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Materials Chemistry
Cite this: J. Mater. Chem., 2011, 21, 5693
www.rsc.org/materials PAPER
Tuning pore diameter of platelet SBA-15 materials with short mesochannels
for enzyme adsorption†
Shih-Yuan Chen,a Yi-Ting Chen,b Jey-Jau Leec and Soofin Cheng*a
Received 22nd October 2010, Accepted 8th February 2011
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B

DOI: 10.1039/c0jm03591b
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A novel route for preparing highly ordered platelet SBA-15 materials with short mesochannels
(ca. 200 nm) and large pore diameters up to 12 nm is reported for the first time. Appropriate quantities
of Zr(IV) ions and trimethylbenzene (TMB) were added to the conventional SBA-15 synthesis solution
to obtain platelet SBA-15 (SBA-15-p) materials with expanded pores. Based on the results of
conventional characterization techniques and in situ small-angle X-ray scattering experiments, the key
step to obtain a well-ordered 2D hexagonal pore structure without vesicle contamination was the
pre-hydrolysis of tetraethyl orthosilicate (TEOS) in the Zr(IV) containing synthesis solution for about
25 min before adding TMB as the pore swelling agent. The resultant SBA-15-p materials had high
surface areas (
800 m2 g1), large pore volumes (
1.2 cm3 g1) and short mesochannels (
200 nm).
More importantly, the mesopore diameters Fa_BdB, analyzed by a modified Broekhoff-de Boer method
with the Frenkel-Halsey-Hill equation (BdB-FHH) on the nitrogen adsorption isotherms, could be
finely tuned to 7–12 nm by varying the amount of swelling agent and the hydrothermal temperature.
When adsorbing cytochrome c enzyme at pH 4–10, the short-channel SBA-15-p materials
demonstrated higher adsorption capacities and adsorption rates compared to conventional fiber-like
SBA-15 materials (SBA-15-f). Furthermore, the uptakes of cytochrome c enzyme per surface area
increased significantly on the large pore materials.

Introduction
Mesoporous silica materials, which have high surface area and
well-ordered mesostructure, have potential applications in sepa-
ration,1 catalysis,2 microelectronic devices,3 and enzyme immo-
bilization.4 The mesoporous SBA-15 of two-dimensional (2D)
cylindrical pores arranged in hexagonal p6mm symmetry has been
studied extensively because of its relatively larger pore and higher
hydrothermal stability in comparison to MCM-41, which is its
analog in the M41S family.5,6 However, the cylindrical pores of
conventional SBA-15 particles are usually with pore lengths in
tens of micrometres and pore diameters (Fa-BJH) ca. 5–6 nm,
determined from the BJH (Barrett–Joyner–Halenda) adsorption
pore size distribution (PSD) profiles. Although the pore diameter
(Fa-BJH) of SBA-15 can be expanded to ca. 8 nm by increasing the
hydrothermal temperature and period,6 molecular diffusion
a
Department of Chemistry, National Taiwan University, Taipei, 106,
Taiwan. E-mail: chem1031@ntu.edu.tw; Fax: +886-2-23636359; Tel:
+886-2-33661662
b
Molecular Medicine Research Center, Chang Gung University, Tao-Yuan,
333, Taiwan
c
Research Division, National Synchrotron Radiation Research Center,
Hsinchu, 300, Taiwan
† Electronic supplementary information (ESI) available: Supplementary
information. See DOI: 10.1039/c0jm03591b
through the lengthy channels and pore blockage along the chan-
nels are the main concerns when applying SBA-15 in the sorption
and catalysis of bulky molecules. In recent years, numerous efforts
have been devoted to the synthesis of mesoporous SBA-15 with
short mesochannels, in the sub-micrometre length range, by
adding co-surfactant, co-solvent, electrolytes and organosilanes
to the synthesis solutions.7–23 Han and Ying15 have synthesized
pure siliceous mesoporous silica materials with mesochannels of
300–500 nm by combining triblock copolymer with a cationic
fluorocarbon surfactant in weakly acidic condition. Pure siliceous
SBA-15 materials, with cuboid or flake morphology and
mesochannels in the sub-micrometre scale, were also synthesized
by adding fluoride additives such as NH4F to the conventional
SBA-15 synthesis solution with long-chain alkanes, such as
heptane, octane and decane as the co-solvent.9,10 The co-solvents
and fluorocarbon surfactant were suggested to surround the
mesoporous silica particles and thereby limit the aggregation and
growth of the mesochannels. These synthesis routes, however, are
inapplicable for preparing organic functionalized mesoporous
materials in one pot because the organosilanes may interfere with
the self-assembly process involving the co-solvents and
co-surfactants, and NH4F may also react with the organosilanes.
Mesoporous silica materials have been used as enzyme supports
because of their high surface area and large pore diameter, espe-
cially for SBA-15.24–27 For example, pure siliceous SBA-15 with an

This journal is ª The Royal Society of Chemistry 2011 J. Mater. Chem., 2011, 21, 5693–5703 | 5693

