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Microporous and Mesoporous Materials 110 (2008) 111118

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Eect of synthesis conditions on the pore structure and degree

of heteroatom insertion in Zr-doped SBA-15 silica-based
materials prepared by classical or microwave-assisted
hydrothermal treatment
Karol Szczodrowski a, Benedicte Prelot a,*, Sebastien Lantenois a, Jerzy Zajac a,
Marc Lindheimer a, Deborah Jones a, Anne Julbe b, Arie van der Lee b
a
Institut Charles Gerhardt, Equipe Agregats, Interfaces et Materiaux pour lEnergie, CNRS UMR 5253, Universite Montpellier 2,
C.C.015, Place Euge`ne Bataillon, 34095 Montpellier Cedex 5, France
b
Institut Europeen des Membranes, CNRS UMR 5635, Ecole Nationale Superieure de Chimie, C.C.47, Place Euge`ne Bataillon,
34095 Montpellier Cedex 5, France

Received 1 June 2007; received in revised form 17 September 2007; accepted 26 September 2007
Available online 1 October 2007

Abstract

Zirconium doped mesoporous SBA-15 materials with initial Si/Zr ratios of 10 and 20 have been prepared under microwave-hydro-
thermal conditions using a non-ionic triblock copolymer surfactant as structure-directing agent, as well as zirconyl chloride and zirco-
nium propoxide as two zirconium sources. The eect of a short (5 min) and long (1.5 h) sol ageing time on the degree of heteroatom
incorporation was tested. Changes in the mesopore size and arrangement were monitored with the aid of powder X-ray diraction
(XRD) and gas nitrogen adsorption/desorption at 77 K. The degree of Zr incorporation into the silica framework of the nal product
was inferred from the analysis by energy-dispersive X-ray spectroscopy and compared with the starting value based on the amount of
zirconium added to the reaction mixture. In the case of samples with the lowest initial theoretical molar ratio, the synthesis conditions did
not aect the degree of heteroatom incorporation into the silica framework and all zirconium could be introduced under the conditions
applied. The structure of materials was strongly dependent on the conditions used, and a more regular pore arrangement was obtained
for longer maturation stages. The classical hydrothermal synthesis did not result in a signicantly higher eciency in the heteroatom
insertion, though microwave-assisted treatment yielded materials with thicker pore walls. Further increase in the amount of zirconium
added to the initial gel did not contribute to a greater heteroatom loading in the nal product under microwave conditions.
2007 Elsevier Inc. All rights reserved.

Keywords: Mesoporous SBA-15; Zr insertion; Synthesis; Microwave; Hydrothermal treatments

1. Introduction thermal stability and low catalytic reactivity of MCM-41,

The M41S materials discovered in the early 90s by
Mobil researchers have attracted much interest due to their
high surface area, uniform pore size distribution and pore
diameter in the mesopore size range. However, poor hydro-
*
Corresponding author. Tel.: +33 (0) 4 67 14 33 05; fax: +33 (0) 4 67 14
33 04.
E-mail address: prelot@univ-montp2.fr (B. Prelot).
MCM-48, or MCM-50 materials appeared a serious draw-
back limiting their industrial uses [1]. The necessity of
manipulating structures of porous solids on a nanometer
scale became so obvious to the research community, that
many limitations have been addressed and overcame dur-
ing the last decade. In 1998, Zhao and co-workers [2]
reported the synthesis of SBA-15, thick-wall analogue of
mesoporous silica with a two-dimensional (2D) hexagonal
pore arrangement prepared making use of amphipilic

