J Porous Mater

DOI 10.1007/s10934-013-9728-9

SO3H-functionalized mesoporous carbon/silica composite

with a spherical morphology and its excellent catalytic
performance for biodiesel production
Binbin Chang Yanlong Tian Weiwei Shi
Jiyang Liu Fengna Xi Xiaoping Dong

Springer Science+Business Media New York 2013

Abstract Mesoporous carbon/silica composites functionalized with SO3H groups were prepared via polymerization and carbonization of glucose into mesoporous
silica SBA-15 and a followed sulfonation by sulphuric
acid. These composites were characterized by powder
X-ray diffraction, N2 adsorptiondesorption and transmission electron microscopy, which suggested the preservation
of ordered mesoporous structure, as well as a novel
spherical morphology. The result of fourier transform
infrared spectroscopy indicated the successful modification
of SO3H groups and the acidity of catalysts was determined by an indirect titration method. The composite with
40 % carbon loading possessing the highest acidity in
synthesized catalysts and the ordered mesoporous structure
without pore blocking exhibited a remarkable catalytic
activity for biodiesel production. Experimental parameters
including the carbon loading, molar ratio of reactants,
reaction time and reaction temperature were optimized. In
addition, a superior recycling property was exhibited after
five consecutive cycles.
Keywords Mesoporous carbon/silica composite  Porous
solid acid  Catalysis

1 Introduction
Biodiesel, an eco-friendly fuel production, has exhibited
great potential as substitute for traditional fossil energy

B. Chang  Y. Tian  W. Shi  J. Liu  F. Xi  X. Dong (&)

Department of Chemistry, School of Sciences, Zhejiang
Sci-Tech University, 928 Second Avenue, Xiasha Higher
Education Zone, Hangzhou 310018, China
e-mail: xpdong@zstu.edu.cn

resources [15]. During the past decade, biodiesel has

been derived from either the transesterification of triglycerides or the esterification of free fatty acids with
short-chain alcohols. In these reactions, catalysts play an
important role in accelerating the transesterification and
esterification process. Traditional liquid acids (such as
HCl and H2SO4) are widely used in chemical industry,
however, the difficulty to separate from products makes
them lose the recyclability. Furthermore, the consumption
of liquid acids generally produces considerable toxic
waste and results in serious environmental problems.
Thus, out of the concept of environmentally friendly,
the developments of efficient solid acid catalysts to
instead of traditional liquid acids have became an inevitable trend.
In recent years, acid functionalized materials as solid
acid such as inorganic-carbon composite [6], organiccarbon composite [7], mesoporous silicas [8, 9] and so on
[1012], have been paid much attention by researchers.
Mesoporous silica based on self-assembly principles are
novel materials with high surface area, large pore volume,
uniform channels, tailored and ordered structures, which
make them become potential catalysts or catalytic supports.
Currently, the preparation of acid functionalized mesoporous silica mainly concentrates on the doping of metal
ions in silica framework and the modification of acidic
groups on pore surface [1315]. Though metal dopants
bring strong acid sites in the inert silica wall, the doped
amount is limited because the mesoporosity of silica
decreases with the increase of metal amount [16]. The
surface acidic groups, mainly SO3H groups, are usually
obtained from the oxidation of SH groups by a postgrafted method [17]. Unfortunately, the acidity is also
constrained by the low concentration of SiOH groups on
pore surface in post-grafted strategies.

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J Porous Mater

Another important kind of acid functionalized solid

catalysts used in catalysis of biodiesel products is carbonbased materials bearing SO3H groups. These acid groups
can be loaded on the surface of carbon by a sulfonation
treatment of incompletely carbonized sugar in concentrated
sulfuric acid. It has been confirmed that amorphous carbons
bearing SO3H groups possess high catalytic activity for
the production of biodiesel [18, 19]. However, these carbon-base acid catalysts prepared from sugars possess low
surface area (\5 cm2 g-1), poor porosity and relatively
low acid density ranging from 0.37 to 1.34 mmol H? g-1
[18, 19]. Mesoporous carbon (MC) presents high chemical
stability, high surface area, and simplification of functionalization with active groups [20, 21]. Consequently, it
has been widely used as an admirable catalyst or catalyst
support in a variety of industrial and environmental
applications [2224]. SO3Hmodified MC materials with
excellent catalytic performance have been successfully
synthesized by different routes [2528]. These materials
retain mesoporous structure with high surface area and
regular pore size, whereas, the acidity is much lower than
those of incompletely carbonized catalysts. The modification of SO3H groups on carbon surface involves the
reaction of COH and COOH with H2SO4 [29]. In other
words, the acidity is mainly determined by the concentration of surface oxygen-containing groups. However, carbonizations at high temperature are necessary for MC
synthesis, which would result in the lack of oxygen-containing groups on pore surface. Therefore, the increase of
surface acid sites meantime keeping of the mesoporosity is
vital for developing efficient MC solid acid catalysts.
Herein, we reported the preparation of SO3Hfunctionalized mesoporous carbon/silica composite (C/SiSO3H)
with a novel spherical morphology. The hydrothermal condition for the carbonization of precursors is favorable for
remaining abundant oxygen-containing groups, accordingly,
a high acidity produced after the sulfonation by concentrated
sulphuric acid. These mesoporous carbon/silica composites
exhibited relative high specific surface area, connected pore
structure, high acidity and excellent catalytic activity, as well
as superb recycled performance for the esterification of oleic
acid (OA) with methanol.

