 c m - 1 appears in the form
of a small shoulder for F 1000 and becomes significant for F 2500. This band was
previously observed in the spectra of sodium containing alumina samples C [7]
and related to the influence of Na ÷ . For series C samples, the band at 3755 c m -
was significant, even for the sample with a very small content of Na20 (300 ppm).
In order to determine the relative basicity of hydroxyl groups giving rise to the
3755 cm-~ band, carbon dioxide has been adsorbed on samples C and C 1000.
Subtracted spectra evidence that on both samples OH bands near 3765, 3730 and
3670 c m - 1 are perturbed and in the case of C 1000, no preferential perturbation
appears for the 3755 c m - t band (Fig. 4). Note that the 3622 c m - t band is due to
the u (OH) vibration of hydrogencarbonate species. In order to specify the basicity
of the 3755 cm-1 OH group, the sample C containing 1% ( 10 000 ppm) of Na20
was prepared. Its IR spectrum mainly shows two u ( O H ) bands at 3752 and 3680
c m - t (Fig. 5) in agreement with the literature [3 ]. Carbon dioxide adsorption on
this sample leads to carbonate (bands at 1580, 1367 c m - J) and hydrogencarbonate
species, the latter at the expense of the two types of OH groups.

tn

0.

ii

362o aho
NRVENUMBER
ae6o 3 & a o a~oo

Fig. 4.1R spectra of the C 1000 sample in the v (OH) absorption region after evacuation at 673 K (a) ; the effect
of CO2 addition (Pe = 10 Torr) is shown in spectrum b obtained by subtracting spectra before and after CO2
introduction.
 V.A. lvanov et al. /Applied Catalysis A: General 131 (1995) 323-334 329

3~zo a->~,o s~so 3~eo 3~oo

NRVENUHBER
Fig. 5. IR spectra of C l0 000 sample in the v(OH) absorption range after evacuation at 673 K (a) ; the effect of
CO2 addition (Pe --- I 0 Tort) is shown in spectrum b obtained by subtracting spectra before and after CO2 addition
introduction.

3.4. Carbon dioxide adsorption and desorption

Among the different probe molecules used to determine the surface basicity of
metal oxides, sulphur dioxide and carbon dioxide appear to be the most convenient
[8]. However, SO2 adsorption on alumina basic sites is difficult to study by IR
spectroscopy due to the fact that alumina is not transparent below 1000 c m - i .
Carbon dioxide adsorption leads to the formation of various species. Bands near
2400-2350 cm i have already been used to study the alumina Lewis acidity [ 1 ].
Those at 1234, 1457, 1650 and 3620 cm-~ are due to carbon dioxide interaction
with OH groups giving rise to hydrogencarbonate species. Bands in the 1700-1850
cm -1 and 1150-1250 cm i frequency regions have been assigned to bridged
('organic-like') carbonate ions, or, more recently, to vibrations of strongly per-
turbed carbon dioxide molecules [ 20]. Other bands between 1710 and 1315 c m -
have been assigned to bidentate and monodentate carbonates [21 ].
Spectra of species formed from carbon dioxide adsorption on samples C, C 1000
and C 5000 are reported in Fig. 6. They show very slight modifications when adding
Na + , except for the NazO amount of 5000 ppm. In that case, the hydrogencarbonate
species predominate. Due to the superimposition of the bands characterizing the
different carbonate species formed, it is not possible to assess quantitatively the
variation of each type of species with the amount of Na + introduced. It is the reason
why we used TPD measurements to determine the global variation. In order to
eliminate the physisorbed carbon dioxide species leading to IR bands in the 2400-
2350 cm i range, the carbon dioxide precovered samples have been treated under
helium flow at 323 K.
The curves of carbon dioxide thermodesorption on some alumina samples are
presented in Fig. 7. There are no large differences in the character of thermode-
sorption curves of sodium containing alumina samples. All of them have a large
330 V.A, lvanov et al. /Applied Catalysis A: General 131 (1995) 323 334

ii

/A / /I ,..ClOOO
,
_ J ~._______J ',J -,j,

~oo a~zs ~so z~Ts z~oo 2tzs i%o i~7s i~oo

NRVENUHBER
Fig. 6. IR spectra of CO2 adsorbed species on C, C 1000 and C 5000 samples (Pe = 10 Tow).

i
373 473
T,K

Fig. 7. C Q TPD curves.