expanded pore diameter (Fa-BJH) of ca. 7 nm was found to
give higher adsorption capacity and a faster adsorption rate toward
FeHeme chloroperoxidase with a size of ca. 6.5 nm, in comparison
to those of the M41S family with pore diameters (Fa-BJH) in 3–
4 nm.26 However, the major challenge is the difficulty to enlarge the
pore diameter of SBA-15 to exceeding 10 nm so that enzymes, such
as organophosphorus hydrolase (4–9 nm), cytochrome (ca. 3–
9 nm), glucose oxidase (5–8 nm) and metmyoglobin (ca. 17.6 nm),
which are selective oxidation catalysts, may be immobilized and
reused.24,28 Particularly, SBA-15 functionalized with organic
groups is usually required for immobilization of biomolecules, and
the pore diameters (Fa-BJH) can be reduced to ca. 5 nm.25,27
By adding swelling agents such as TMB in the conventional
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
synthesis solution, the pore diameter of SBA-15 was reported to
increase.6 However, phase transformation from the well-ordered
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2D hexagonal p6mm pore structure to randomly distributed
mesocellular foams (MCF) occurs when the amount of swelling
agent added exceeds TMB/P123 weight ratio ca. 0.2.29–32 A
modified route was recently reported to synthesize large-pore
SBA-15 up to 15 nm in diameter with the simultaneous additions
of TMB and KCl.33 Nevertheless, the pore size distributions of
the resultant materials were rather broad (ca. 2–3 nm). More-
over, a strict temperature range near 15  C was needed for the
self-assembly process,33 and the effects of TMB and KCl addi-
tives on the morphology of the resultant materials were not
reported. Therefore, many challenges still remain in the synthesis
of large-pore SBA-15 material with short mesochannels.
It is also noteworthy that the 15 nm pore diameter (Fa-BJH)33,
estimated from the adsorption branch of the N2 sorption isotherm
by BJH calculations, was probably overestimated and theoreti-
cally incorrect.34 On the contrary, the pore diameter (Fd_BJH),
determined from the desorption branch, is reported to underes-
timate by ca. 20–25% due to the fact that the BJH method neglects
the effect of the pore wall curvatures on the adsorbed gas layer
thickness.34 The pore diameters of mesoporous silica materials,
such as SBA-15 and mesocellular silica foam, have been more
precisely determined by non-local density function theory
(NLDFT) and modified BdB-FHH method.30,34,35
Our laboratory has recently developed a facile route to synthesize
functionalized SBA-15 with platelet morphology and short meso-
channels (ca. 200 nm) by adding appropriate amounts of Zr(IV) ions
to the conventional SBA-15 synthesis solution as the Zr(IV) ions can
accelerate the self-assembly of P123 micelles and TEOS.12,19
However, the pore diameters (Fd_BJH) of these platelet SBA-15
materials are around 5 nm, which is insufficient for the sorption of
bulky molecules such as enzymes. Therefore, the purpose of this
study is to enlarge the pore diameters of platelet SBA-15 materials.
Possible factors including the amount of swelling agent, the dura-
tion of the TEOS pre-hydrolysis, and hydrothermal temperature
were examined. The adsorption of cytochrome c on the resultant
platelet SBA-15 materials at various pH values were studied and
compared with that of fiber-like analogues.
Experimental
Reference materials
Conventional SBA-15-f material of fiber-like morphology was
prepared as described by Zhao et al.6 In some cases, the
5694 | J. Mater. Chem., 2011, 21, 5693–5703
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hydrothermal temperature was increased to 120  C in order to
obtain SBA-15-f with relatively large pores (ca. 9.4 nm). Short-
channel SBA-15-p with pore sizes of ca. 7.6 nm was synthesized
without TMB as described by our previous study.19
Pore expanded materials
A modified route was developed to prepare short-channel SBA-15-
p materials with expanded pore diameters. In a typical synthesis,
0.32 g of zirconyl chloride octahydrate (ZrOCl2$8H2O, Acros) and
2 g of Pluronic P123 triblock copolymer (EO20PO70EO20, Mn ¼
5800, Aldrich) were thoroughly dissolved in 80 g of 2 M HCl
solution at 35  C. To this solution, 4.2 g of TEOS (Acros) was
added and pre-hydrolyzed for various time periods, followed by
adding 1 g of TMB (Acros). The gel composition was
0.017P123 : 1TEOS : 0.41TMB : 0.05ZrOCl2 : 7.9HCl : 220H2O.
The mixture solution was sealed in a polypropylene (PP) bottle and
stirred at 35  C for 24 h, and followed by hydrothermal treatment
at 90  C for another 24 h under static conditions. Materials were
also prepared by varying the TMB/P123 weight ratios and
hydrothermal temperatures in 0.05–2.5 and 50–150  C, respec-
tively. White precipitates recovered by filtration were thoroughly
washed with de-ionized water and dried at 50  C overnight. The
P123 was removed by calcining the as-made materials at 500  C for
12 h in air.
Characterizations
Powder X-ray diffraction (XRD) patterns were measured by
a Philips X’pert Pro diffractometer with Cu Ka radiation oper-
ated at 40 mA and 45 kV. The divergent slits of 1/32 and 1/2 were
set for measuring small- and wide-angle XRD patterns. Nitrogen
adsorption-desorption isotherms were measured at liquid
nitrogen temperature (77 K) using a Micrometerics TriStar 3000
instrument. Before the experiment, the materials were degassed
at 200  C under vacuum (103 Torr) for at least 8 h. The specific
surface area was calculated by Brunauer–Emmett–Teller (BET)
method in the P/P0 range of 0.05–0.25. A modified BdB-FHH
method based on both the adsorption and desorption profiles
was used to calculate the pore size distributions (PSDs) of mes-
oporous materials.30,36 The materials were photographed with
a Hitachi S-800 field emission scanning electron microscope
(SEM) and a Hitachi H-7100 transmission electron microscope
(TEM). The in situ SAXS experiments were performed at Beam
line 17A of National Synchrotron Radiation Research Center
(NSRRC), Hsinchu, Taiwan. The standard operating condition
was around 1.5 GeV and 360 mA. The gelled sample was pumped
into a Teflon sample cell by a wriggle pump with a 17 mL min1
circulating rate. In situ SAXS patterns were collected by Mar345
Imaging Plate Area Detector (182 s for acquring a pattern).
Thermogravimetric (TG) analysis was performed using a Hi-Res
TA 2950 TG analyzer under a 50 mL min1 air flow and a 10  C
min1 ramping rate. The UV-vis spectra were visualized by
a Hitachi U-3310 spectrometer.
Adsorption properties
The adsorption of cytochrome c (MW ¼ 12384 Da, Sigma) was
performed in a 5% CH3CN aqueous solution with pH values
varied in 4–10. The uptake of cytochrome c was measured by
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comparing the cytochrome c concentrations (0.20–10 g L1)
in the supernatant liquids before and after adding adsorbent
(ca. 3–10 mg) using UV-vis absorption at 407 nm.
Results and discussion
Effect of TMB addition on the formation of platelet SBA-15
First, the effect of swelling agent on the pore structure and
morphology of SBA-15-p materials was examined by adding
various amounts of TMB in the SBA-15-p synthesis solution
directly. The small-angle XRD patterns in Fig. 1(a) indicate that
the materials prepared with TMB/P123 weight ratios less than
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
higher P/P0 regions as the TMB/P123 weight ratios increase.
As for the materials prepared with TMB/P123 weight ratios of
0.20–0.25, the hysteresis loops are no longer parallel, indicating
the presence of disordered pore structures. When the TMB/P123
weight ratio is higher than 0.25, the resultant materials have wide
hysteresis loops at P/P0 in 0.45–0.95. The significant separation
of adsorption and desorption branches of the hysteresis loop is
akin to that of mesocellular silica foam with closed window
cells.30,36 Table 1 shows the structural analysis results. The
materials prepared with TMB have larger surface areas and
surface volumes than those without TMB. The unit cell param-
eters (a0), wall thicknesses (Wt), and pore diameters (Fa-BdB),
analyzed from the adsorption branches of N2 sorption isotherms

