15172 J. Phys. Chem.

B 2006, 110, 15172-15185

Nature, Structure and Strength of the Acidic Sites of Amorphous Silica Alumina: An IR
and NMR Study

G. Crépeau,† V. Montouillout,†,‡ A. Vimont,† L. Mariey,†,§ T. Cseri,| and F. Maugé*,†

Laboratoire de Catalyse et Spectrochimie, UMR CNRS, ENSICAEN, UniVersity of Caen,
14050 Caen Cedex, France, Centre de Recherche sur les Matériaux à Haute Température, UPR CNRS 4212,
45071 Orléans Cedex, France, Equipe de Recherche en Physico-chimie et Biotechnologies, EA 3914,
IUT-UFR de Sciences, 14032 Caen Cedex, France, and Institut Français du Pétrole, IFP - Lyon,
Direction Catalyse et Séparation, Département Catalyse Hétérogène, 69390 Vernaison, France
ReceiVed: April 11, 2006; In Final Form: June 8, 2006

IR spectroscopy of probe molecules (pyridine, 2,6-dimethylpyridine, and CO) as well as high-resolution solid
state NMR and especially double-resonance experiments give a new insight into the acidic sites of amorphous
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silica alumina (ASA). ASA samples are heterogeneous compounds that contain a silica alumina mixed phase
as well as aluminum clusters and pure silica zones. The distribution of various forms depends both on the
preparation method and on the Si/Al ratio. Formation of mixed phase leads to the creation of acidic hydroxyl
groups of various strength, up to that present in dealuminated HY zeolite. Detailed spectroscopic analyses
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show that these acidic OH groups correspond to the silanol groups located in close vicinity to an Al atom in
tetrahedral environment. The strength of the acidity of the OH species of ASA could be modified both by the
location of the vicinal Al atom on the surface or in the bulk and by the number of aluminum atoms in the
vicinity of silanol group. Cogelification of high silica-containing ASA appears as the best mean to prepare
homogeneous amorphous aluminosilicate, which exhibits the strongest Brønsted acidity.

Introduction in different ASA samples that can be used as support of the

hydrocracking catalyst.
Developments of fuel market as well as specifications for
more environmental-friendly products lead refiners to invest in Several papers reported the analysis of acidic properties of
processes for heavy oil conversion. Among them, hydrocracking ASA or related materials using adsorption of probe molecule
is a key process that produces selectively high quality fuels with followed by IR spectroscopy.9,10 The first papers dealing with
low sulfur content.1 The Hydrocracking catalyst is a bifunctional the characterization of the surface acidic sites of ASA appeared
solid, which combines hydro-dehydrogenation and acidic in the 70s.11,12 In these studies, nature of the acidic sites as well
function. The hydro-dehydrogenation component is usually a as their evolution versus Si/Al ratio was examined using pyridine
sulfide phase, while the acidic component is generally a zeolite or CD3CN chemisorption. These papers show that the formation
or an amorphous silica alumina (ASA). To obtain a good of the mixed silica-alumina phase leads to the creation of acidic
selectivity toward gas oil and kerosene, the acidity developed OH groups able to protonate pyridine. More recently, using CO
by hydrocracking catalysts should be moderate and significantly adsorbed at low temperature, a detailed analysis of the nature
lower than that of zeolites. Nevertheless, too weak acidic and the strength of the acidic sites of ASA prepared via different
properties lead to a catalyst of low activity. Consequently, routes was reported.3,13,14 These studies confirm the presence
balanced acidity is crucial to obtain high conversion and of some highly acidic OH groups on ASA. However, even with
appropriate selectivity. the benefit of the improved signal-to-noise ratio of the last
The use of oxides presenting moderate acidic properties as generation of the Fourier transform infrared (FTIR) spectrom-
ASA is preferred to maximize middle distillate products. eters, papers report for high-silica-containing ASA samples only
Recently, important developments in the synthesis of this type the presence of one main OH band located at a wavenumber
of oxide such as the synthesis of ASA via the sol-gel method equivalent to that of SiOH groups of silica, i.e., a very weakly
or coprecipitation method have been reported,2,3 or of alumi- acidic material. Thus, although several structures were proposed
nosilicates with controlled mesoporosity or micro-mesoporosity4-7 in the literature to account for this feature,13,15 the exact origin
have been reported. However, the adjustment of these new of the strong Brønsted acidity of ASA is still under discus-
preparations to hydrocracking application requires an accurate sion.
control of their acidic properties.8 IR spectroscopy is a tool of choice to characterize the acidic
Therefore, the aim of this work is to determine the nature, properties of oxides, particularly when using different basic
strength, concentration and environment of acidic sites present probe molecules, which present complementary chemical and
spectroscopic properties. Hence in this work, we will study
* To whom correspondence may be addressed. E-mail: adsorption of (i) pyridine, the most widely used probe on ASA,
francoise.mauge@ensicaen.fr. (ii) 2,6-dimethylpyridine (DMP), which presents strong affinity
† Laboratoire de Catalyse et Spectrochimie.
‡ Centre de Recherche sur les Matériaux à Haute Température. for weak Brønsted acid sites, and (iii) carbon monoxide, which,
§ Equipe de Recherche en Physico-chimie et Biotechnologies. when adsorbed at low temperature, is particularly suited to probe
| Institut Français du Pétrole. the strength of acidic OH groups.
10.1021/jp062252d CCC: $33.50 © 2006 American Chemical Society
Published on Web 07/15/2006
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15173

TABLE 1: Characteristics of the Studied Samples

name wt % SiO2 wt % Al2O3 preparation method Ssp (m2/g)
γ-Al2O3 0 100 273
Si30Al70 30 70 impregnation of alumina with silica gel 339
Si40Al60 40 60 impregnation of alumina with silica gel 324
Si88Al12 88 12 cogelification 449
Si94Al6 94 6 cogelification 488