I I I I !

~ 5

_-.,\
° ~ ° ~

&B

Io~o 20'o0 3o'oo 4o~o 50'o0 eooo

NaO (ppm)

Fig. 8. Variation of desorbed CO2 amounts obtained from TPD curves as a function of Na20 amount.

desorption peak with their maximum at about 400-410 K. The samples with high
sodium content (2500, 5000 ppm) show a small shift towards higher temperatures.
It can be supposed that addition of sodium in large amounts gives rise to creating
somewhat stronger basic centres, which is in accordance with [ 10]. The amount
of adsorbed carbon dioxide as a function of sodium content is given in Fig. 8. These
data can correspond to the total basicity of samples. The quantity of adsorbed
carbon dioxide, calculated per m 2 of sample, passes a minimum at 600-1000 ppm
 V.A, Ivanov et al. /Applied Catalysis A: General 131 (1995) 323-334 331

15AI [ I i I I

E
r ~.~_ x F . c

~3.75

0
o'oo 2o'0o 3o'oo 4o~o 5o'o0 6o00
NaO (ppm)
Fig. 9. Variation of COS conversion with Na20 amount. ( e ) series F; ( × ) series C.

of Na20 for alumina samples of series F. The basicity of commercial aluminium

oxide C increases almost linearly with the increase of sodium content.
The amount of desorbed carbon dioxide on the amorphous sample (A) is in
agreement with that observed on the starting compounds C or F. As for the well
crystallized alumina (B), the amount of desorbed carbon dioxide is two times
lower. This clearly indicates an effect of the crystallinity towards the basicity.

3.5. Catalytic activi~

The activities of the alumina samples in the hydrolysis of COS were compared
under such conditions as to avoid diffusion effects. The data of COS conversion
on the samples of both series are given in Fig. 9. Alumina samples having high
concentrations of sodium oxide possess high activity in COS hydrolysis. Very small
quantities of introduced Na20 strongly decrease the activity of alumina F. Further
addition of sodium oxide increases it. The activity of sample C remains almost
stable after incorporation of trace amounts of sodium up to 1000 ppm and then
increases for the sample with a high concentration of Na20.
Comparison of the activity of amorphous (A) and well crystallized (B) samples
shows that basicity also strongly depends on the crystallinity. It significantly
increases with the amorphization. The explanation of this fact can be found in [ 1].
The relative quantity of octahedral aluminium ions increases with the amorphiza-
tion, increasing the basicity of the samples.

4. Discussion

Surface acidity is relatively well studied and can be assessed either using adsorp-
tion of probe molecules like pyridine or test reactions such as skeletal butene
isomerization or isopropanol dehydration. All these methods have been used to
study the effect of crystallinity [ 1] or sodium impurity [7] on the Lewis acidity
332 V.A. lvanov et al. /Applied Catalysis A: General 131 (1995) 323-334