0.2 contain three diffraction peaks corresponding to the (100), by a modified BdB-FHH method, increase progressively with the
(110), and (200) planes of 2D hexagonal p6mm pore structure, TMB contents. It is also noticeable that the Fa-BdB and Fd-BdB
which are akin to those of conventional SBA-15.6 By increasing
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the TMB/P123 weight ratios, the diffraction peaks shift slightly
toward lower angles, inferring that the pore diameters are
probably enlarged by swelling the P123 micelles with TMB
molecules. However, the diffraction peaks decrease gradually in
intensities when TMB/P123 weight ratios exceed 0.2, indicating
less ordering of the pore structure.
Fig. 1(b) shows the nitrogen adsorption-desorption isotherms
of SBA-15-p materials prepared with various TMB/P123 weight
ratios. Materials prepared with TMB/P123 weight ratios less
than 0.15 exhibit the classic type IV isotherms with parallel H1
type hysteresis loops. The hysteresis loops shift slightly toward
Fig. 1 (a) Small-angle XRD patterns and (b) N2 sorption isotherms of
SBA-15-p materials prepared with various TMB/P123 weight ratios.
values (from the desorption branches) are in a close range for the
materials prepared with TMB/P123 weight ratio lower than 0.1.
Then, the differences increase with the TMB/P123 weight ratio.
The large differences of the Fa-BdB and Fd-BdB values imply that
the materials contain MCF structures, and the Fa-BdB and Fd-BdB
values correspond to the cell and window sizes of MCF,
respectively.30,36
The effect of directly adding TMB to the synthesis solution on
the morphology and pore structures of the resultant SBA-15-p
materials was further examined by electron microscopy. When
the TMB/P123 weight ratios are 0.05 or lower, the platelet
aggregates are seen (Fig. 2(a)). Each platelet is 1–1.5 mm in width
and 200 nm in thickness. The TEM photograph (Fig. 3(a)) shows
that the cylindrical pores are aligned along the short axis of the
platelet and the pore diameter is around 7 nm. Restated, the
mesochannels are only 200 nm long. These experimental results
are similar to our previous studies, demonstrating that the short-
channel SBA-15 platelet materials could be obtained by adding
a small amount of Zr(IV) ions in the conventional SBA-15
synthesis solution.12,19 When the TMB/P123 weight ratio is
increased to 0.1, the platelets pile up one on top of another. Each
platelet is 500–600 nm in width and 300–400 nm in thickness. The
TEM photograph (Fig. 3(b)) shows that the lengths of the mes-
ochannels increase to ca. 400 nm and the diameters are around 8
nm. When the TMB/P123 weight ratios are 0.2 or larger, the
aggregates of spherical particles ca. 2 mm in diameter are
observed. In addition, the vesicle structures are seen on the
particle surfaces, as indicated by the thick arrows in Fig. 2(c) and
2(d). The TEM photographs (Fig. 3(c) and 3(d)) show that the
cylindrical pores and vesicle structures are coexistent in the

Table 1 Effect of TMB/P123 weight ratios on the structural properties of SBA-15-p materials prepared without TEOS pre-hydrolysis

TMB/P123
(weight ratio) Pore Structurea a0b (nm) SBET (m2 g1) VTotal (cm3 g1) Fa_BdB (nm) Fd_BdB (nm) FTEMa (nm) Wtc (nm)

0 p6mm 11.7 815 1.0 7.6 8.0 7.0 4.1

0.05 p6mm 12.1 820 1.1 7.8 8.2 8.0 4.3
0.1 p6mm and MCF 12.2 880 1.3 8.7 8.4 — n.d.
0.2 p6mm and MCF 14.2 890 1.3 13.9 9.0 — n.d.
0.3 MCF and worm pore 14.5 820 1.2 14.8 6.4 — n.d.
0.4 MCF 15.0 760 1.2 20.2 6.2 — n.d.
0.5 MCF n.d.d 790 1.3 26.9 5.0 — n.d.
a
On the basis of TEM photographs. b
Unit cell parameter (a0) ¼ 2(d(100)/O3). c Wall thickness (Wt) ¼ a0  Fa_BdB. d Not detectable.

This journal is ª The Royal Society of Chemistry 2011 J. Mater. Chem., 2011, 21, 5693–5703 | 5695

Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
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Fig. 2 SEM photographs of SBA-15-p materials prepared with TMB/
P123 weight ratios of (a) 0.05, (b) 0.1, (c) 0.2, and (d) 0.5.
sample prepared with TMB/P123 ¼ 0.2 and only vesicle structure
akin to MCF with closed window cells are observed in the sample
with TMB/P123 ¼ 0.5. The variations in the hysteresis loops and
pore diameters of the SBA-15-p materials indicate that the self-
assembly of P123 micelles and TEOS is significantly disturbed by
adding small amounts of TMB into the synthesis solution.
Based on the results of XRD, nitrogen physisorption, and
electron microscopes, the hexagonal pore structure of short-
channel SBA-15 are obtained only when the TMB/P123 weight
Fig. 3 TEM photographs of SBA-15-p materials prepared with TMB/
P123 weight ratios of (a) 0.05, (b) 0.1, (c) 0.2, and (d) 0.5.
5696 | J. Mater. Chem., 2011, 21, 5693–5703
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ratios are in 0–0.05. If the TMB/P123 weight ratios are increased
to 0.1–0.2, the mixture of hexagonal pore and MCF structures
coexists. When the TMB/P123 weight ratios are higher than 0.2,
the resultant materials only contain the MCF structure.
However, the pore diameters of short-channel SBA-15 platelet
materials could only be expanded to ca. 8 nm when TMB is
directly added to the SBA-15 synthesis solution containing
ZrOCl2.
Effect of pre-hydrolysis of TEOS
To expand the pore diameter of platelet SBA-15 materials and
simultaneously retain the well-ordered 2D hexagonal p6mm pore
structure, a key step was found to be the pre-hydrolysis of TEOS
in the synthesis solution before the addition of TMB. Fig. 4(a)
and 4(b) show the small-angle XRD patterns and the nitrogen
adsorption-desorption isotherms, respectively, of SBA-15-p
materials prepared with a TMB/P123 weight ratio of 0.5 and
varying the TEOS pre-hydrolysis period. For the materials
prepared with TEOS pre-hydrolysis for less than 15 min, only
broad diffraction peaks are seen. However, three distinct
diffraction peaks of (100), (110), and (200) planes of 2D hexag-
onal p6mm pore structure appear when the TEOS pre-hydrolysis
periods exceed 15 min. As the TEOS pre-hydrolysis period is
prolonged, the X-ray diffraction peaks increase in intensities and
shift toward higher angle region.
In the nitrogen adsorption-desorption isotherms, the materials
prepared with TEOS pre-hydrolysis for 10 min or shorter have
the hysteresis loops similar to that of MCF with closed-window
cells,30,36 appearing at a wide P/P0 region of 0.65–0.95. Regarding
the materials prepared with TEOS pre-hydrolysis for 15 min or
longer, the classic type IV isotherms with parallel H1 type
hysteresis loops is observed, indicating the presence of well-
ordered mesopores.
The morphologies and pore structures of SBA-15-p material
prepared with a TMB/P123 weight ratio of 0.5 and varying the
TEOS pre-hydrolysis period were examined with electron
microscopy. Fig. 5(a) shows that the materials prepared
with TEOS pre-hydrolysis for shorter than 5 min are aggregates
of 2–3 mm spherical particles. As indicated by the thick arrows,
Fig. 4 (a) Small-angle XRD patterns and (b) N2 sorption isotherms of
SBA-15-p materials prepared with a TMB/P123 weight ratio of 0.5 and
various TEOS pre-hydrolysis periods.
This journal is ª The Royal Society of Chemistry 2011

large pore mouths can be seen on the particle surfaces. The TEM
photograph (Fig. 6(a)) reveals that this material contains vesicles
and worm pores. When the TEOS pre-hydrolysis period was
15 min, the material contains numerous spherical nanoparticles
adhered to platelet surfaces (Fig. 5(b)). Its TEM photograph
shows well-ordered 2D hexagonal pore structure and the spher-
ical vesicles (Fig. 6(b)). When the TEOS pre-hydrolysis period
was increased to 25 min or longer, platelet materials with clean
surfaces were obtained (Fig. 5(c,d)). The TEM photographs in
Fig. 6(c) and 6(d) show that the pore diameters and wall thick-
nesses are 10.5 and 4.6 nm, respectively, which are consistent
with the data estimated from the XRD pattern and BdH-FHH
adsorption pore size analysis.
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
For mesoporous materials with cylindrical pores, the BdB-
FHH method should give the same pore diameter from both
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adsorption and desorption isotherms.30 In the present study, the
pore diameters Fa-BdB and Fd-BdB values determined from the
adsorption and desorption isotherms are slightly different. It was
told that the step size in the sorption experiments may affect the
pore size analysis. Moreover, the SBA-15 type materials do not
have dense pore walls and very straight cylindrical pores as the
model assumed in the modified BdB-FHH method. Although the
above mentioned factors may cause the slight differences
between the Fa-BdB and Fd-BdB values, the Fa-BdB values deter-
mined from the adsorption branches were found to be extremely
close to the data determined by TEM photographs in the present
study. Therefore, the Fa-BdB values are used to estimate the pore
diameters of SBA-15 type materials hereafter.
The structural properties of SBA-15-p materials prepared with
a TMB/P123 weight ratio of 0.5 and varying the TEOS pre-
hydrolysis periods are tabulated in Table 2. The well order 2D
hexagonal p6mm structure was obtained only when TEOS was
pre-hydrolyzed for 25 min or longer. For the sample prepared
Fig. 5 SEM photographs of SBA-15-p materials prepared with a TMB/
P123 weight ratio of 0.5 and varying the TEOS pre-hydrolysis periods of
(a) 5, (b) 15, (c) 25 and (d) 60 min.
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Fig. 6 TEM photographs of SBA-15-p materials prepared with a TMB/
P123 weight ratio of 0.5 and varying the TEOS pre-hydrolysis periods of
(a) 5, (b) 15, and (c,d) 25 min.
with TEOS pre-hydrolysis for 25 min, the Fa-BdB value is
10.6 nm. When the TEOS pre-hydrolysis periods are further
prolonged, the Fa-BdB values gradually decrease. The materials
obtained from TEOS pre-hydrolysis for several hours have
Fa_BdB values around 7.5 nm, which is similar to that observed on
the SBA-15-p material prepared without adding TMB (entry 1,
Table 1). These data reveal that the pore-swelling agent can no
longer expand the pores effectively when the silicate condensa-
tion is for longer than 25 min and the silica framework becomes
too rigid.
To study the mechanism of TMB as a swelling agent, in situ
SAXS was utilized to monitor the early self-assembly process of
short-channel SBA-15-p materials using the synchrotron X-ray
radiation source (l ¼ 1.33093 A)
at beam line 17A of NSRRC,
Taiwan. In a typical synthesis, 0.32 g of zirconyl chloride octa-
hydrate (ZrOCl2$8H2O, Acros) and 2 g of Pluronic P123 triblock
copolymer (EO20PO70EO20, Mn ¼ 5800, Aldrich) were thor-
oughly dissolved in 80 g of 2 M HCl solution at 35  C. The in situ
SAXS patterns were recorded right after TEOS was added. Fig. 7
compares the patterns when TMB and TEOS were added
simultaneously and those prepared with TEOS pre-hydrolysis for
25 and 60 min before the addition of TMB. The TMB/P123
weight ratio was kept at 0.5.
When TMB and TEOS were simultaneously added to the
SBA-15-p synthesis solution, a broad and weak scattering peak
centered at 2q ¼ 0.641 (d spacing ¼ 11.9 nm) appeared imme-
diately (Fig. 7(a)). In the next 10 min, the scattering peak grew
and shifted toward 2q
0.482 (d spacing
15.8 nm), indicating
the swell of P123 micelles by dissolving TMB. Meanwhile, the
signal intensity was slightly enhanced, inferring that the hydro-
lysis and condensation of TEOS is on-going slowly. After 90 min,
only a broad scattering peak with medium intensity at
2q
0.528 (d spacing
14.4 nm) was seen. Since no scattering
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Table 2 Effect of TEOS pre-hydrolysis periods on structural properties of SBA-15-p materials prepared with a TMB/P123 weight ratio of 0.5