High-resolution solid-state NMR is another well-established samples were activated in situ in the IR cell. The activation
method to probe the local environment of both aluminum and treatment consists of a ramp up to a given temperature (423,
proton atoms and provide important information about the solid 573, or 723 K) under primary vacuum. When the activation
acidity of zeolites and ASA materials. In particular, 1H magic temperature was reached, the cell was pumped under secondary
angle spinning (MAS) NMR with the development of double- vacuum down to a residual pressure of 5 × 10-6 Torr. For the
resonance NMR, which combines the high-resolution 1H MAS three activation temperatures, the heating time was kept constant,
experiment with the reintroduction of the dipolar coupling, has i.e., the heating rates were different: V ) 2 °C/min for Tact )
become a relatively popular tool to identify the different OH 423 K, V ) 3 °C/min for Tact ) 573 K, and V ) 3.5 °C/min for
groups present in the materials. In this work, we used a 27Al Tact ) 723 K.
MAS experiment to probe the environment of aluminum atoms, Catalyst acidity was characterized by IR spectroscopy using
and 1H {27Al} TRAPDOR16 (transfer of population in double pyridine, DMP, and CO as probe molecules. Two different IR
resonance) experiment to assign the different proton lines on cells were used depending on the temperature of adsorption
the basis of their vicinity with Al centers. The combined use of probe molecule. For pyridine and DMP experiments, a con-
double resonance NMR experiments and IR spectroscopy ventional glass cell was used, while for CO experiments, a low-
appears as a unique mean to specify the environment of protonic temperature cell was chosen. The latter IR cell is equipped with
species in ASA. CaF2 windows and presents double walls with a space for
cooling agent (liquid nitrogen in this work).
Experimental Section After activation, 1 Torr of pyridine or of DMP was introduced
in the cell where the wafer was maintained at 323 K (or 373 K
2.1. Catalysts. The ASA samples studied in the present work for DMP). An adsorption temperature higher than ambient
are either prepared at the Institut Français du Pétrole or temperature was used to ensure a good diffusion of the probe
commercial materials. They are named SiXAlY where X and molecule through the catalyst pellet. After adsorption of the
Y are respectively the weight percentage in SiO2 and in Al2O3 probe molecule, the sample is then evacuated at increasing
(Table 1). Si88Al12 and Si94Al6 were prepared by cogelifica- temperatures, up to the temperature of sample activation.
tion using sodium metasilicate and aluminum sulfate as precur-
For CO-adsorption experiments, the activated sample was first
sors. Sulfuric acid was added to the solution to adjust the pH.
cooled to 100 K under vacuum. Then, small doses of CO were
The synthesis was performed at 293 K. After cogelification,
introduced and IR spectra were recorded for each dose.
the samples were washed, dried at 393 K, and calcined in dry
The spectra presented in this paper are all normalized to a
air at 823 K. Si30Al70 and Si40Al60, which were supplied by
constant mass of wafer (m ) 10 mg for a disk diameter of 16
Condea, were prepared by impregnation of alumina with silica
mm). The IR spectra following adsorption of probe molecule
gel. The specific surface areas were determined by the Brunauer-
correspond to difference spectra, i.e., spectra of the samples
Emmett-Teller (BET) method. Characteristics of the studied
taken in the presence of probe molecule after subtracting the
ASA are summarized in Table 1.
spectrum before probe molecule adsorption.
2.2. NMR. High-resolution solid-state NMR experiments
The IR spectra were recorded with a FTIR Magna spectrom-
were conducted at 9.4 T on a Bruker AVANCE 400 spectrom-
eter from Thermo Optek. To obtain high-quality spectra
eter, operating at 400.33 and 104.5 MHz for 1H and 27Al,
(particularly in the zone 4000-3000 cm-1), the spectrometer
respectively. 27Al MAS NMR spectra of hydrated samples were
was equipped with a XT-KBr beam splitter and with a MCT/A
acquired with a MAS frequency of 15 kHz after a single, short
detector. The spectra were scanned using 256 scans with a
pulse, ensuring quantitative excitation of the central transition.
resolution of 4 cm-1.
For 1H experiments, the samples previously dehydrated at 700
K for 4 h, were placed inside a 4-mm MAS NMR rotor, under
Results and Discussion
vacuum, using a home-built device, described elsewhere.17,18
The 1H MAS spectra were recorded using a rotor-synchronized 3.1. NMR Characterization. 3.1.1. Al Environment. Figure
Hahn-echo pulse sequence in order to remove the background 1 shows the 27Al MAS NMR spectra of the ASA samples. The
signal arising from residual probehead protons. The spinning spectrum of the Si94Al6 sample, containing the lower amount
rate was fixed to 10 kHz and the evolution period to 600 µs. of aluminum shows a main signal centered at 53.4 ppm and a
The 1H nutation frequency was set to 59 kHz and the recycling weaker, broader signal at around 1 ppm, respectively, attributed
delay to 30 s to avoid no saturation. Similar 1H excitation to 4-fold (AlIV) and 6-fold (AlVI) oxygen-coordinated aluminum.
conditions were used for 1H {27Al} TRAPDOR experiment,16 This suggests that, in this sample, aluminum atoms are almost
combined with a continuous irradiation on the quadrupolar 27- exclusively in a tetrahedral environment. The signal is Gaussian
Al nuclei during the first evolution period of the Hahn-echo like and does not exhibit a specific quadrupolar line shape. It
sequence (i.e., 600 µs). The 27Al nutation frequency was set to is characteristic of a quite symmetric environment for the
70 kHz to satisfy adiabaticity conditions. The 1H and 27Al aluminum. The spectra of the two samples obtained by
chemical shifts were referenced relative to TMS and Al(NO3)3 impregnation, Si40Al60 and Si30Al70, are quite similar. They
1 M, respectively. are composed of two main peaks with maximum at around 60
2.3. IR Spectroscopy. The ASA samples were grounded, and and 5 ppm, attributed to aluminum in tetrahedral and octahedral
pressed into self-supported wafers (disk of ca. 5 mg cm-2). The environment. These spectra are similar to that of γ-alumina.
15174 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

Figure 2. 1H {27Al} TRAPDOR experiment of Si40Al60 (B0 ) 9.4

T, rotation 10 kHz). The full and the dotted lines correspond,
respectively, to 1H MAS spectrum acquired without and with 27Al
irradiation.

distinction between different hydroxyl groups. Moreover, it is

possible to discriminate the protons adjacent to aluminum from
other OH groups using double resonance experiments, such as
1H {27Al} TRAPDOR sequence, based on the analysis of the
Figure 1. 27
Al MAS NMR spectra of ASA (B0 ) 9.4 T, rotation 14
kHz). effect of dipolar 1H/27Al interaction on MAS proton spectra.
The 1H MAS NMR spectrum of the Si40Al60 sample,
However, the nonzero intensity between the two main lines previously outgassed at 700 K for 4 h, is presented in Figure 2.
indicates the presence of a third, weaker component, not present In addition to the main peak at 1.8 ppm, attributed to silanol
in alumina. The signals exhibit an asymmetric line shape with groups,22 a weak shoulder can be observed at about 2.8 ppm.
a steep low-field edge and a trailing high-field edge, charac- No signal at 7 ppm characteristic of Brønsted acid sites Si-
teristic of distorted environment. Finally the spectrum of the (OH)Al was detected.23 The assignment of the weak signal at
Si88Al12 sample, obtained by cogelification, exhibits clearly 0.8 ppm is not straightforward. Indeed, according to the literature
three components with isotropic chemical shift in the range of it can be attributed to either a SiOH group interacting with the
60-70, 30-40, and 0-10 ppm. The signals at 60-70 and 0-10 oxygen of the framework24 or to a AlOH species of pure
ppm are unambiguously assigned to AlIV and AlVI species.19 γ-alumina.25
According to the literature,20 the third signal (30-40 ppm) is The environment of the two types of proton is probed using
ascribed to a pentacoordinated aluminum center. This type of 1H {27Al} TRAPDOR sequence. In this experiment, the use of

environment is commonly observed in oxides obtained by sol- continuous-wave 27Al irradiation during 1H signal acquisition
gel routes.19 results in a loss of intensity of resonances attributed to proton
All the spectra have been simulated using Dmfit software21 in close spatial proximity with aluminum (at about 5 Å or less).
to extract a precise isotropic chemical shift, mean quadrupolar The TRAPDOR experience (dotted line in Figure 2) shows that
coupling as well as the relative intensity of the various the irradiation of 27Al leads to the disappearance of the shoulder
components. The results are summarized in Table 2. Despite centered at 2.8 ppm, while the main peak at 1.8 ppm is not
the different synthesis routes used, the results indicate that the affected. One may thus conclude that a small fraction of
fraction of 6-fold coordinated aluminum increased with the hydroxyl groups is close to aluminum atoms, while the majority
amount of alumina. In fact, the AlIV/AlVI ratio is maximum at of proton species are silanol groups, distant from aluminum.
low Al concentration. Moreover, the comparison between the 3.1.3. Conclusion. The 27Al NMR experiments clearly
spectra of γ-Al2O3 and those of impregnated samples indicates evidence the difference in aluminum local environment induced
that these samples (Si40Al60, Si30Al70) are mainly composed by the synthesis conditions. In the ASA prepared by impregna-
of a core of alumina surrounded by silica layer. By contrast, tion of alumina by silica gel (Si30Al70, Si40Al60), the
the presence of an important amount of penta and tetracoordi- environment of aluminum atoms remains very close to that of
nated aluminum in the Si88Al12 obtained by cogelification pure alumina, in variance with the ASA prepared by cogelifi-
suggests a better incorporation of aluminum in the silica cation (Si88Al12, Si94Al6), where indication of mixed phase
network. was detected. At least, two types of OH groups can be
3.1.2. Proton Environments. 1H MAS spectral resolution distinguished on the ASA surface: silanol groups, as observed
improves with the dehydration process thus allowing the in pure silica, and hydroxyl groups close to aluminum atoms.