1387-1811/$ - see front matter 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.09.038
112 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118
triblock copolymers as templates. This material possessed
all advantages of MCM-41 but additionally exhibited a
higher hydrothermal stability. Incorporation of heteroat-
oms such as Al [1,3,4], Ti [5,6] and Zr [5,7,811] into the sil-
ica framework was envisaged as the simplest way to
enhance the surface acidity of ordered mesoporous materi-
als, thereby increasing their catalytic reactivity. The choice
of the type and the amount of the heteroatom was shown
to be crucial in preparing catalysts and adsorbents with
tuneable properties for various industrial uses [11]. Acid
properties of mesoporous materials containing zirconium
have attracted much interest in view of their potential
applications in heterogeneous catalysis.
Several synthesis methods have been used for years to
prepare Zr-doped mesoporous SBA-15. Landau and co-
workers [5] tested chemical solution decomposition (CSD)
and internal hydrolysis (IH) using a 70 wt% solution of zir-
conium propoxide in n-propanol as post-synthesis derivati-
sation procedures to aord Zr-doped SBA-15 solids. The
amount of the heteroatom incorporated into the silica
framework was proven to exceed 30 wt%. Chen et al. [8] car-
ried out a direct synthesis of Zr-SBA-15 mesoporous molec-
ular sieves making use of zirconyl chloride (ZrOCl2 8H2O)
as source of zirconium. They did not use a mineral acid dur-
ing the synthesis to achieve materials with a Zr/Si molar
ratio higher than 0.1. Recently, Fuxiang et al. [7] reported
another direct synthesis of mesoporous Zr-SBA-15 with a
Zr/Si molar ratio ranging from 0 to 2.32. The synthesis
route was based on the use of two surfactant templates: a
cationic (CTAB) and a non-ionic (P123), as well as zirconium
nitrate Zr(NO3)4 3H2O as zirconium precursor. To
increase the eciency of Zr incorporation into the SBA-15
silica framework, Newalkar and co-workers [9] performed
their synthesis with zirconyl chloride under microwave
(MW)-hydrothermal conditions. Their procedure led to
the preparation of mesoporous SBA-15 silica with a Zr
loading corresponding to a Si/Zr ratio of 10, 20, 40, and 80.
The ability to control the heteroatom insertion during
the co-condensation stage and its amount remaining in
the material after the template removal are the main chal-
lenges when preparing ordered mesoporous materials con-
taining zirconium. The intention of the present study was
to test thoroughly the impact of such factors as the type
of Zr compound, sol ageing time, and microwave-hydro-
thermal treatment on the porous structure of Zr-doped
SBA-15 based materials and on the heteroatom incorpora-
tion eciency. The samples were routinely characterised by
X-ray diraction and nitrogen gas adsorption. The ultimate
Si/Zr molar ratio in the calcined solid products was deter-
mined by means of energy-dispersive X-ray spectroscopy.
2. Experimental
2.1. Chemicals
Zirconium functionalised SBA-15 materials were syn-
thesized using tetraethyl orthosilicate (TEOS, Fluka),
zirconyl chloride (ZrOCl2 8H2O, Aldrich) or zirconium
propoxide in 70% propanol (Aldrich) solutions, and non-
ionic tribloc copolymer EO20PO70EO20 (P123, Aldrich).
Water was deionised and puried with the aid of MilliQ
system (18.2 MX). A dilute HCl (VWR) aqueous solution
was used to obtain acidic pH during synthesis. All chemi-
cals were used as received.
2.2. Materials preparation strategy
Four sample series were prepared for the purpose of the
present study. The rst one was synthesized under ambient
condition using zirconium propoxide as the source of zirco-
nium. These samples are referred to as SiZrX(C)AL, X
denotes the initial Si/Zr molar ratio in the gel, C stands
for the classical synthesis method used, A indicates the
use of alkoxide as Zr precursor and L the long sol ageing
time (1.5 h). Other series of materials were aorded using
a microwave-assisted heating with two zirconium sources
and dierent sol ageing times. For the second material ser-
ies, zirconium propoxide served as precursor and the mat-
uration time was also long (1.5 h). The third and the fourth
series were obtained still making use of zirconyl chloride as
zirconium source, whereas the sol ageing time was 1.5 h
and 5 min, respectively. These samples are denoted SiZrX-
(M)AL (M for microwave conditions, A for alkoxide as pre-
cursor and L for long sol ageing time), SiZrX(M)SL (SL
indicates the use of a salt as precursor and the long sol age-
ing time) and SiZrX(M)SS (SS = Salt as precursor and
Short time of synthesis). The synthesis conditions have
been gathered in Table 1.
2.3. Materials synthesis procedure
The materials were synthesized following the procedure
previously reported by Newalkar et al. [9]. Some minor
alterations of the typical synthesis were programmed. The
molar composition of all gels corresponding to 1 mol of
TEOS was the following: 0.017 mol, P123; X mol, Zr pre-
cursor (Si/Zr = 10, 20); 5.7 mol, HCl; and 191.8 mol,
H2O. The typical preparation procedure of Zr-SBA-15
involved dissolution of 0.5 g of P123 in 3.66 g of MilliQ
water and stirring overnight to obtain a homogeneous mix-
ture (Sol 1). Zirconium precursor was mixed with 14.65 g
of 2 M HCl solution and stirred to obtain a homogeneous
Table 1