Perioda (min) Pore structure a0 (nm) SBET (m2 g1) VTotal (cm3 g1) Fa_BdB (nm) Fd_BdB (nm) FTEM (nm) Wt (nm)

0 MCF n.d. 792 1.3 26.9 5.0 — n.d.

5 MCF 17.6 818 1.4 16.1 11.0 — n.d.
10 MCF and worm pore 16.6 804 1.2 14.9 9.8 — n.d.
15 MCF and p6mm 16.3 813 1.4 11.7 11.4 — 4.6
20 p6mm and MCF 16.2 803 1.4 11.2 11.4 — 5.0
25 p6mm 15.6 854 1.4 10.6 10.7 10.5 5.0
30 p6mm 14.3 832 1.4 9.9 10.0 10.0 4.4
40 p6mm 13.6 844 1.5 9.0 9.7 8.9 4.6
50 p6mm 13.1 848 1.3 8.5 8.7 8.5 4.6
60 p6mm 12.6 836 1.3 8.1 8.5 8.2 4.5
360 p6mm 12.4 885 1.3 7.8 8.3 7.7 4.6
720 p6mm 12.4 891 1.2 7.5 7.7 7.5 4.9
1480 p6mm 12.4 895 1.2 7.5 7.7 7.4 4.9
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B

a
TEOS pre-hydrolysis period.
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peaks corresponding to (110) and (200) plans were observed,
a worm-like pore or MCF structure was probably formed. The
TEM photographs confirm that the material has the MCF
structure.
Fig. 7(b) shows that no apparent scattering signal was
observed at the beginning of first 10 min when only TEOS was
added to the SBA-15-p synthesis solution. After ca. 10 min,
a distinct scattering peak appeared at 2q ¼ 0.606 (d spacing ¼
12.6 nm), and the intensity grew with time. When TMB was
added to the synthesis solution at 25 min, the scattering peak
dramatically shifted from 2q ¼ 0.640 (d spacing ¼ 11.9 nm)
toward 2q ¼ 0.559 (d spacing ¼ 13.6 nm) in 10 min and the peak
intensity is double (Fig. 7(b)). The significant shift and growth of
the scattering signal suggests that the TMB molecules are indeed
dissolved in P123 micelles. It also implies that the swelling of
P123 micelles by dissolving TMB takes place in ca. 10 min. As the
self–assembly further proceeded, the (100) scattering peak
continuously grew up and the (110) and (200) scattering peaks

Fig. 7 In situ SAXS patterns of SBA-15-p materials prepared (a) with simultaneous adding TMB and TEOS, and those prepared with TEOS pre-
hydrolysis of (b) 25 min and (c) 60 min before the addition of TMB.

5698 | J. Mater. Chem., 2011, 21, 5693–5703 This journal is ª The Royal Society of Chemistry 2011

