10th International Symposium “Scientific Bases for the Preparation of Heterogeneous Catalysts”

E.M. Gaigneaux, M. Devillers, S. Hermans, P. Jacobs, J. Martens and P. Ruiz (Editors)

© 2010 Elsevier B.V. All rights reserved.

Mesoporous SBA-15 silica modified with cerium

oxide: Effect of ceria loading on support
modification
L.F. Liottaa, G. Di Carlob, F. Puleob, G. Pantaleoa, G. Deganelloa,b
a
Istituto per Lo Studio dei Materiali Nanostrutturati (ISMN)-CNR via Ugo La Malfa,
153, 90146 Palermo, Italy. E-mail: liotta@pa.ismn.cnr.it
b
Dipartimento di Chimica Inorganica e Analitica “Stanislao Cannizzaro”, Università di
Palermo, Parco d’Orleans II, Viale delle Scienze pad.17, Palermo 90128, Italy.

Abstract
The present work investigates the effect of ceria loading on silica SBA-15. Five
CeO2/SBA-15 samples with CeO2 content equal to 5, 10, 15, 20 and 30 wt% were
prepared by wetness-impregnation of the support with cerium nitrate hexahydrate, as
precursor, dissolved in ethanol. After drying at room temperature, the resulting samples
were calcined at 400°C for 2h. Characterizations by BET surface area and pore-size
distribution, XRD, NH3-TPD and H2-TPR were performed.

Keywords: SBA-15, ceria impregnation, acidic and reduction properties, NH3-TPD,

H2-TPR.

1. Introduction
Since the discovery, in 1992, of mesoporous silica molecular sieves, such as MCM-41
[1], surfactant-templated synthetic procedures have been applied to the preparation of
other mesoporous silicas, such as worm-like HMS and hexagonal well-ordered SBA-15,
characterized by large surface area (> 700 m2/g) and uniform pores size ranging from 2
to 5.8 nm and from 5 to 30 nm, respectively [2,3]. In the recent years, such ordered
mesoporous silicas have attracted worldwide attention as new supports for catalysts. A
tailored porous structure is beneficial for catalytic applications because allows to control
the optimum size of supported metal nanoparticles and/or metal oxides. Au and Pd
nanoparticles dispersed on mesoporous silica are currently being explored for
environmental catalysis, such as CO oxidation and CH4 combustion [4-7]. The textural
properties of ordered mesoporous silicas, such as large specific surface area, a hexagonal
array and uniform pore channels with size ≥ 5nm) meet the requirements for the
achievement of the optimal size, between 2-5 nm, for Au nanoparticles [8]. However,
due to the inertness of silica, a typical non-interacting support, sintering of noble metal
particles during long time activity occurs [4,9]. Addition of modifiers, such as Cu, Fe,
Nd, Ce, Ce1-xZrxO2 in appropriate concentration to mesoporous silicas is reported to
modify the surface and acidic properties of the matrix and to stabilize against sintering
the supported metal nanoparticles through interaction with the promoter [6,9-11].
On these grounds, the present work focus on the synthesis and characterization of
ceria functionalized mesoporous SBA-15, as support for noble metals deposition. SBA-
15 with hexagonal porous structure was synthesized by using triblock co-polimer, as
template and, then, impregnated with different amounts of cerium nitrate hexahydrate.
Calcination at 400°C was performed to favor crystallization of the ceria fluorite
structure, characterized by high mobility of lattice oxygen [12]. Characterizations of
402 L.F. Liotta et al.

structural and morphological properties were performed by XRD, BET surface area and
pore-size distribution measurements. Acidic and reduction properties were investigated
by NH3-TPD and H2-TPR experiments.

2. Experimental
Mesoporous SBA-15 was prepared starting from tetraethyl orthosilicate (TEOS, Aldrich
98%), as silica source and using a triblock poly (ethylene oxide)-poly(propylene oxide)-
poly(ethylene oxide) (EO20PO70EO20, Pluronic P123, Aldrich), as template, according
to published procedure [3]. In a typical preparation, 8.1 g Pluronic P123 was dissolved
in 146.8 g de-ionized water and 4.4 g of conc. HCl (37%) and stirred over night at 35°C
in a 250 ml one neck flask. To this solution 16 g of TEOS was quickly added and stirred
for 24 h at 35°C. The milky suspension was annealed at 100°C for 24 h in closed
polypropylene bottle. The solid product was filtered, washed with an HCl/water-mixture
and calcined at 550°C for 5h in air.
Five CeO2/SBA-15 samples, with CeO2 content equal to 5, 10, 15, 20 and 30 wt%,
were prepared by successive incipient wetness-impregnations. The SBA-15 was
impregnated with 0.8 ml/g of an ethanolic solution of cerium nitrate hexahydrate, whose
concentration was selected to obtain 5 wt% of CeO2. For higher ceria loadings, the
impregnations were repeated until the target value. After drying at room temperature,
the resulting samples calcined at 400°C for 2h were labeled as CexSBA, where x refers
to the ceria weight content.
Physico-chemical characterizations were performed on the finished ceria-doped
silicas. Surface area measurements (BET) and mesopore size distribution (BJH) were
carried out by means of Sorptomatic 1900 (Carlo Erba) instrument. X-ray diffraction
patterns were recorded with a D 5005 X-Ray Diffractometer (SIEMENS) using Cu Kα
radiation coupled with a graphite monochromator. The crystallite sizes of ceria phase
were calculated from the line broadening of the most intense reflection using the
Scherrer equation [13].
The surface acidity of the ceria-doped SBA-15 samples was studied by a
temperature-programmed desorption of ammonia (NH3-TPD). The measurements were
performed with a Micromeritics Autochem 2910 apparatus equipped with a thermal
conductivity detector (TCD) and a mass quadrupole spectrometer (Thermostar,
Balzers). Prior to the ammonia sorption, the samples (∼100 mg) were outgassed in a
flow of O2 (5% in He) at 500°C for 1h, then, cooled to room temperature under He and
saturated in a flow of NH3 (5% in He, 30 mL/min) for 1h. Subsequently, the catalysts
were purged in a He flow at 100°C for 1h until a constant baseline level was reached.
The ammonia desorption was carried out with a linear heating rate (10°C/min) up to
1050°C under a flow of He (30 mL/min). Calibration of the TCD were carried out in
order to evaluate the ammonia desorption peaks.
Temperature programmed reductions with hydrogen (H2-TPR) were carried out
with the same Micromeritics Autochem 2910 apparatus. The samples (∼ 50 mg) were
pre-treated with O2 (5% in He) at 600°C for 30 min, cooled in He and then H2 (5% in
Ar, 50 mL/min) was flowed from room temperature to 1050°C (heating rate 10° C/min).