TABLE 2: NMR Parameters Characteristics of the Different Aluminum Environment in ASA Samples
AlIV AlV AlVI
sample δiso (ppm) CQ (MHz) % δiso (ppm) CQ (MHz) % δiso (ppm) CQ (MHz) %
Si94Al6 55 2.3 84 7 6.7 16
Si88Al12 58 4.3 40 34 4.7 15 5 4.9 45
Si40Al30 72 5.4 30 30 2.8 4 12 4.8 66
Si60Al40 72 5.4 31 60 2.8 4 12 4.8 65
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15175

Figure 3. (A) IR spectra of the ASA activated at different temperatures. (B) Enlargement of the ν(OH) zone for the ASA activated at 723 K.

3.2. IR Characterization. The effects of the composition,

preparation method and activation treatment on the acidic sites
of ASA samples were examined by IR spectroscopy. The present
study focuses on the ASA Si30Al70, Si40Al60, and Si88Al12
solids.
3.2.1. Hydroxyl Groups. Figure 3 presents the OH stretching
zone of the different ASA after activation under vacuum at 423,
573, and 723 K. For the three samples, an asymmetric and sharp
band at ∼3748 cm-1 characteristic of silanol groups is de-
tected.26 The zoom on the ν(OH) band of ASA activated at 723
K shows that the SiOH band shifts from 3746 up to 3749 cm-1
with increasing Si content. When activation is performed at 423
K, a broad envelope, which extends from 3700 to 3300 cm-1, Figure 4. Evolution of the silanol group number per square nanometer
can also be detected. This envelope completely disappears on with silica amount for the ASA samples and silica activated at 723 K.
activation at 723 K, indicating the presence of silanol groups
in interaction with water molecules at low activation temper- composition on the surface and in the core of the particles. By
ature. Indeed, the molecular water (band at 1640 cm-1) is contrast, on Si30Al70 and Si40Al60 samples, the Si composition
completely eliminated only for activation temperatures higher was higher than that expected, indicating an enrichment in silica
than 573 K. on the surface. Such differences can be related to the synthesis
It is worth noting that, even for samples containing 60 and methods since Si30Al70 and Si40Al60 samples are prepared
70 wt % of alumina, no bands characteristic of alumina ν(OH) by impregnation of alumina with silica gel while Si88Al12 is
vibrations are detected (absence of bands at 3790-80, 3775- obtained via cogelification.
70, 3730-25, and 3700-3675 cm-1). In the literature, the 3.2.2. Pyridine Adsorption. Introduction. Pyridine is the
absence of hydroxyl group characteristic of alumina has already most commonly used probe molecule to assess the acidic sites10
been reported on ASA in the case of samples containing less and one of the first molecules used to characterize the acidic
than 50 wt % of alumina.27 For ASA samples containing 75 wt properties of ASAs.11,12 Pyridine presents the advantage of
% of Al2O3, Cairon et al. detected a shoulder at 3725 cm-1 and giving rise to very distinct vibrationnal bands according to its
a relatively large envelope centered at 3700 cm-1.28 In our case, mode of interaction with the surface. For instance, wavenumbers
the absence of Al-OH band, even in the spectrum of the of ν8a and ν19b bands are commonly used to discriminate
Si30Al70 sample, indicates a lower concentration of surface pyridine coordinated to Lewis acid sites (LAS), protonated on
Al atoms probably due to the preparation method. Indeed, the Brønsted acid sites (BAS), or in interaction via a H bond.32,33
high alumina-containing ASA of the present study were prepared Regarding the site strength, the wavenumber of the ν8a band is
by impregnation of alumina by silica gel, whereas the samples a good indicator of the Lewis strength, whereas no information
studied by Cairon et al.28 were obtained by cogelification. about the BAS acidic strength can be drawn from the wave-
The concentration of silanol groups can be assessed using numbers of ν8a and ν19b bands specific of Brønsted acid sites.
values of molar extinction coefficient of silanol band, (SiO- Such an information can, nevertheless, be obtained by study of
H) about 3 µmol-1 cm, previously determined by different pyridine thermodesorption.
authors.29-31 Thus, the amount of silanol groups per square Nature of Acidic Sites. Figure 5 presents evolution of the
nanometer of oxide was calculated. Figure 4 reports silanol pyridine vibration bands vs thermodesorption temperature for
group concentrations vs silica content for the three ASA studied Si40Al60 activated at 573 K. The other ASA samples show
and compares these values to that obtained for a pure silica qualitatively very similar spectra. Three interaction modes of
(SiO2 Degussa, SBET ) 450 m2/g). From the comparison between pyridine can be distinguished:
the number of silanol per square nanometer and the silica content Protonation (PyH+), characterized by bands at 1640, 1547,
measured by chemical analysis, one can assess the surface and 1492 cm-1. From pyridine thermodesorption, one can note
concentration in silica. In general, the concentration of silanol that the major fraction of the pyridinum species is elimi-
groups increases with silica content, as expected from the band nated on evacuation at 473-523 K. However some OH species
assignment. However, a more detailed analysis shows that, on still retain pyridine at temperature as high as 573 K, indicating
Si88Al12, the concentration of silanol groups corresponds to the existence of a small amount of very strongly acidic OH
that expected from chemical analysis, indicating a similar Si groups.
15176 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

perturbed by pyridine coordinated species, and thus even after

thermodesorption at 573 K, these species are still detected on
ASA.
The effect of the chemical composition on the ASA acidic
sites is presented in Figure 6. From pyridine adsorption spectra,
the results show the higher the silica content, the larger the
amount of BAS (1640 and 1547 cm-1). Conversely, the increase
of silica percentage decreases the amount of LAS (1622 and
1451 cm-1). It should be mentioned that weak LAS (shoulder
at 1615 cm-1) are specifically diminished on the high silica
sample.
Activation temperature changes the nature of ASA acidic
Figure 5. IR spectra of pyridine adsorbed on Si40Al60 activated at sites. As expected, the higher the activation temperature, the
573 K and pyridine adsorbed at 323 K and evacuated at: (a) 298 K, larger the amount of LAS (spectra not shown). Conversely, the
(b) 323 K, (c) 373 K, (d) 423 K, (e) 473 K, (f) 523 K, (g) 573 K.
increase of the activation temperature decreases the amount of
BAS.
3.2.3. DMP Adsorption. Introduction. The use of methyl-
substituted pyridine such as 2,6 dimethylpyridine (DMP or
lutidine) to probe the acidic properties of alumina was reported
for the first time by Knözinger et al.35,36 DMP is more basic
(pKB ) 7.3) than pyridine (pKB ) 8.8), due to the presence of
the two methyl groups in the R position. Consequently, DMP
can protonate on more weakly acidic OH groups compared to
pyridine.37 Protonation of the DMP is clearly evidenced by the
appearance of ν8a and ν8b bands in the 1650-1625-cm-1 zone
(Table 3), as well as by the appearance of a δ(NH) band at
1270 cm-1. With respect to the bands in the zone 1618-1603
cm-1, some confusion appears in the literature about their
assignment. Corma et al.38 ascribed the band detected at 1618
cm-1 on γ-alumina to DMP protonated on weak Brønsted acidic
Figure 6. IR spectra of pyridine evacuated at 373 K on the ASA sites, whereas Matulewicz et al.39 and Morterra et al.40 attributed
samples activated at 573 K.
it to DMP coordinated to Lewis acidic sites. The attribution of
this band to DMP in interaction with weak BAS appears,
Hydrogen bond (PyH), characterized by bands at 1597, 1492, however, inconsistent with several experimental observations.
and 1451 cm-1. The band at 1597 cm-1 completely disappears Indeed, the band at 1618 cm-1: (i) is more clearly visible on
following evacuation at 373 K, confirming its attribution to samples activated at high temperature, (ii) is no longer observed
weakly interacting species. on alumina following H2O or H2S adsorption,41 and (iii) is still
Coordination (PyL), characterized by bands at 1622, 1615 detected after DMP evacuation at temperature as high as 573
(sh.), 1578, 1492, and 1451 cm-1. After evacuation up to 423 K. Thus, the band at 1618 cm-1 should be assigned to the ν8a
K, the shoulder at 1615 cm-1 disappears, whereas the band at vibration of DMP coordinated to strong Lewis acid sites of
1451 cm-1 shifts to 1458 cm-1. These features indicate the alumina, i.e., on Al3+ in incomplete tetrahedral coordinance.
presence of weak LAS. By contrast, the bands at 1622 and at On alumina, DMP adsorption also leads to the appearance of a
1458 cm-1 are still clearly observed even after evacuation at band at 1603-1606 cm-1 that was assigned by Morterra et al.40
573 K indicating the presence of very strong LAS. to DMP coordinated to weaker LASs. It should be mentioned
It should be mentioned that, when pyridine is evacuated at that H bonding of DMP with silanol groups also gives rise to
temperatures higher than 473 K, no variation in the position of a band at such a wavenumber (1604 cm-1). Therefore, contrary
the bands at 1622 and 1458 cm-1 is observed. This is in variance to previous reports,38 DMP can interact with various acidic sites
with what is generally observed on pure γ-alumina where these of the surface, including with LAS. DMP is particularly well
two bands shift progressively from 1623 to 1626 cm-1 and from suited to distinguish the BAS from the LAS (Table 3).
1451 to 1456 cm-1 when the temperature of evacuation of Difficulties arise for discriminating the nature of weak acidic
pyridine increases from 373 up to 573 K.34 The absence of shift sites. DMP signal is sensitive to the LAS strength. Recently,
in the position of the LAS bands when pyridine coverage we evidenced that the DMPH+ signal can also monitor the
decreases can be an indication of a very homogeneous environ- strength of the BAS.42 Thus, the wavenumbers of ν8a and ν-
ment of the strong Lewis acid sites on ASA or a weaker lateral (NH) bands of DMPH+ vary with the strength of Brønsted
interaction effect between adsorbed pyridine molecules due to acidity: the lower the ν8a wavenumber and the higher the ν-
a smaller LAS density on ASA compared to Al2O3. (NH) wavenumber, the stronger the OH acidity.
It is also worth noting that it is not possible to specify which Nature of Acidic Sites. Figure 7A presents spectra of DMP
OH groups are responsible for the protonation of pyridine by adsorbed on Si40Al60 activated at 573 K in the 1700-1550-
analyzing the OH group region. Indeed, OH groups are also cm-1 region, i.e., the most characteristic zone of various DMP