Working conditions used in materials preparation
Samples Series Zr Microwave Sol ageing
no. source heating time
SiZrX(C)AL 1 Alkoxide No 1.5 h
SiZrX(M)AL 2 Alkoxide Yes 1.5 h
SiZrX(M)SL 3 Salt Yes 1.5 h
SiZrX(M)SS 4 Salt Yes 5 min
X Si/Zr molar ratio, C classical synthesis, M microwave synthesis, A
alkoxide, SL salt and long time of sol ageing, SS salt and short time
of sol ageing.
 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118
solution (Sol 2). Sol 1 and Sol 2 were further mixed up and
stirred again during 15 min. 1.04 g of TEOS was then
added and the overall reaction mixture carefully homoge-
neised. The subsequent procedure was dierent for the four
sample series:
(1) First sample series: white precipitate formed after
about 0.5 h of stirring and then the resulting mixture
was still stirred for 3 h under ambient conditions.
The product was ltered, washed with MilliQ
water, dried at 373 K, and calcined at 813 K in air
for 6 h.
(2) Second and third sample series: white precipitate
formed after about 0.5 h of stirring and the resulting
mixture was further stirred for 1 h under ambient
conditions. Then, it was hydrothermally treated
under microwave conditions at 373 K for 2 h using
a constant heating power of 400 W. The product
was ltered, washed, dried and calcined as the previ-
ous series of samples.
(3) Fourth sample series: the conditions of synthesis were
the same as those used to obtain the second and the
third series, except that the stirring time used to
homogenize the solution was decreased to 5 min.
The MW oven used in this study was a computer con-
trolled ETHOS 1600 [12,13].
2.4. Materials characterisation
Powder X-ray diraction patterns of the samples were
collected from a PanAlytical Xpert pro diractometer
equipped with an ultrafast Xcelerator detector (Cu Ka
radiation, ltered with an incident Ni-foil). Gas nitrogen
adsorption and desorption isotherms were measured at
77 K using a Micromeritics ASAP 2010 system. Prior to
measurements, the calcined samples were outgassed over-
night under vacuum at 423 K. The specic surface area
was determined based on the BET model taking a cross-
sectional area of 0.162 nm2 per nitrogen molecule. The
pore size distributions were obtained from the desorption
branch of the nitrogen isotherms using the BarrettJoy-
nerHalenda (BJH) method. The Si/Zr molar ratio in the
solid phase was determined from the results of energy-dis-
persive X-ray spectroscopy studies (EDX, Quanta 200
Table 2
Surface area, porous structure parameters and Si/Zr molar ratios of the calcined Zr-SBA-15 materials obtained using dierent sol ageing times
Sample SBET (m2 g 1) Pore volume (cm3 g 1)
SiZr10(M)SS 866 0.92
SiZr20(M)SS 820 0.84
SiZr10(M)SL 840 1.11
SiZr20(M)SL 858 1.04
a
Pore diameter representing the most probable value taken from the related BJH distribution.
b
Lattice parameter calculated based on the XRD results and a simple geometrical construction as depicted in Fig. 2.
113
FEG Electron Microscopy, FEI, and calibrated using Co
as optimization element). All results were obtained at high
vacuum mode.
3. Results and discussion
The preparation of mesoporous silica-based materials
with controllable and predictable properties is subject to
numerous physical factors. In the case of Zr-containing sil-
ica synthesized under acidic conditions, the use of a slowly
hydrolysing source of zirconium may lead to a well crystal-
lised SBA-15 framework [9]. Rapid heating and fast super-
saturation under the action of microwaves is believed to
enhance the degree of heteroatom insertion. The eects of
sol ageing time and Zr source on the eectiveness of Zr
incorporation are discussed in the following sections.
3.1. Eect of the sol ageing time
The most important results showing the eect of hydro-
lysis time on the surface area and porous structure param-
eters, as well as on the nal Si/Zr molar ratio have been
collected in Table 2. The pristine data obtained with four
calcined samples are illustrated in Figs. 14.
Fig. 1 presents the XRD patterns of the calcined Zr-
SBA-15 (Si/Zr = 10, 20 in the initial gel) samples prepared
with dierent sol ageing times under microwave conditions.
For a shorter sol ageing procedure (5 min), XRD patterns
of the resulting samples do not show any peak, irrespective
of the molar ratio (Fig. 1a and c). Only a little shoulder is
observed for Si/Zr = 20. This means that SiZr10(M)SS and
SiZr20(M)SS do not have a well-organised mesostructure.
The degree of framework organisation in the other two
materials, prepared with the same Si/Zr molar ratios under
the same conditions with the sole exception of a longer sol
ageing time (1.5 h), is much higher, as evidenced by XRD
patterns in Fig. 1b and d. These diraction patterns show
three well-resolved peaks at about 0.8 (1 0 0), 1.4 (1 1 0),
and 1.6 (2 0 0). These peaks can be attributed to materials
characterised by a 2D hexagonal mesostructure with a
p6mm planar space group. In the case of SiZr20(M)SL,
the peaks are shifted to higher values of 2h, compared to
those obtained for SiZr10(M)SL (Fig. 1b and d). This indi-
cates that the unit cell size of SiZr10(M)SL is larger than
that of SiZr20(M)SL. The main parameters related to the
Pore diametera (nm) ab (nm) Wall thickness (t) (nm) Si/Zr ratio
Gel Product
10 17
20 18
6.6 11.8 5.2 10 16
6.0 10.7 4.7 20 20
114 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118