of alumina. Basic properties are much more difficult to determine. As regards

alumina itself, two papers have been published recently using the same microca-
lorimetric technique but with different probe molecules. They both revealed that
the alumina surface exhibits a chemical heterogeneity with a very small amount of
strong basic sites [22,23]. However, this technique is not very precise and, to reach
the goal of the present study, we used different methods specific to basicity.
Among the alumina samples used before [ 1] we choose the standard C sample
as starting compound for sodium impregnation. However it contains a large amount
of titanium oxide (1800 ppm), which could modify its acidic or basic properties
and its morphology. To avoid such phenomena, we also prepared a second series
of samples, starting from a chemically pure alumina F, obtained from aluminium
isopropylate. The results obtained are different and discussed below in terms of
morphology or basicity.
Table 1 shows that the surface area of sample F is higher than that of sample C.
However, the former decreases after introduction of small amounts of sodium
whereas the latter remains constant. The decrease of surface area of sample F cannot
be ascribed to Na + incorporation since it occurs after water impregnation followed
by calcination ( sample F* ). Both Fig. 1 and Fig. 2 suggest a better crystallinity of
sample F* relative to sample F, explaining the difference in surface area. This can
be due to the conditions of thermal treatment of sample F, insufficient for complete
stabilization. Impregnation by water rehydroxylates the surface. Further heating
favours dehydroxylation and thus sintering.
A further decrease of the surface area of sample F is observed by adding large
amounts of sodium (Table 1 ). In agreement with Figs. 1 and 2, this can be ascribed
to a better crystallinity, due to sodium incorporation, suggesting that a part of
sodium migrates into the bulk. Due to the larger radius of Na +, relative to that of
A13 +, it tends to occupy preferentially octahedral vacancies. This would distort the
framework, minimising the A1-O distance of neighbouring atoms and so favouring
the AI w ~ A1TMtransformation. This migration needs a partial positive charge
compensation of this positive charge Nav. This can be related to the defect structure
of y-alumina, where oxygen vacancies Vo and hydroxyl ions in oxygen position
OHo have been identified by thermoluminescence [ 24], in addition to the structural
vacancies on some cationic positions. The compensation can thus happen either by
migration of oxygen into the network, for example:

20H~urface + go" --+ H2Oga~ + 0~3 ( 1)

or migration of a proton out of the network, for example:

OHo --+ O~ + H~urface

Hsurface + OH~urfac e ---+ H2Ogas (2)
(In Krtiger notation, ' refers to a negative charge, • to a positive charge and x to a
neutral effect).
 V.A. lvanov et al./Applied Catalysis A: General 131 (1995) 323-334 333

We can notice that in each case, the consequence of the process is to decrease
the abundance of defects in the anion subnetwork.
Results relative to A and B samples show that crystallization decreases the
alumina basicity. This could be related to the higher number of AI TM in crystallized
samples since the A13 +-02 bond strength should be greater and the charge on
oxygen smaller for A13 + in tetrahedral coordination than in octahedral position
[25].
The decrease of activity from F to F* is relative to the increase of crystallinity
as observed by comparison of A and B samples. Addition of very small amounts
of Na + still decreases the OH basicity of F samples (Fig. 9). This is not due to an
effect of crystallinity relative to F* but certainly to the sodium migration in the
bulk. Taking into account the presence of bulk OH group as shown by Tsyganenko
et al. [26], we propose that the Na + migration provokes the formation of bulk O~
groups and water with the liberated proton and an OH' group of the surface. Another
possibility, noted above, is the formation of water from two surface OH' groups
and a cationic vacancy. In both cases, the number of OH' groups decreases explain-
ing the lower basicity. The increase of basicity only arises when a larger amount
of Na + is introduced (more than 1000 ppm) preventing sodium migration into the
bulk and leading to surface O H - groups.
For samples C, basicity does not vary for a Na + loading less than 1000 ppm. In
this series, no change of crystallinity is observed and therefore no Na + migration
occurs. Moreover, the 3755 cm 1 OH band assigned to sodium addition appears
even for the smallest amount of Na + introduced. If the basicity of this type of
hydroxyl group is higher than that of OH groups of alumina, an increase of the C
1000 activity is expected relative to that of C. This was not observed and we can
conclude in agreement with carbon dioxide results, that the 3755 c m - ~ OH groups
are not more basic than those characterized by the ca 3780 cm I band. In samples
C, Na ÷ certainly occupies surface cationic vacancies as already discussed from
pyridine adsorption experiments [ 7 ].

Acknowledgements

The authors acknowledge Dr. O. Saur for helpful discussions and Dr. J. Bachelier,
deceased, who initiated the study.

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