TABLE 3: 2,6-DMP Vibration Frequency According to Its Mode of Adsorption (cm-1)

vibration modes DMP physisorption DMP‚‚‚H DMP-L (coordination) DMPH+ (protonation)
ν8a 1595 1600 1618-1603 1650-1640
ν8b 1580 1580 1573 1630
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15177

Figure 7. (A) IR spectra of DMP adsorbed on Si40Al60 activated at 573 K; DMP adsorbed at 373 K and evacuated at: (a) 298 K, (b) 323 K,
(c) 373 K, (d) 423 K, (e) 473 K, (f) 523 K, (g) 573 K. (B) Difference between spectra corresponding to two successive temperatures of
evacuation.

adsorption modes. On the ASA samples, three interaction modes

of DMP can be distinguished:
Protonation (DMPH+), characterized by the ν8a and ν8b bands
at ∼1650-1640 and 1630 cm-1 and by the δ(NH) band at 1270
cm-1.
Coordination (DMPL), characterized by the band at ∼1618
cm-1 and by a part of the band at 1583 cm-1
Hydrogen bonding (DMPH‚‚‚H) or interaction with the weak
LASs, characterized by the band at 1604 cm-1 and by a part of
the band at 1583 cm-1.
Figure 7A, which presents the effect of DMP thermodesorp-
tion, shows that the bands at 1604 and 1583 cm-1 preferentially
disappear, as expected from their assignment to DMP in weak Figure 8. IR spectra of DMP evacuated at 573 K on Si40Al60 and
interactions with the surface (H-bond or weak LAS). The band Si88Al12 activated at 573 K.
at 1618 cm-1 resists to increasing the evacuation temperature
up to 573 K, in agreement with its attribution to DMP comparison of the two DMP spectra reveals some differences
coordinated to the strong LAS. Thermodesorption leads also to in the DMPH+ envelope. The high-frequency part of the
a progressive decrease of the intensity of the two bands specific DMPH+ envelope on Si88Al12 does not extend up to wave-
of protonated DMP species. However, these two bands are still number as high as on Si40Al60. This difference in frequency
observed after pumping at 573 K indicating the presence of some reflects the difference in acidic strength of ASA OH groups.
strong BAS on the ASA surface. In addition, one can note a The Si88Al12 solid exhibits stronger BASs.
shift of the νa DMPH+ band when evacuation temperature In summary, DMP confirms the presence of BAS and strong
increases. LAS on the ASA, as detected by pyridine. Moreover, the
To more accurately analyze the temperature of elimination wavenumber of DMPH+ bands indicates that Si88Al12 exhibits
of each DMP species, difference spectra for two successive a larger concentration of strong Brønsted acidic sites than low
temperatures of evacuation were also calculated (Figure 7B). silica-containing ASA samples.
Thus on this figure, the negative bands characterize the species 3.2.4. Carbon Monoxide Adsorption. Introduction. Carbon
that are eliminated in the considered temperature range. The monoxide, a weak base, is a very powerful probe molecule. It
shift of the bands characteristic of DMPH+ species with can coordinate on Lewis acid sites, and if adsorbed at low
evacuation temperature is more clearly visible. For mild temperature (T ≈ 100 K), it can also form a H bond with acidic
evacuation temperatures (between 373 and 423 K), DMPH+ OH groups. Depending on its interaction mode, wavenumbers
species, which are eliminated, give rise to bands at 1651 and of ν(CO) bands can be directly related to the acidic strength of
1630 cm-1 (see negative bands). When the evacuation temper- Lewis acid sites or hydroxyl groups. The vibration frequency
ature increases, the ν8a band of eliminated protonated DMP of CO in interaction with LAS can reach 2230 cm-1 for very
species shifts progressively down to 1644 cm-1, while the strong LAS and shifts down to 2157 cm-1 for very weak LAS.
wavenumber of ν8b vibration remains constant (∼1630 cm-1). For CO in interaction with acidic OH groups, the ν(CO)
These observations are in agreement with our previous study,42 frequency range is located between 2180 and 2152 cm-1
since the lower the ν8a frequency, the stronger the BAS site. depending on the OH acidic strength. Thus, discriminating
The present work indicates that the ν8a band of DMPH+ formed between CO in interaction with LAS from CO in interaction
on ASA contains several components and, accordingly, only with acidic OH groups is not always staightforward from
DMP in interaction with the strongest acidic OH groups resists analyzing the CO stretching frequency zone. A parallel study
to the highest temperatures of evacuation. of ν(CO) and ν(OH) zone is often necessary to distinguish
Figure 8 compares the spectra of DMP adsorbed on Si40Al60 between CO interaction via coordination or via H bonding. CO
and Si88Al12 after DMP evacuation at 573 K. The two samples in interaction with OH groups of metal oxides or zeolites leads
present bands characteristic of DMP coordinated to strong LASs to the formation of H-bond and the extent of ν(OH) band
(ν8a band at 1618 cm-1) and of DMPH+ (bands in the zone perturbation, ∆ν(OH/CO), is proportional to the OH group
1650-1630 cm-1). The absence of H-bond DMP is consistent acidity. As reported by Maache43 and Cairon,13 correlation
with the high temperature of evacuation (573 K). Detailed between ν(CO) frequencies and ∆ν(OH/CO) values could be
15178 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

Figure 9. Relationship between ∆ν(OH/CO) shift and ν(CO) wavenumber for CO adsorbed on various zeolites and oxides: (×) values issued
from literature data; (f) values obtained on ASA (solid star, when both ∆ν(OH/CO) and ν(CO) are determined in the present study; open star,
when only ∆ν(OH/CO) is determined.)