gradually appeared, inferring the formation of a ordered 2D
hexagonal pore structure. Similar results were observed when
TEOS pre-hydrolysis period was extended to 60 min before the
addition of TMB (Fig. 7(c)). However, the scattering peak only
shifts slightly from 2q ¼ 0.643 (d spacing ¼ 11.9 nm) to 2q ¼
0.630 (d spacing ¼ 12.2 nm). Nevertheless, the peak intensity
still increased significantly, suggesting that TMB was indeed
dissolved in the P123 micelles of silica-P123 nanocomposites.
Our previous studies, by in situ XRD and freeze-fraction
replica TEM of the SBA-15 synthesis solution containing a small
amount of ZrOCl2, reveal that a silica-P123 nanocomposite with
thread-like channels is first formed after TEOS is added for ca. 10
min.19 After 25 min, the ordered 2D hexagonal pore structure is
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
already formed by straightening and rearrangement of thread-
like channels. Nevertheless, at this moment the silicate conden-
Downloaded by University of Michigan Library on 26 February 2013
sation is far from complete and the silica framework is still soft.
The pore-swelling agent dissolved in the micelle can therefore
expand the pores effectively. Hence, the pore diameter (Fa_BdB)
of the sample prepared with TEOS pre-hydrolysis for 25 min can
be expanded to 10.6 nm by adding TMB as the swelling agent.
However, when the TEOS pre-hydrolysis period is further pro-
longed, the Fa-BdB value gradually decreases, implying that the
silica framework becomes too rigid and the pore-swelling agent
can no longer expand the pores effectively. The materials
obtained from TEOS pre-hydrolysis for several hours have
Fa_BdB values around 7.5 nm, which is similar to that observed on
the SBA-15-p material prepared without adding TMB (entry 1,
Table 1). These data reveal that the silica framework, after such
a long hydrolysis period, is too rigid to be swollen by the TMB
molecules.
The structural properties of short-channel SBA-15-p materials
prepared with TEOS pre-hydrolysis for 25 min and varying the
TMB/P123 weight ratios were further examined by XRD,
nitrogen physisorption, and electron microscopy. The small-
angle XRD patterns in Fig. 8(a) show that all materials prepared
with TMB/P123 weight ratios up to 2.5 have well-ordered 2D
hexagonal p6mm pore structures. Moreover, the diffraction
peaks shift gradually towards the lower angle region with the
increase of TMB/P123 weight ratios up to 0.25. Above this TMB/
P123 ratio, the peak positions do not substantially vary, indi-
cating that excess TMB do not positively increase the unit cell
parameter.
Fig. 8(b) clearly shows that the parallel and narrow hysteresis
loops shift toward higher P/P0 region by increasing the TMB/
P123 weight ratios up to 0.25. The pore size analysis in Table 3
shows that the Fa-BdB values substantially increase to around 11
nm by increasing the TMB/P123 weight ratios up to 0.5. Above
this ratio, the pore diameters do not significantly alter. The wall
thicknesses (4.1–5.1 nm), however, exhibit the opposite trend.
The materials with lower surface areas and pore volumes were
obtained when excess amounts of TMB were added in the
synthesis solution. SEM and TEM photographs show that the
materials prepared with TEOS pre-hydrolysis for 25 min still
retain the platelet morphology (Fig. S1 and S2, ESI†).
The TG analysis (Fig. S3, ESI†) shows that the contents of
organic moieties increase gradually from 40 wt% to 54 wt% when
TMB was added until the TMB/P123 weight ratio was 1.5 (Table
3). Further increase in the TMB did not increase the organic
contents in the solids. The decomposition temperatures of P123
This journal is ª The Royal Society of Chemistry 2011
View Article Online
Fig. 8 (a) Small-angle XRD patterns and (b) N2 sorption isotherms of
SBA-15-p materials prepared with TEOS pre-hydrolysis for 25 min and
various TMB/P123 weight ratios.
triblock copolymer determined at the peak maxima of DTG
profiles are all around 310  C, which are similar to those
observed in the previous report.19 This implies that TMB has
a limited solubility in the P123 micelles and the addition of TMB
does not significantly affect the interaction between P123
triblock copolymer and silica framework. In other words, only
the TMB molecules dissolved in the P123 micelles can expand the
pore diameter of the resulting mesoporous materials effectively.
If excess TMB is present, they may then disturb the self-assembly
processes of P123 micelles and TEOS, and the resultant materials
have less ordered structure and relatively low surface areas and
pore volumes.
Other swelling agents, such as tripropylbenzene (TPB) and
octane, were also applied in the present synthesis condition.
Fig. 9 shows that using TPB and octane as swelling agents
increases the pore diameters of platelet SBA-15 materials to
around 8.7 and 9.9 nm, respectively. Compared to bulky benzene
and linear alkane molecules, TMB is undoubtedly a more effi-
cient swelling agent.
Effect of hydrothermal temperature
When the TEOS pre-hydrolysis periods were kept around 25–
30 min and TMB/P123 weight ratio was around 0.5, the pore
diameters of short-channel SBA-15-p materials could be further
expanded by increasing the hydrothermal temperature. The
small-angle XRD patterns in Fig. 10 shows that all the materials
have at least three diffraction peaks corresponding to the (100),
(110) and (200) planes of 2D hexagonal p6mm pore structure.
The diffraction peaks progressively shift towards the lower angle
region as the hydrothermal temperatures increase from 50 up to
100  C. Then they remain in the similar 2q region when hydro-
thermal temperatures are further increased to 150  C. In the
wide-angle region, the prepared materials obtained from
hydrothermal temperatures lower than 120  C exhibit a broad
band at 20
40 , which is the characteristics of amorphous silica
frameworks.2 However, a sharp diffraction peak at 26.9 and
several weak diffraction peaks at 35.6, 43.7 and 53.5 are seen in
materials hydrothermally treated at 150  C. The peak positions
resemble those of crystalline zirconium silicate.37 These results
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 View Article Online

Table 3 Effect of TMB/P123 weight ratios on structural properties of short-channel SBA-15-p materials prepared with TEOS pre-hydrolysis for 25 min

TMB/P123
(weight ratio) a0 (nm) SBET (m2 g1) VTotal (cm3 g1) Fa_BdB (nm) FTEM (nm) Wt (nm) Organic moietya (wt%)

0 11.7 815 1.1 7.6 7.0 4.1 40

0.05 12.9 855 1.2 8.5 8.4 4.4 43
0.1 13.8 890 1.3 8.7 8.6 5.1 43
0.25 14.3 861 1.5 9.6 9.4 4.7 43
0.5 15.6 854 1.4 10.6 10.5 5.0 47
1 15.6 814 1.4 10.7 10.8 4.9 51
1.5 15.6 750 1.3 10.7 11.1 4.9 54
2 15.6 737 1.2 10.9 10.7 4.7 55
2.5 15.6 647 1.1 11.1 11.1 4.5 54
a
Based on the weight losses at 800  C in TG analyses.
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
Downloaded by University of Michigan Library on 26 February 2013

loops clearly shift to higher P/P0 regions as the hydrothermal

Fig. 9 Effect of different swelling agent-to-P123 (S/P123) weight ratios
on BdB-FHH adsorption pore sizes (Fa_BdB) of SBA-15-p materials
prepared with TEOS pre-hydrolysis for 25 min.
temperature increases. The corresponding pore diameters
determined from the peak maxima of the PSD curves, based on
the BdB-FHH adsorption isotherms, progressively shift toward
higher values as the hydrothermal temperatures increase (Fig. 11
(b)). The structural properties of these materials are listed in
Table 4. The unit cell parameters increased significantly from
11.8 to 15.6 nm after hydrothermal treatment at temperatures up
to 90  C. Above this temperature, the unit cell parameters do not
significantly change. Similar trend can be seen for the pore
volumes. On the other hand, the surface area reaches
a maximum, for the material hydrothermally treated, at 70–90  C
and then decreases as the hydrothermal temperature is further
increased. A significant decrease in surface area is seen for the
materials prepared with hydrothermal temperature of 150  C.
The XRD patterns showed that zirconium silicate was formed at
such a high temperature, the optimal hydrothermal temperature
to expand the pore diameter of platelet SBA-15 should be around
120  C.
The pore diameter Fa-BdB values (6.8–13.2 nm) are positively
correlated with hydrothermal temperature, whereas wall thick-
nesses, micropore volumes and micropore surface areas are
negatively correlated with hydrothermal temperature. Because
the unit cell parameters are almost unchanged for the materials

Fig. 10 XRD patterns of SBA-15-p materials prepared at different

hydrothermal temperatures (HT) with TEOS pre-hydrolysis for 25 min
and TMB/P123 weight ratio of 0.5. The asterisk peaks are due to crys-
talline zirconium silicate.

indicate that zirconium silicate nanocrystallites are formed when

the hydrothermal temperature is around 150  C. Fig. 11 (a) N2 sorption isotherms and (b) BdB-FHH adsorption PSD
Fig. 11(a) shows that all the materials have the classic type IV curves of SBA-15-p materials prepared at different hydrothermal
isotherms with H1 hysteresis loops at P/P0 in 0.6–0.9, indicating temperatures with TEOS pre-hydrolysis for 25 min and TMB/P123
the presence of well-ordered channeling pores. The hysteresis weight ratio of 0.5.