3. Results and discussion

In Table 1 the morphological properties of CexSBA samples are listed. Doping silica
with ceria (up to 15 wt%) resulted into a gradual reduction of the specific surface area
and cumulative pore volume, indicating deposition of ceria nanoclusters inside pores. In
addition, no evidences of crystalline ceria features were found by XRD. By further
Mesoporous SBA-15 silica modified with cerium oxide: Effect of ceria loading 403

increasing the loading up to 30wt%, broad peaks indicative of fluorite-type cubic

structure of ceria were detected. The calculated average particle size was of 5 nm.
Surface area sintering and pore volume decrease were also observed, likely because of
the crystallization process.

Table 1. Morphological properties of CeO2-doped SBA-15 samples.

Sample BET (m2/g) Pore size Total pore volume
(BJH) (nm) (cm3/g)
SBA-15 840 7.4 0.81
Ce5SBA 620 6.7 0.70
Ce10SBA 580 6.4 0.68
Ce15SBA 569 5.9 0.55
Ce20SBA 392 5.1 0.48
Ce30SBA 385 5.0 0.34

In Fig. 1 the nitrogen adsorption/

desorption isotherms of CexSBa
(a) SBA-15
(b) Ce10SBA samples are displayed. A H1 hys-
(c) Ce20SBA
(d) Ce30SBA
teresis, which is typical of cylin-
Volume adsorbed (cm STP/g)

(a)
drical mesopores and wide bottle-
shaped mesopores, was observed
3

(b) in any case, although the hysteresis

(c)
shape slightly changes by increase-
ing ceria content and the relative
(d)
pressure where capillary condensa-
tion step occurs shifts to lower P/Po
values. No evidences of micropo-
0.0 0.2 0.4 0.6 0.8 1.0 res were found. According to XRD
Relative pressure, P/P0
results, these findings suggest that,
Fig. 1. Nitrogen adsorption/desorption isotherms for at high loading, ceria crystallizes,
CexSBA samples. partially obstructing the mesopores.
The surface acidity of ceria-doped
silica samples was studied NH3-
(a) SBA-15
(b) Ce10SBA TPD. Desorption of ammonia from
(c) Ce20SBA
(d) Ce30SBA
SBA-15 was detected with a peak
centered at 105 °C. No additional
(a) desorption occurred at higher temp-
TCD Signal (a.u.)

erature. For CexSBA samples the

(b)
quantity of chemisorbed NH3 incre-
(c)
ased from 0.09 mmol/g for pure
SBA-15 to 0.35 mmol/g for Ce30
(d) SBA. The observed values are in
line with literature results [10].
50 100 150 200 250 300 350 400
Temperature (°C)

Fig. 2. NH3 -TPD curves for CexSBa samples.

Moreover, the desorption started at slightly higher temperature, around 120°C, with
a broad and asymmetric peak ranging up to 350-400°C. Therefore, it seems that ceria-
404 L.F. Liotta et al.

modification of silica resulted in an increased acidity, in terms of higher concentration

and strength of surface acid sites. Accordingly, it has been reported that modification of
mesoporous silica with transition metals considerably increases the surface acidity by
the generation of Lewis acid sites, to which ammonia molecules are bonded by donor-
acceptor bond [10]. TPR experiments were carried out for studying the reduction pro-
perties of ceria in CexSBA oxides. For all samples high reducibility was observed, the
reduction started at around 300°C and two peaks, generally, were observed at ~ 400°C
corresponding to surface reduction and at 700°C due to bulk reduction of ceria. Stoichio-
metrically, 1g of ceria requires 2905 µmol H2/g for a complete reduction to Ce2O3,
therefore, ceria in CexSBA samples was almost completely reduced, being for instance
the overall consumption of 834 µmol H2/gCe30SBA for Ce30SBA and of 415 µmol
H2/gCe20SBA for Ce20SBA. The presence of grain boundaries and defects in the small
ceria crystallites may account for the enhanced reducibility [14], which is a very
important property for catalytic application, in particular, CO oxidation reactions [12].

4. Conclusions
Ceria-modified SBA-15 oxides with increased surface acidity and high reducibility were
prepared. The specific surface area was ranging between 620-385 m2/g, and well
dispersed ceria crystallites (mean diameter ≤5 nm) were obtained. The so far reported
results suggest that CexSBA oxides, prepared by incipient wetness-impregnation
approach, are suitable supports for preparation and stabilization of noble metal
nanoparticles.

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