a b (100)

Intensity / a. u.
Intensity / a. u.

(110)
(200)

0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7

c d (100)
Intensity / a. u.

Intensity / a. u.
(110)
(200)

0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7

Fig. 1. XRD powder patterns of Zr-SBA-15 materials prepared using dierent sol ageing times: (a) SiZr10(M)SS, (b) SiZr10(M)SL, (c) SiZr20(M)SS and (d)
SiZr20(M)SL.

2r relative pressures (Fig. 3b and d). The location of the hys-

t cylindrical mesoporous channels, in line with the interpre-
a
d
Fig. 2. Graphical representation of the 2D hexagonal pore structure with
a p6mm space group, showing the interdependencies between the main cell
parameters.
pore arrangement were calculated based on a simple geo-
metrical construction depicted in Fig. 2. The values
obtained are given in Table 2.
The porosity of the Zr-SBA-15 materials described in
this section was studied by measuring gas N2 adsorption
at 77 K. Fig. 3 shows the adsorption/desorption isotherms
of the four samples. It is clear that the adsorption curves
dier markedly in shape. For the SL-type materials, the
isotherms possess a clear H1-type hysteresis loop at high
teresis loops in the interval of P/P0 ranging from 0.4 to 0.9,
the steep increase in the adsorption value in this pressure
range, together with the fact that the adsorption and
desorption branches are parallel to each other suggest that
the SL samples possess a highly ordered framework with
tation of the XRD patterns shown in Fig. 1b and d. The
pore size distributions have been determined by referring
to the BJH model applied to the desorption isotherm
branch (the desorption branch better meets the require-
ments of ideal wetting inherent in the model). The distribu-
tion curves are reported in insets to Fig. 3b and d. Contrary
to this adsorption behaviour, the samples corresponding to
a shorter sol ageing time (SS) are characterised by an E-
type hysteresis loop in the P/P0 range relevant to capillary
condensation in mesoporous solids possessing ink-bottle-
type pores. Therefore, any desorption-related BJH curve
cannot reect correctly the real pore structure in these
materials. Nevertheless, the porosity of these samples is
very heterogeneous. Suce to note that the adsorption
branch in the capillary condensation region shows a very
gradual increase in the adsorption value.
The results of elemental analysis inferred from the EDX
studies show that the zirconium added to the reaction mix-
ture during the synthesis has been completely introduced
into the framework of SiZr20(M)SS and SiZr20(M)SL,
independently of the length of the maturation stage, as
 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118 115

a 600
b 800

Volume Adsorbed / (cm3.g-1) 700 0.08

Volume Adsorbed / (cm3.g-1)

dV/dD / (cm /g-A)

500

3
600 0.04

400 500
0.00

2 4 6 8 10
400 Pore Diameter / nm
300
300
200
200
100
100

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Presure p/p0 Relative Presure p/p0

c 800 d 800
0.08

700 700

dV/dD / (cm /g-A)

Volume Adsorbed / (cm3.g-1)

Volume Adsorbed / (cm3.g-1)

3
0.04
600 600

500 500 0.00

2 4 6 8 10
400 400 Pore Diameter / nm

300 300

200 200

100 100

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Presure p/p0 Relative Presure p/p0

Fig. 3. Nitrogen adsorption/desorption isotherms at 77 K and BJH pore size distributions (inset) determined on the basis of the desorption branches (only
for samples with a well-ordered porosity) for Zr-SBA-15 materials prepared using dierent sol ageing times: (a) SiZr10(M)SS, (b) SiZr10(M)SL, (c)
SiZr20(M)SS and (d) SiZr20(M)SL.