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 View Article Online

Table 4 The effect of hydrothermal temperatures on the structural properties of short-channel SBA-15-p materials.a

Organic moietyb
T/ C a0 (nm) SBET (m2 g1) SMicro. (m2 g1) VTotal (cm3 g1) VMicro. (cm3 g1) Fa_BdB (nm) FTEM (nm) Wt (nm) (wt%)

non 11.8 798 256 0.82 0.12 6.8 6.6 5.0 56

50 12.5 844 200 0.92 0.10 7.5 7.7 5.0 58
70 13.7 895 169 1.2 0.081 8.8 9.1 4.9 56
90 15.6 854 160 1.4 0.070 10.6 10.5 5.0 56
100 15.6 775 149 1.6 0.064 11.2 10.9 4.4 56
110 15.6 642 135 1.6 0.059 11.2 11.5 4.4 51
120 15.6 616 130 1.5 0.055 12.3 12.1 3.3 50
150 15.6 366 110 1.4 0.048 13.2 12.9 2.4 54
a
The materials were prepared with a TMB/P123 ratio of 0.5 and a TEOS pre-hydrolysis period of 25 min. b Based on the TG analysis.
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B

prepared at hydrothermal temperatures between 100–150  C, the Langmuir equation, ns/nm ¼ Kc/(1 + Kc), where ns is the amount
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wall thickness shrinks with the expansion of the pore diameters in of cytochrome c adsorbed on the materials, nm is the monolayer
this temperature range. The decrease in wall thickness with adsorption capacity, and c is the concentration of cytochrome
hydrothermal temperature is due to the more complete conden- c.38 The K values are 0.501, 1.06 and 1.15 L mmol1 at pH values
sation of the silicate at higher temperatures. As a result, the of 4, 7 and 10, respectively, confirming that the cytochrome
micropore volumes and micropore surface areas are also c preferentially adsorbs on the materials at a pH close to its pI.
decreased. It is also noted that without adding the swelling Table 5 compares the uptakes of horse heart cytochrome c at
agents, the largest pore diameters (Fa-BdB) of SBA-15-p mate- pH 7 and 10 over short-channel SBA-15-p materials with pore
rials, prepared by increasing the hydrothermal temperatures up diameters in 7.6–12.3 nm, in comparison to those of long-channel
to 150  C, are only ca. 9.5 nm (Figure S4, ESI†). Therefore, the SBA-15-f with pore diameters in 6.2–9.4 nm. Again, the uptakes
addition of TMB as a swelling agent in the synthesis solution is of cytochrome c on the materials at pH 10 are higher than those
necessary in further expanding the pore diameters of SBA-15-p at pH 7. For the conventional SBA-15-f materials, the one with
materials. pore diameter and volume of 9.4 nm and 1.2 cm3 g1 has higher
In summary, given a suitable TEOS pre-hydrolysis period of uptake amount than that with pore diameter and volume of
25–30 min, the pore diameters of short-channel SBA-15-p 6.2 nm and 0.91 cm3 g1 at pH 7. At pH 10, the difference in
materials of well-ordered pore structure can be expanded up to adsorption capacities of SBA-15-f materials with different pore
12 nm by adding TMB as the swelling agent with TMB/P123 sizes is almost negligible. The higher adsorption capacity of SBA-
weight ratios around 0.5 and a hydrothermal temperature of 15-f materials with a large pore opening of 9.4 nm at pH 7 is an
120  C. Excess amounts of TMB may interfere the self-assembly indication that the molecular diffusion through the lengthy
of P123 micelles and TEOS and result in materials with low channels can be enhanced by expanding the pore openings.
surface areas and pore volumes. Over the short-channel SBA-15-p materials, much higher
uptakes of cytochrome c (23.9–36.6 mmol cyto c/g SiO2) were
Adsorption study
Fig. 12 shows the adsorption isotherms of horse heart cyto-
chrome c on short-channel SBA-15-p materials with a pore
diameter of 10.6 nm at pH values in 4–10. The symbols represent
the experimental data and the solid curves are the fitting results
based on the Langmuir model. The uptakes of cytochrome c on
the SBA-15-p materials raise rapidly when the final solution
concentrations are below ca. 5 mmol L1 at pHs 7–10 and ca.
10 mmol L1 at pH 4. Further increase in the concentrations does
not significantly increase the uptakes of cytochrome c. The
maximum uptakes of cytochrome c on the SBA-15-p materials at
pH values of 4, 7 and 10 are 22.8, 25.4 and 36.6 mmol g1 SiO2,
respectively. Noticeably, the adsorption capacity of cytochrome
c at pH 10 is significantly higher than those at pH 4 and 7. Similar
data have been reported by other research groups.38,39 The
isoelectric point (pI) of cytochrome c is around 9.8, at which
point the sum of the protein charges approach zero.24 Since
cytochrome c molecules may pack closer at pI, due to less
repulsion among them, higher uptake of cytochrome c is Fig. 12 Adsorption isotherms of cytochrome c at 20  C on SBA-15-p
obtained at pH 10 than at lower pH values. The equilibrium material with a pore diameter in 10.6 nm at various pH values of (-) 4,
constants (K) of cytochrome c adsorption on SBA-15-p materials (O) 7 and (C) 10. The solid curves are the fitting results based on the
were calculated by fitting the experimental data with the Langmuir model.