Figure 10. IR spectra of CO adsorbed on Si88Al12 activated at 723 K: (a) 10 µmol/g, (b) 30 µmol/g, (c) 80 µmol/g, (d) 160 µmol/g, (e) 260
µmol/g. (A) Zone ν(OH); (B) zone ν(CO). Inset: enlargement of the ν(OH) zone for 10, 30, and 80 µmol/g.

established for a large number of acidic materials (Figure 9). the OH perturbed band appears at 3393 cm-1. The introduction
Thus, these two values are good indicators of the acidic strength of additional doses leads to the appearance of a second OH
of the OH groups. perturbed component at 3456 cm-1. The first OH perturbed
Acidic Sites of Si88Al12. To determine the nature and the component corresponds to a downward shift of the silanol band
strength of the acidic sites of ASA and that for acidic sites of 367-356 cm-1, while the extent of OH perturbation of the
eventually present in low concentrations, both very small and second component is of 293 cm-1. For these CO doses, only a
large doses of CO were adsorbed on the samples. In the very small fraction of isolated silanol groups is perturbed. For
following, we will successively analyze spectra corresponding more important CO doses, another component appears at 3560
to these two ranges of CO doses. cm-1 (∆ν(OH/CO) ) 189 cm-1 ), while an intense perturbed
Figure 10 presents spectra of the adsorption of small CO doses OH band develops at 3656 cm-1 (∆ν(OH/CO) ) 93 cm-1),
on Si88Al12 activated at 723 K. It shows, even for the first which becomes predominant for more important CO doses.
CO dose, the partial disappearance of the 3749-cm-1 band. It should be noted that the difference spectrum corresponding
Concomitantly, a broad OH envelope appears at a lower to the introduction of the very first CO dose reveals the
wavenumber (Figure 10A). This envelope contains several appearance of a positive band at 3752 cm-1 (Figure 10A). This
components whose ratios vary according to the CO amount. upward shift indicates a small decrease of the sample temper-
They reveal the presence of hydroxyl groups with different ature. Indeed, the introduction of CO in the cell improves
acidic strengths. Indeed, the very first CO dose (10 µmol g-1) thermal conduction between the cell reservoir full of liquid
adsorbed on Si88Al12 shifts a small fraction of the ν(OH) band nitrogen and the wafer. This change of the sample temperature
from 3749 cm-1 down to 3382 cm-1. After the second CO dose, leads to a slight shift of the ASA OH bands toward higher
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15179

Figure 11. IR spectra of CO adsorbed (130 µmol of CO per gram of catalyst) on Si30Al70, Si40Al60, and Si88Al12 activated at 723 K. (A) Zone
ν(OH); (B) zone ν(CO).

wavenumber, and thus, a part of the band at 3749 cm-1 shifts (2) strong acidic OH groups (sites A2) giving rise to a ν(OH)-
up to 3752 cm-1. perturbed band at 3456 cm-1, i.e., a ∆ν (OH/CO) equal to 293
On Si88Al12, the analysis of the ν(CO) region shows that cm-1, and a ν(CO) band at 2174 cm-1;
the addition of small CO doses leads to the emergence of a (3) medium acidic OH groups (sites B) giving rise to a ν(OH)-
band at 2178 cm-1 (clearly detected for the very first doses perturbed band at 3565 cm-1, i.e., a ∆ν (OH/CO) equal to 189
and then present as a shoulder), and of a band at 2230 cm-1 cm-1;
with a shoulder at 2196 cm-1. The increase of the amount (4) low acidic OH groups (sites C) giving rise to a ν(OH)-
of CO introduced leads to a shift in the wavenumber of the perturbed band at 3656 cm-1, i.e., a ∆ν(OH/CO) equal to 93
2178 cm-1 band down to 2174 cm-1 and to the development cm-1 and ν(CO) band at 2157 cm-1;
of a new component at 2157 cm-1 that increases in intensity (5) strong and medium Lewis acidic sites characterized by
with subsequent addition of CO doses and becomes predomi- bands at 2230 and 2196 cm-1, respectively. The presence of
nant. LAS of weak acidity could not be excluded. Indeed, the
From their frequency range values, the ν(CO) bands at 2230 envelope at 2178-2157 cm-1 can contain the contribution of
and at 2196 cm-1 can be attributed to CO coordination to strong CO coordinated to weaker LAS in addition to the contribution
and medium LAS. The attribution of the ν(CO) bands with of acidic hydroxyl groups.
wavenumbers lower than 2180 cm-1 to CO in interaction with Effect of the Composition on the Acidic Sites. Figure 11 shows
LAS or with acidic OH groups is not always straightforward the effect of catalyst composition for ASA samples activated
considering only their frequencies. More definite assignments at 723 K following adsorption of small CO doses. With respect
can be made using the CO small doses experiments and the to LAS, two types are detected on the three samples. The
correlation with corresponding shift in the ν(OH) region. Thus, abundance of the LAS (2230 cm-1) is constant for all Al content,
the ν(CO) band at 2178 cm-1 can be clearly assigned to CO in whereas that of weaker strength (2196 cm-1) increases with the
interaction with acidic OH groups. Indeed, first the band at 2178 Al amount. As for the acidity of OH group, the region of
cm-1 appears with the first CO doses, while the band at 2230 perturbed OH groups is similar on Si40Al60 and Si30Al70.
cm-1 is barely detectable. If the band at 2178 cm-1 was Thus, the very first dose gives rise to a perturbed ν(OH) band
characteristic of coordinated CO, it should be formed after that at 3395-3400 cm-1. When CO coverage increased, this band
specific of the strongest LAS (at 2230 cm-1). Second, the shifts to 3460-3475 cm-1, while a second perturbed OH band
appearance of the band at 2178 cm-1 correlates with the appears at 3550 cm-1. In parallel, in the CO stretching zone, a
development of the OH perturbation of 367 cm-1. The position band at 2174 cm-1 and a shoulder at 2170 cm-1 are detected.
of the ν(CO) band agrees with the expected OH shift from These two bands are associated with the perturbed OH groups
Figure 9. By use of the same methodology, the ν(CO) band at at ∼3400 and ∼3560 cm-1, respectively. Thus, the three ASA
2174 cm-1 can be associated to the perturbed OH band at 3456 samples present very strong BAS (sites A1 and A2) and medium
cm-1 (∆ν(OH/CO) ) 293 cm-1) and the band at 2157 cm-1 to BAS (sites B). It can be noted that the frequency of the ν(OH/
the perturbed OH band at 3656 cm-1 (∆ν(OH/CO) ) 93 cm-1). CO) band corresponding to the sites A1 is located at lower value
However, the perturbed OH band observed at 3560 cm-1 cannot for Si88Al12 (3382 cm-1) compared to that observed for
be clearly related to a specific ν(CO) band (expected at 2165 Si40Al60 and Si30Al70 (3395 cm-1). This reveals that the ASA
cm-1 from Figure 9), because of potential overlap with adjacent which contains the highest amount of Si exhibits the strongest
CO bands at 2174 and 2157 cm-1 (Figure 10). Note that as BAS. Note that quantitative comparison is difficult to draw from
shown on Figure 9 there is very good agreement between ∆ν- these spectra, since CO does not saturate all the acidic sites
(OH/CO) values and corresponding ν(CO) frequency observed present.
on acidic OH groups of ASA and those detected on oxides and Figure 12 compares the spectra obtained on the three ASA
zeolites. after saturation of the surface with CO (1 Torr of CO at
This study shows that Si88Al12 sample exhibits: equilibrium). This figure shows that the OH bands associated
(1) very strong acidic OH groups (sites A1) giving rise to a with sites of weak acidity (sites C) are predominant and increase
ν(OH)-perturbed band at 3382-93 cm-1, i.e., a ∆ν(OH/CO) in intensity with the silica content. This confirms that the amount
equal to 367-356 cm-1, and a ν(CO) band at 2178 cm-1; of LAS with medium acidity increases with Al content.
15180 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

Figure 12. IR spectra of CO adsorbed (dose corresponding to the saturation of the surface in CO) on Si30Al70, Si40Al60, and Si88Al12 activated
at 723 K. (A) Zone ν(OH); (B) zone ν(CO).