20
may indicate that there is a limit of Zr incorporation into
20 20
17 18 20
the SBA-15 framework.
16
18 The comparison of the surface area and porosity param-
16 eters among the samples studied here indicates that there is
little eect of the sol ageing time on the BET specic sur-
SiZr molar ratio

14
12 10 face area (the maximum variation is within 5%), regardless
10
10 the initial Si/Zr ratio. On the other hand, there is much
8 evidence that the structure order increases as the sol
6 maturation is lengthened. For longer sol ageing times, the
4 framework structure is better organised with uniformly
2 sized cylindrical pores. This demonstrates that certain min-
0 imum duration of maturation is required to maintain a ne
a
b and regular self-assembly of the templating objects, inde-
c
d pendently of the condensation reaction among the partially
hydrolysed inorganic species.
Fig. 4. Results of the elemental analysis of Zr-SBA-15 materials prepared
using dierent sol ageing times: (a) SiZr10(M)SS, (b) SiZr10(M)SL, (c)
Generally, the values of pore volume in the inorganic
SiZr20(M)SS and (d) SiZr20(M)SL. A white column represents the initial materials framework are greater for long sol ageing treat-
Si/Zr molar ratio in the reactive gel, whereas a grey column refers to the ments by about 20% in the case of samples corresponding
nal Si/Zr molar ratio in the nal product. to a Si/Zr ratio of 20 and by about 25% for the other cou-
ple of samples. This increase in the pore volume may be
illustrated in Fig. 4c and d and Table 2. On the contrary, obviously attributed to better organisation of uniformly
the incorporation of all zirconium into the silica framework sized pores induced under the conditions of longer matura-
to obtain a Si/Zr molar ratio of 10 seems questionable tion. One of the reasons may be that longer hydrolysis
under the experimental conditions applied in the light of condensation stage leads to a more condensed inorganic
the results reproduced in Fig. 4a and b and Table 2. This framework, leaving more free space for the templating
116 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118

micelles without compromising their shape and size. The
most probable pore diameter may be compared only in
the case of samples aorded through long ageing proce-
dures. The increase in the overall Zr amount inserted seems
to disturb the mesoporous framework. It may be argued
that the dierence in the precursor reactivity and its hydro-
lysis in the case of its greater amount in the reaction mix-
ture, result in a disordered hydrolysiscondensation,
thereby contributing to the overall heterogeneity of the
nal product. It should be also noted that the sol ageing
time has no much inuence on the amount of heteroatom
inserted into the silica framework, at least in the range of
experimental conditions tested in this study.
3.2. Eect of the zirconium source
In the case of aluminium-doped mesoporous materials,
it is commonly admitted that the heteroatom source has
a great inuence on the insertion degree [14]. Similar
hypothesis has been forwarded for the Zr-functionalised
silicas studied in the present work. Zirconyl chloride and
zirconium propoxide used in the synthesis of Zr-SBA-15
resulted in SiZr20(M)SL and SiZr20(M)AL samples. The
surface area and porosity parameters as well as the nal
Si/Zr molar ratio of these samples are given in Table 3.
The eect of the zirconium source is illustrated in Figs. 5
and 6 and Table 3.
The XRD patterns of the calcined samples are compared
in Fig. 5. There is a pronounced dierence in the shape of
XRD patterns. For SiZr20(M)SL, three well resolved peaks
at 0.9 (1 0 0), 1.6 (1 1 0) and 1.8 (2 0 0) can be observed,
which argues in favour of well-ordered mesoporous mate-
rials with a 2D hexagonal framework (see Fig. 5a). The
three peaks of the 2D hexagonal mesostructure can be also
seen in the XRD patterns of SiZr20(M)AL reported in
Fig. 5b. They are located at the same positions but their
intensity is much lower than those encountered in the
XRD patterns of SiZr20(M)SL. This means that both mate-
rials possess a hexagonal framework characterised by a
similar unit cell parameter. Nevertheless, the porous struc-
ture of SiZr20(M)SL is more ordered than that of SiZr20-
(M)AL. The nitrogen adsorption/desorption isotherms of
both samples are compared in Fig. 6. The adsorption
curves are of type IV according to the IUPAC classication
with an H1-type hysteresis loop in a P/P0 range from 0.4 to
0.8 typical of mesoporous solids. The adsorption/desorp-
tion branches within the hysteresis loop region are parallel.
Once more again, this points to materials with a well-
organised porous framework and cylindrical pore shape,
thereby allowing the BJH model to be exploited for the
determination of pore size distributions. Narrow pore size
distributions centred about 6 nm are inferred in each case
from the related desorption branch, as can be seen in the
insert to Fig. 6.