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 View Article Online

Table 5 Adsorption of cytochrome c over short-channel SBA-15-p materialsb,c with various pore diameters in comparison with conventional SBA-15-f
materials

cyto c mmol g1 SiO2

Channel (cyto c nmol m2)
Morph. Length Zr/Sid TMB/P123d HT/ SBET VTotal Fa_BdB

Entry (SEM) (TEM) (molar ratio) (weight ratio) C (m2 g1) (cm3 g1) (nm) pH ¼ 7.3 pH ¼ 10.3

1a Fiber >10 mm 0 0 90 913 0.91 6.2 5.49 (6.01) 19.8 (21.7)

2a Fiber >10 mm 0 0 120 830 1.2 9.4 10.7 (12.8) 19.9 (23.9)
3b Platelet 150–350 nm 0.05 0 90 815 1.1 7.6 23.9 (29.3) 32.9 (40.4)
4c Platelet 150–350 nm 0.05 0.5 90 854 1.4 10.6 25.4 (29.7) 36.6 (42.8)
5c Platelet 150–350 nm 0.05 0.5 120 616 1.5 12.3 25.9 (42.1) 33.0 (53.6)
a
SBA-15-f reference materials are prepared according to the procedures reported by Zhao et al.6 b SBA-15-p reference material is prepared based on the
procedures of our previous study.12,19 c Short-channeled SBA-15-p materials are prepared based on the procedures of the present study. d In the gels.
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
Downloaded by University of Michigan Library on 26 February 2013

obtained, compared to those of SBA-15-f materials. Although
horse heart cytochrome c has a thermodynamic dimension of
approximately 2.6 nm  3.2 nm  3.3 nm, the present study
shows that the diffusion of cytochrome c in the channels of
conventional SBA-15-f materials still seems to be hindered. The
difference in adsorption capacities of short-channel SBA-15-p
materials with 7.6–12.3 nm pores appears to be insignificant.
However, after normalization by surface area, short-channel
SBA-15-p with the largest 12.3 nm pore opening gives the highest
adsorption capacities (42.1–53.6 nmol cyto c/m2).
Fig. 13(a) shows the uptakes of cytochrome c at pH 10 as
a function of time period. The adsorption of cytochrome c
requires only 120–250 min to reach equilibrium on the short-
channel SBA-15-p materials, with large pore openings of 10.6–
12.3 nm, but it requires 6 h or longer on conventional SBA-15-f
materials with long mesochannels and relatively small pore
openings (9.4 nm). Fig. 13(b) compares the uptakes at the
beginning of the adsorption experiments. Between the two short-
channel SBA-15-p materials, slightly slower adsorption rate and
lower uptake of cytochrome c is observed in the one with 12.3 nm
pores than that with 10.6 nm pores. It is attributed to the lower
surface area of the larger pore material. On the other hand, the
uptake of cytochrome c in the first 10 min by SBA-15-p with 10.6
nm pores is almost four times that of the SBA-15-f with 9.4 nm
pores, although both samples have almost the same surface area.
Clearly, molecular diffusion is indeed facilitated through the
short mesochannels of platelet materials, and large pore openings
provide rapid and efficient adsorption of the enzyme molecules.

Fig. 13 Cytochrome c uptakes as a function of adsorption time over
SBA-15 of different morphologies and pore diameters: (-) short-channel
SBA-15-p with 10.6 nm pores, (B) SBA-15-p with 12.3 nm pores, and
(:) conventional SBA-15-f material with 9.4 nm pores.
Conclusions
A facile synthesis for preparing SBA-15 platelet materials with
short mesochannels (ca. 200 nm) and large pore diameter up to
12 nm was developed by adding Zr(IV) ions and TMB to the
conventional SBA-15 synthesis solution. According to the results
of conventional characterization techniques and in situ small-
angle X-ray scattering experiments, pre-hydrolysis of TEOS for
at least 25–30 min was an essential step in obtaining a well-
ordered 2D hexagonal pore structure and platelet morphology
without vesicle contamination. More importantly, the meso-
pores, estimated by BdB-FHH adsorption pore size analysis, of
short-channel SBA-15 platelet materials, which have high surface
areas (
800 m2 g1) and large pore volumes (
1.5 cm3 g1), could
be controllable within 7–12 nm by varying the amount of TMB
and the hydrothermal temperature. Adsorption of cytochrome c
was dependent on the channel length and pore diameter of the
prepared materials and the pH value of adsorbing solution. At
a pH value of ca. 10, where the net change in cytochrome c
approaches zero, the adsorption rate and capacity of short-
channel SBA-15 platelet materials with large pore openings were
substantially higher than those of conventional fiber-like

5702 | J. Mater. Chem., 2011, 21, 5693–5703 This journal is ª The Royal Society of Chemistry 2011

SBA-15-f materials with small pore openings and long meso-
channels in the micrometre scale. Therefore, the adsorption of
the prepared materials was enhanced by the increased molecular
diffusion and the reduced pore blockage through the short
mesochannels and large pore openings. We are currently
extending the synthesis route for organic-functionalized SBA-15
platelet materials with short mesochannels and large pore
openings. The materials obtained by this synthesis route exhibit
unique properties in their sorption of biomolecules from human
urine samples, which are used as protein biomarkers for moni-
toring urological cancer, and asymmetric adol reduction of large
molecules with good results in terms of yield and enantiose-
lectivity. Further details will be published in the near future.
Published on 04 March 2011 on http://pubs.rsc.org | doi:10.1039/C0JM03591B
Acknowledgements
Downloaded by University of Michigan Library on 26 February 2013
This research was supported by a grant from National Science
Council, Taiwan. Chih-Yuan Tang and Ching-Yen Lin of
Instrumentation Center, National Taiwan University, Taiwan,
were acknowledged for their assistance in TEM and SEM
experiments. S.-Y.C. would like to thank Prof. G. D. Stucky
of University of California at Santa Barbara, USA, and
Dr W. Lukens of Lawrence Berkeley National Laboratory,
USA, for the helpful discussion and for providing the modified
BdB-FHH program to analyze the pore structure and PSD of
SBA-15 and MCF materials. Ted Knoy was appreciated for his
editorial assistance.
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