Figure 13. IR spectra of CO adsorbed on Si94Al6 activated at 723 K: (a) 30 µmol/g, (b) 90 µmol/g, (c) 170 µmol/g, (d) 290 µmol/g, (e) 440
µmol/g, (f) 590 µmol/g. (A) Zone ν(OH); (B) zone ν(CO).

Acidic Sites of Si94Al6. The Si94Al6 sample is an interesting

model catalyst since this ASA contains aluminum atoms almost
exclusively in a tetrahedral environment, as evidenced by 27Al
NMR (Figure 1). Therefore, its study should allow one to
identify the environment of acidic sites.
On Si94Al6 sample (Figure 13), CO adsorption presents only
one band characteristic of LAS, observed at 2230 cm-1. As for
the previously studied ASA samples, different types of hydroxyl
groups are detected. The strongest acidic OH groups (site A1)
are characterized by a perturbed OH band at 3376 cm-1 which
shifts up to 3390 cm-1 (∆ν(OH/CO) ) 373-359 cm-1). Sites
A2 give rise to a ν(OH/CO) band at about 3460 cm-1
(∆(ν(OH/CO)) ) 286 cm-1). Sites B correspond the perturbed
OH at 3560 cm-1. In addition, OH groups of weak acidity (sites
C) are detected at 3656 cm-1. These results illustrate the effect Figure 14. IR spectra of CO adsorbed (130 µmol of CO per gram of
catalyst) on Si30Al70 activated at different temperatures.
of catalyst composition on the OH acidic strength since the
acidity of sites A1 and A2 is stronger for Si94Al6 than on
Si88Al12 and greater on these high silica containing catalysts Si30Al70, the interaction of CO with OH groups gives rise to
than on Si40Al60 and Si30Al70. a broad perturbed OH band, which does not change in aspect
Effect of the ActiVation Temperature. The effect of the when the activation temperature is modified (zone not pre-
activation temperature on the acidic sites of Si30Al70 is sented). However, a downward shift of the maximum of this
presented in Figure 14 for small amounts of CO adsorbed. On envelope is observed when activation temperature increases from
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15181

Figure 15. IR spectra of CO adsorbed (dose corresponding to the saturation of the surface in CO) on Si30Al70 activated at different temperatures.
(A) Zone ν(OH); (B) zone ν(CO).

423 up to 723 K (on Si30Al70, ν(OH)/(CO) ) 3420 cm-1 for

Tact ) 423 K and 3399 cm-1 for Tact ) 723 K). In the ν(CO)
region, the ν(CO) frequency of the strongest OH groups is
clearly affected by the activation temperature. Thus, for the first
CO dose adsorbed, the band of CO in interaction with the
strongest OH groups is observed at 2170 cm-1 after activation
at 423 K, at 2172 cm-1 if the sample is activated at 573 K, and
appears at 2174 cm-1 after activation at 723 K. Hence, both
ν(OH)- and ν(CO)-vibration zones illustrate the strengthening
of OH groups acidity with increasing activation temperature.
Regarding LAS, the amount of LAS increases with Tact. A close
inspection of Figure 14 also shows that the strength of the
strongest Lewis acidic sites is also increased (2226-2230 cm-1)
when activation temperature increases. Note that after activation
at 423 K the 2230 cm-1 band is barely detectable. This can be Figure 16. IR spectra of CO adsorbed (dose corresponding to the
attributed to the presence of residual water at this activation saturation of the surface in CO) on Si88Al12 activated at different
temperature, which is mainly adsorbed on the strongest Lewis temperatures. (A) Zone ν(OH); (B) zone ν(CO).
acidic sites.
The same evolution with activation temperature is observed low activation temperature, i.e., when the amount of silanol
for the other silica alumina samples, i.e., increase of OH acidic group is high.
strength, and of LASs number and strength with activation Conclusion. CO adsorption on ASA samples allows a more
temperature. precise description of the surface compared to pyridine and DMP
When large amount of CO are adsorbed, quantitative com- adsorption. Thus, two types of Lewis acidic sites and five types
parison can be performed (Figures 15B and 16B). Thus, the of OH groups with different acidity were evidenced.
lower the activation temperature, the larger the intensity of the 3.3. Structure and Environment of the ASA Acidic Sites.
ν(CO) band at 2157 cm-1. This indicates an increase in the 3.3.1. Structure of the LAS. The adsorption of pyridine, DMP,
amount of weakly acidic OH groups (sites C). This increase is and CO on the ASA samples shows the presence of surface
consistent with the larger amount of silanol groups detected in Al3+ sites with Lewis acidic properties. At least two types of
the OH zone (see section 3.2.1). Another interesting feature LAS are evidenced: a very strong acidic LAS and a medium
evidenced by Figure 16 is the increase of the amount of sites acidic LAS, characterized, respectively, by the bands at 1622
A, with increasing activation temperature. and 1615 cm-1 using pyridine adsorption and by the bands at
In addition, it should be noted that the activation temperature 2230 and 2196 cm-1 using CO adsorption. Both probe molecules
affects the shape of the ν(OH) envelope, when perturbed by reveal that the medium LASs strongly decrease in abundance
CO (Figures 15 and 16). Thus, Figures 15A and 16A show that for the high silica containing sample, Si88Al12, and are no
the adsorption of CO on ASA activated at low temperature leads longer detected in the Si94Al6.
to the disappearance of two ν(OH) components at 3749 and On pure alumina, using pyridine adsorption, Morterra et al.44
3720 cm-1 (negative bands). In parallel, the formation of a broad suggested that the differences in Lewis acid strengths are due
perturbed OH band at 3660(56) cm-1 with a shoulder at 3624 to differences in the coordination number of surface Al atoms.
cm-1 (positive bands) is detected. In contrast, after evacuation The presence of vacancies located on AlIV sites, and AlIV-AlVI
at 723 K, only a band at 3749 cm-1 (negative band) is perturbed paired sites would be responsible for the two PyL bands at 1622
by CO while one H-bonded OH band appears at 3660(56) cm-1. and at 1615 cm-1. CO adsorption on pure alumina also
Hence in addition to site C (∆ν(OH/CO) ≈ 90 cm-1) previously evidences the presence of coordination sites with different acidic
described, a second type of weakly acidic silanol groups can strengths. In that case, it is surprising to note that papers
be distinguished: site C′ (∆ν(OH/CO) ) 96 cm-1). Thus, site generally related these changes to the presence of Al sites on
C′ is slightly more acidic than site C and is more abundant for regular planes, edges, or corners and not to sites in tetra- or
15182 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