Table 3
Surface area, porous structure parameters and Si/Zr molar ratios of the calcined Zr-SBA-15 materials obtained with dierent zirconium sources
Sample SBET (m2 g 1) Pore volume (cm3 g 1) Pore diametera (nm) ab (nm) Wall thickness (t) (nm) Si/Zr ratio
Gel Product
SiZr20(M)SL 858 1.04 6.0 10.7 4.7 20 20
SiZr20(M)AL 854 1.08 6.1 11.2 5.1 20 22
a
Pore diameter representing the most probable value taken from the related BJH distribution.
b
Lattice parameter calculated based on the XRD results and a simple geometrical construction as depicted in Fig. 2.

a b
(100)
(100)
Intensity/a.u.
Intensity/a.u.

(110)

(200)
(110)

(200)

0 2 4 6 0 2 4 6

Fig. 5. XRD powder patterns of Zr-SBA-15 materials prepared using dierent zirconium sources: (a) SiZr20(M)SL and (b) SiZr20(M)AL.
 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118 117

a 3.3. Inuence of the microwave treatment

800
Volume Adsorbed / (cm3 STP g-1)

a In the present section, the properties of Zr-SBA-15 sam-

dV/dD

b
ples achieved under microwave conditions are compared to
b
600 those prepared by a classical hydrothermal synthesis. The
2 4 6 8 10
Pore Diameter/ nm XRD patterns and adsorptiondesorption curves are
reported in Figs. 7 and 8, respectively. Since the related
400
hysteresis loops are of the H1-type, the desorption
branches can serve as basis for the BJH modelling. Table
200
4 summarises the values of surface area and pore structure
parameters, together with the theoretical and eective Si/Zr
molar ratio.
0.0 0.2 0.4 0.6 0.8 1.0 In accordance with the XRD patterns shown in Fig. 7,
Relative Presure p/p
0 SiZr20(C)AL and SiZr20(M)AL samples possess a 2D hex-
agonal mesostructure. Three peaks observed in each dif-
Fig. 6. Nitrogen adsorption/desorption isotherms and BJH pore size
fraction pattern at about 0.9, 1.51.6 and 1.71.8 can
distributions (inset) determined on the basis of the desorption branches for
Zr-SBA-15 materials prepared using dierent zirconium sources: (a)
SiZr20(M)SL and (b) SiZr20(M)AL.
(100)
a
The Si/Zr molar ratios obtained for both samples are
(110)
compared in Table 3. Clearly, the dierence between the
theoretical Si/Zr ratio (initially added to the reactive mix-
Intensity/a.u.

(200)
ture) and its nal value in the calcined material is not very
signicant. Under microwave conditions, the reactivity of
the two zirconium sources is thus comparable. (100)
The use of an alkoxide or a salt as zirconium precursor b
(110)
inuences neither the specic surface area nor the pore vol- (200)
ume/diameter. It does not enhance much the amount of zir-
conium inserted into the silica framework. In the case of
salt precursor, the XRD patterns reveal a more ordered 0 2 4 6
porous network. The heterocondensation polymerisation
between TEOS and Zr source is likely more disturbed in Fig. 7. XRD powder patterns of Zr-SBA-15 materials prepared by: (a)
the case of alkoxide leading to a more heterogeneous pore classical hydrothermal treatment and (b) micro-wave assisted hydrother-
arrangement. mal treatment.

a b
0.14
0.06
0.12
800 800
dV/dD / (cm3/g-A)

dV/dD / (cm3 /g-A)