octahedral environment.44 Regardness of the exact environment end of a silanol chain (see Scheme 1). The interaction of the
of the Al3+ surface sites on alumina (plane, edge, and corner oxygen atom of the SiOHt group with a nearby OH group of
sites, or AlIV and AlIV-AlVI sites), it appears that the smaller the chain increases SiOHt group acidity. Indeed, CO in
the coordination number, the stronger the Lewis acidic strength. interaction with these terminal hydroxyl groups gives rise to a
On the ASA studied in the present work, 27Al NMR study ∆ν(OH/CO) of 105 cm-1. Morrow46 showed that, on pure silica,
shows the presence of AlIV and AlVI atoms. The AlIV/AlVI ratio these terminal silanol groups preferentially disappear, when the
increases with the Si amount with the Si94Al6 sample containing activation temperature increases up to 673 K.
essentialy AlIV. In addition, Si88Al12 possesses also AlV sites. Therefore, there is a great similarity between the character-
Thus, the absence of medium Lewis acidic sites observed on istics of the weakest acidic OH groups of ASA and those of
Si94Al6 appears to be associated with the quasiabsence of AlVI pure silica. Thus, the ν(OH) band at 3749-46 cm-1 to which
on this sample. Similarly, the low amount of medium LAS on corresponds the OH group perturbed by CO at 3656 cm-1 (∆ν-
Si88Al12 is consistent with the low concentration of AlVI sites (OH/CO) ≈ 93-90 cm-1), can be assigned to isolated silanol
on this sample. From these results and in agreement with the groups (called sites C). On the other hand, another ν(OH) band
assignments proposed on pure alumina, the strongly acidic LAS at 3720 cm-1 is specifically observed on ASA activated at low
can be assigned to surface AlIV while the medium LAS would temperature. It corresponds to OH groups slightly more acidic
involve AlVI sites. It should be noted that no specific acidity since their perturbation by CO gives rise to a band at 3624 cm-1
for the AlV atoms detected on Si88Al12 is evidenced. This (∆ν(OH/CO) ) 96 cm-1). It can be assigned to the terminal
suggests that the Al atoms in a pentahedral environment are silanol groups (called sites C′). These results suggest the
located in the bulk of the ASA. presence of large silica zones in the ASA samples.
In fact, AlIV sites (characterized by PyL ν8a at 1622 cm-1 Surface composition of the ASA samples can be inferred from
and ν(CO) bands at 2230 cm-1) can be present both on the quantification of silanol groups and compared to what is
mixed silica alumina phase and on the pure alumina region, expected from chemical analysis (Figure 4). The results show
whereas sites characterized by PyL ν8a at 1615 cm-1 and ν(CO) that surface composition depends on the Si/Al ratio and on
bands at 2196 cm-1, which involved AlVI, are specific of the the method of preparation. Oxide prepared via impregna-
alumina domains. The distribution of these two sites depends tion of alumina with silica gel presents a gradient of con-
on the Al content and on the synthesis mode. Thus, on poor centration between bulk and surface since surface Si con-
aluminum containing samples (Si88Al12 and Si94Al6), which centration is greater on than that expected from chemical
correspond to the ASA prepared by cogelification, the fraction analysis. By contrast, cogelification favors mixed oxide forma-
of the silica alumina mixed phase is more important. By contrast, tion.
for high aluminum containing samples (Si30Al70 and Si40Al60),
3.3.3. Structure of the Strong Acidic OH Groups of ASA.
which correspond to the samples prepared by impregnation,
As already reported in the literature, the most outstanding feature
development of alumina domains is observed. Previous 27Al
of ASA is the development of strong Brønsted acidic properties,
NMR study also shows the presence of silica alumina regions
which are not present on pure silica or alumina.
as well as alumina domains.45
On ASA, the amount of Lewis acidic sites increases with Indeed, a small fraction of OH groups of ASA are able to
increasing activation temperature. Such result, which is expected protonate pyridine and lutidine. CO adsorption allows one to
on pure alumina, is surprising on ASA. Indeed on ASA, the determine accurately the acidic strength of these OH groups.
creation of LAS cannot be explained by a surface dehydroxy- This work reveals that the strongest OH groups (sites A1) of
lation via elimination of Al-OH surface species, since such the studied ASA exhibit a ∆ν(OH/CO), which can reach 367
species are not detected. Therefore on ASA, the creation of cm-1, and a ν(CO) band at 2178 cm-1, indicating that their
Lewis acidic sites is explained by the elimination of adsorbed acidic strength is as strong as that present in H-beta zeolite or
water on Al3+ sites. in dealuminated Y zeolite (see Figure 9). Another fraction of
3.3.2. Structure of the Weakly Acidic OH Groups of ASA. these strongly acidic hydroxyl groups (sites A2) presents acidic
From previous studies on pure silica, at least three different strength (∆ν(OH/CO) ≈ 293 cm-1) close to that observed on
environments for silanol groups were distinguished (see Scheme non-dealuminated HY zeolite. In addition, some OH groups of
1):26 medium acidity (sites B, ∆ν(OH/CO) ≈ 186 cm-1) present an
acidity close to that reported on partially alkali-exchanged
SCHEME 1: Structures of Weakly Acidic Silanol faujasites.
Groups of ASA The question of the structure and of the environment of these
OH groups evidently arises. Indeed, even if the BAS of the
studied ASA present acidic properties as high as those of
zeolites, no evidence for the presence of hydroxyl groups
bridged between silicon and aluminum atoms are observed on
these solids. As a matter of fact, IR spectra (Figure 3) does not
evidence any ν(OH) band at about 3630 and 3550 cm-1
Isolated silanol groups, characterized by a ν(OH) band at 3748 characteristic of H-Y zeolites. 1H NMR, which was shown to
cm-1 and 1H NMR signal at 1.8 ppm. The acidity of this OH be more sensitive than IR spectroscopy for the detection of
group is very weak. Indeed, CO in interaction with this specific hydroxyl species, fails to reveal the presence of bridged OH
hydroxyl group gives rise to a perturbation of the ν(OH) band, groups.18 Indeed, Figure 2 does not show any peaks at 3.7 and
∆ν(OH/CO) of only 90 cm-1. 0.1 ppm characteristic of HY zeolite. Hence on ASA samples,
Silanol groups located in a chain, characterized by a ν(OH) the IR spectrum of OH groups only presents a band character-
band at ∼ 3715 cm-1: such OH groups barely interact with a istic of silanols at about 3746 cm-1 as the proton NMR spectrum
weakly basic probe molecule such as CO. that reveals that the major species are silanol groups (peak at
Terminal silanol groups (SiOHt), characterized by a band 1.8 ppm). NMR also shows the existence of a small fraction of
toward 3720 cm-1: such hydroxyl groups are located at the hydroxyl groups nearby aluminum atoms.
Acidic Sites of ASA J. Phys. Chem. B, Vol. 110, No. 31, 2006 15183

To explain the very strong Brønsted acidity in absence of In conclusion, such a result indicates that OH groups
detection of bridged OH groups, some authors proposed the presenting similar stretching vibrations could exhibit strongly
presence of very broad bridged ν(OH) bands difficult to detect different acidities according to their environment. It is well
or even of hidden OH groups.7,13 Indeed, broad ν(OH) bands known that the value of the OH stretching frequency is not an
may escape detection in a direct spectrum. However, after their indicator of acidity. For example, OH groups of magnesia47 give
perturbation or consumption by basic probe molecules interac- rise to a ν(OH) band at about 3750 cm-1, i.e., a similar
tion, they should give rise to a negative band in difference wavenumber than that of silica, while the OH groups of these
spectra (spectra of the samples taken in the presence of probe two oxides present very different acid-base character. For a
molecule after subtracting the spectrum taken before probe given oxide, it is generally considered that the lower the
molecule adsorption). Such a negative band is generally more frequency, the stronger the OH group acidity; such a feature
clearly observable even if it is very broad. Since no nega- being related to an increase of the OH group coordination
tive band is detected in the bridged OH zone, it is pro- number. Therefore, the cases where the OH group acidic strength
posed that the acidity of silanol groups is modified by the is changed, while both the nature of the metal cation to which
presence of aluminum atoms in the neighboring. Thus (SiOH,Al) the OH group is bounded stays unchanged and the coordination
paired sites would generate strongly acidic Brønsted sites number of the OH group is kept constant, are particularly scarce.
(Scheme 2). One example to consider is that of zeolites. Indeed, dealumi-
nation of the zeolitic framework strongly increases the OH group
SCHEME 2: Different Structures of Strongly Acidic
acidity, while the previous parameters stay constant. How-
Sites of ASA and Corresponding Acidities as Probed by
ever, the situation is often not so simple because dealumina-
CO
tion also causes the formation of an extraframework phase,
which interacts by H bonding with the zeolitic OH groups and
consequently strongly changes the zeolitic OH group fre-
quency as well as their acidity.13 Thus, to eliminate the effect
of the amount of extraframework phase on the stretch-
ing frequency and on the acidity of the OH groups, zeolites
dealuminated by isomorphous substitution or by steaming
followed by leaching have been examined. It appears that,
in non-dealuminated HY zeolite ([Si/Al]framework ) 2.748),
OH groups located in supercages give rise to a ν(OH) band
at 3637 cm-1, while for a zeolite dealuminated by steam-
ing at 910 K and leached with HCl 15 M (YS(910)L15-
[Si/Al]framework ) 15) as in ref 13, the band of the OH super-
cage is observed at 3633 cm-1. As shown on Figure 9, the
acidity of these OH groups strongly increases by dealumi-
In a previous paper,15 Trombetta et al. proposed that such nation, since the ∆ν(OH/CO) perturbation increases from
entities could present strong acidity but only after a change of 250 cm-1 on HY up to 350 cm-1 on YS(910)L15. How-
geometry induced by basic molecule adsorption (structure 1 of ever, the corresponding OH stretching frequency is barely
Scheme 2). Thus, SiOH groups of the structure 1 would not be modified by the dealumination of the framework. Therefore,
acidic at the initial stage. The bridged hydroxyl groups that these results provide evidence that the acidity of an OH group
exhibit strong Brønsted acidity are formed by the interaction can be strongly modified without noticeable change of its
of a basic probe molecule with the silanol group in the vicinity stretching frequency.
of Al vacancy. For these authors, this structure would explain CO adsorption also highlights the presence of at least three
both the strong acidity measured and the lack of bridged OH types of strongly acidic OH groups (sites A1, A2, and B).
groups observed in absence of basic probe molecule adsorption. Different structures of (SiOH,Al3+) paired sites are proposed
In such a case, the probing of the OH group acidity by CO to account for the detection of these different types of strongly
should give rise to a ν(CO) wavenumber equivalent to that acidic OH groups on ASA:
measured on bridged SiOHAl groups of zeolites. However, as
Hypothesis a: Silanol groups in the vicinity of a LAS
for the perturbation of the OH group by CO, the ∆ν(OH/CO)
associated with an Al atom either in a tetrahedral environment
value may originate from two components (see Scheme 2): (1)
or in an octahedral environment.
the lowering of ν(SiOH) frequency due to the formation of a
bridged OH group, “ν(SiOHAl)”, and (2) the shift to lower Hypothesis b: Silanol groups nearby Al atom located either
wavenumber of the frequency due to the “ν(SiOHAl)” vibration on the surface or in the bulk.
on CO interaction. Thus, if the OH groups of silica alumina Hypothesis c: Silanol groups in the vicinity of Al atom(s);
samples were only very acidic when bridged, the ∆ν(OH/CO) the amount of Al atoms in the vicinity being smaller for site A
shift should be larger than the one expected from the ν(CO) than for site B.
value and a discrepancy between the values obtained on ASA The Si94Al6 is a very interesting model catalyst to determine
and on zeolite would be expected. This is in variance with the the validity of hypothesis a since almost all the aluminum atoms
results of the present study which show a good agreement of this sample are in a tetrahedral environment. On the basis of
between the ν(CO) values and ∆ν(OH/CO) shift obtained for this hypothesis, only one type of acidic OH groups should be
ASA with the values reported in the literature on a large variety detected on this sample. However, CO adsorption provides
of oxides and zeolites (Figure 9). This agreement allows one to evidence for the presence of several acidic OH groups (sites
rule out the structure 1 given in ref 15 and to propose that a A1, A2, and B) (Figure 13). Consequently, hypothesis a can be
free silanol group located nearby an Al atom can exhibit the rejected. In addition, analysis of this model ASA reveals that
same acidity than that of a bridged hydroxyl group (structure 2 sites A and B are all related to the presence of Al in a tetrahedral
of Scheme 2). environment.
15184 J. Phys. Chem. B, Vol. 110, No. 31, 2006 Crépeau et al.

The hypothesis b concerns the location of the Al atoms of SiOHAl groups whereas in a more open structure such as in
the paired sites. The sensitivity of both the concentration and ASA, (SiOH,AlIV) can exist.
the strength of sites A to the activation conditions is in favor
of their attribution to a (SiOH,AlIV) paired site that contains an 4. Conclusion
Al3+ atom at the surface. Indeed, Figure 16 shows that increasing IR spectroscopy and high-resolution solid-state NMR allow
Tact increases the amount of sites A. Moreover, Figure 14 clearly a deep insight into the structure of ASA prepared either via
indicates that the acidic strength of sites A increases when cogelification or by impregnation of alumina with a silica gel.
activation temperature increases (Si30Al70, Site A: Tact ) 423 In the ASA prepared by impregnation of alumina by silica
K, ν(CO) ) 2170 cm-1; Tact ) 573 K, ν(CO) ) 2172 cm-1; gel, the environment of aluminum atoms remains very close to
Tact ) 723 K, ν(CO) ) 2174 cm-1). When Tact increases, water that of pure alumina. In such samples, Si concentration varies
is eliminated, this increases the amount of unsaturated aluminum between bulk and surface and surface Si concentration is greater
atoms in the vicinity of silanols that would lead to a modification than that expected from chemical analysis. In contrast, the
of the charge distribution. A very simple model could explain composition is more homogeneous on the ASA prepared by
why a (SiOH,AlIV) paired site whose AlIV is a surface site should cogelification and the AlIV/AlVI ratio is greater than on
present stronger acidity after dehydroxylation. Indeed, if the impregnated ASA indicating a higher amount of mixed alumi-
environment of tetrahedrally coordinated Al atom is complete, nosilicate phase.
its positive charge, +3, should be shared by each bond, i.e., On the two types of preparation, the ASA possess large
+3/4 ) +0.75, whereas if Al atom is coordinatively unsaturated, domains of pure silica as well as zones that present strong and
the charge on each bond becomes +3/3 ) +1. Thus, the stronger medium Lewis acid sites related to AlIV and AlVI sites as on
positive charge on the Al atom should induce a larger electron alumina. However, the environment of LAS appears more
transfer via the Al-O-Si bond and therefore, should generate homogeneous than on pure alumina. AlV species detected by
a greater δ+ charge on the proton of the neighboring silanol. NMR analysis does not give rise to specific acidity indicating
However, taking into account the pattern of a (SiOH, AlIV) that they are not located on the ASA surface.
paired site with an AlIV site located at the surface, it is not clear All the studied ASA present a low amount of very strong
why basic probes do not adsorb on this LAS, thus decreasing Brønsted acid sites, whose strength is comparable to that present
the silanol acidity. Another possibility considered is that silanol on Hβ zeolite. Probing the acidic strength using CO or DMP
group is located close to an AlIV of the bulk (Scheme 3). In shows that the OH acidic strength is maximum for ASA with
that case, a negative charge should appear on the Al atom due a large Si/Al ratio and the highest AlIV/AlVI amount. Three
to its 4-fold coordinance. One possibility is that a strong acidity salient experimental results were observed: (i) the lack of
is generated on the proton of the closest silanol group to detection of other hydroxyl species except silanol groups, (ii)
compensate this negative charge. But the large distance between the excellent agreement between the ν(CO) value and the extent
the negative center and the proton makes the existence of such of silanol group perturbation by CO (Figure 9), (iii) the detection
a structure questionable. of strong BAS on ASA containing only Al in tetrahedral
environment. On the basis of these results, the strong Brønsted
SCHEME 3: Structure of Strongly Acidic Silanol Group acidity of ASA was thus related to the presence of (SiOH,AlIV)
with nearby Al Located in the Bulk of ASA paired sites. The differences in OH group acidic strengths was
attributed to the amount of AlIV in the silanol vicinity or the
location of these AlIV atoms.

Acknowledgment. G.C. thanks CNRS and IFP for a grant.

The authors are grateful to Jean Claude Lavalley for stimulating
discussions.
Hypothesis c is proposed by analogy with zeolites where
hydroxyl group acidity increases with dealumination. CO and
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