Volume Adsorbed / (cm3STP g-1)

Volume Adsorbed / (cm3STP g-1)

0.10
0.04
0.08

0.06
0.02
0.04
600 0.02 600
0.00
0.00
2 4 6 8 10 0 2 4 6 8 10
Pore Diameter /nm Pore Diameter /nm

400 400

200 200

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Presure p/p0 Relative Presure p/p0

Fig. 8. Nitrogen adsorption/desorption isotherms and BJH pore size distributions (inset) determined on the basis of the desorption branches of Zr-SBA-
15 materials prepared by: (a) classical hydrothermal treatment and (b) micro-wave assisted hydrothermal treatment.
118 K. Szczodrowski et al. / Microporous and Mesoporous Materials 110 (2008) 111118
Table 4
Surface area, porous structure parameters and Si/Zr molar ratios of the calcined Zr-SBA-15 materials obtained under ambient and microwave conditions
Sample SBET (m2 g 1) Pore volume (cm3 g 1)
SiZr20(C)AL 810 1.34
SiZr20(M)AL 854 1.08
a
Pore diameter representing the most probable value taken from the related BJH distribution.
b
Lattice parameter calculated based on the XRD results and a simple geometrical construction as depicted in Fig. 2.
be assigned to (1 0 0), (1 1 0) and (2 0 0) positions, respec-
tively. The intensity of the peaks is higher for the material
obtained by a classical method (Fig. 7a), which probably
means that the mesoporous network is somewhat less
ordered when the microwave treatment is used. As far as
the N2 gas adsorptiondesorption isotherms are concerned
(Fig. 8), small dierences between the hysteresis loops in
terms of length and slope indicate that SiZr20(C)AL pos-
sesses a more homogenous pore size distribution, which
falls well in line with the XRD results in Fig. 7. The BET
specic area is only slightly inuenced by the microwave
treatment, whereas the pore volume and the pore diameter
are increased by 25% and 20%, respectively. The wall thick-
ness increases when using microwave (1.4 nm), thereby
improving the stability of the material.
The experimental and theoretical Si/Zr molar ratios for
SiZr20(C)AL in Table 4 are very similar, thereby giving a
strong indication that almost all zirconium introduced into
the initial gel during the synthesis has remained in the ulti-
mate material. For SiZr20(M)AL, there is a only small dif-
ference between the experimental and theoretical values. It
appears that rapid heating and fast supersaturation in het-
erocondensation polymerisation under microwave condi-
tions may not always be benecial to Zr incorporation.
Here, the main arguments for the use of microwave treat-
ment are that the overall time of materials preparation is
reduced signicantly and the materials aorded possess
thicker inorganic walls and, consequently, the enhanced
robustness and likely mechanical resistance.
4. Conclusion
Zr-doped SBA-15 materials possessing uniformly sized
mesopores were prepared under dierent synthesis condi-
tions and using two dierent zirconium sources to achieve
a Si/Zr molar ratio of 10 and 20. As evidenced by the
results of EDX study for materials characterised by a the-
oretical molar ratio of 20, the synthesis conditions do not
aect the degree of heteroatom incorporation into the silica
framework and all zirconium can be introduced under the
conditions applied. However, the materials structure
strongly depends on the conditions used, which is con-
rmed by the XRD and gas N2 adsorption results. Even
though the classical hydrothermal synthesis seems a little
Pore diametera (nm) ab (nm) Wall thickness (t) (nm) Si/Zr ratio
Gel Product
7.3 11.2 3.9 20 20
6.1 11.2 5.1 20 22
more ecient in the heteroatom insertion, microwave treat-
ment produces materials with thicker pore walls. For mate-
rials with an initial Si/Zr molar ratio of 10 aorded under
microwave conditions, it seems impossible to introduce the
desired amount of zirconium into the silica framework.
This indicates that there is a limit of zirconium incorpora-
tion into the SBA-15 framework.
Acknowledgments
One of the authors, K. Szczodrowski, greatly acknowl-
edges the nancial support of his work by FP6 INSIDE_
POReS Network of Excellence NMP3-CT-2004-200895.
Emilie Gerardin and Abdeslam el Mansouri are gratefully
acknowledged for their assistance in the materials synthesis
under microwave treatment and N2 adsorptiondesorption
measurements, respectively.
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