2 Experimental
2.1 Preparation of C/SiSO3H composite materials
Mesoporous silica SBA-15 was synthesized using an amphiphilic triblock copolymer, pluronic P123 (EO20PO70EO20)
as a structure directing agent [30]. Carbon/silica composites
were prepared by a simple hydrothermal method. In a typical
experiment, 1.0 g SBA-15 was dispersed in a specific

123

concentration of glucose solution and stirred for 2 h. Then,

the glucose/SBA-15 solution was placed in a Teflonsealed
autoclave and maintained at 453 K for 15 h. The black
products were obtained by filtration, washed repeatedly with
distilled water, ovendried at 353 K, and designated as C/Si
x, where x refers to the mass of loaded carbon and was
determined by a thermogravimetry method. A series of
samples with different carbon loading were obtained by
varying the mass of impregnated glucose in the range of
1.03.0 g. Subsequently, these C/Six materials were sulfonated using concentrated sulfuric acid at 423 K for 10 h in
a Teflonsealed autoclave. Then, these sulfonated C/Six
catalysts were washed repeatedly with hot distilled water
([353 K) until the sulfate ions were no longer detected in the
wash water (BaCl2 precipitation test) and were dried at
373 K for 6 h. The resulting materials were denoted as C/Si
xSO3H.
For comparison, SBA-15 was sulfonated using concentrated sulfuric acid at 423 K for 10 h in a Teflonsealed
autoclave, designated as SBA-15SO3H.
2.2 Characterizations
The Xray diffraction (XRD) patterns of powder samples
were taken by a Bruker D8 Advance diffractometer using
Cu Ka radiation (k = 0.15418 nm) as an Xray source.
Nitrogen adsorptiondesorption isotherms were carried out
at 77 K using a Micromeritics ASAP 2020 analyzer.
Before adsorption, the samples were out-gassed at 373 K
for 4 h. The specific surface area (SBET) was evaluated
using the BrunauerEmmettTeller (BET) method, while
the pore volume and pore size were calculated according to
the BarrettJoynerHalenda (BJH) formula applied to the
adsorption branch. Fourier transform infrared spectroscopy
(FTIR) spectra of a sample in KBr pellet were recorded on
a Nicolet Avatar 370 spectrometer. The morphology and
pore structure were observed from a scanning electron
microscope (SEM, Hitachi S-4800) and a JEOL JEM2100
transmission electron microscope (TEM) with an accelerating voltage of 200 kV. The thermogravimetric (TG)
analysis curves were obtained on a Mettler analyzer (TGA/
SDTA851e/5FL1100).
The number of acid sites was estimated by using an
indirect titration method [31, 32], which involves an
aqueous ion-exchange step of the catalyst H? ions with
base of NaHCO3, followed by titration of the resulting
solution with HCl aqueous solution (0.1 M). In a typical
experiment, 30 mg of the catalyst was dispersed in 50 mL
of 5 9 10-3 mol L-1 NaHCO3 solution, which was stirred
for 24 h and separated by filteration. Then 5 mL of filtrate
was taken out for titration with 0.1 M of HCl aqueous
solution. Titration was performed three times and the
average number was reported. The amount of acid groups

J Porous Mater

in the solid acid catalysts was estimated by the NaHCO3

consumed.
2.3 Catalytic testing
Catalytic esterification of OA with methanol was performed in a 100 mL three necked round bottomed flask
equipped with a reflux condenser, magnetic stirrer and a
water bath maintained at a specified temperature. In a
typical experiment, 0.05 mol of OA was mixed in anhydrous methanol (MeOH) in the round bottom flask and the
required quantity of solid acid catalyst (0.1 g) was added.
At regular time intervals, 4 mL of samples were extracted
to check the progress of esterification reaction. The samples drawn from the reaction mixture were centrifuged to
separate the catalyst powder, then, the methanol and water
were evaporated out of the samples, and the product analyzed for acid value (AV) by titration [33]. The conversion
of OA was calculated using the following formula:

Fig. 1 The TG curves of C/Si-x composites materials

Conversion % 1  AVx =AV0  100%

where AVx is the instant AV of samples drawn from the
reaction mixture, AV0 is the initial AV of oleic acid.

3 Results and discussion

3.1 Characteristics of catalysts
The carbon loading in these carbon/silica composites were
determined by the thermogravimetry method, and Fig. 1
shows the TG curves measured under an air atmosphere for
C/Si composites. In the temperature range from 500 to
800 K, the C/Si composites lost respectively *20, *40
and *60 %, which indicates the relative amounts of carbon in the composites are *20, *40 and *60 %, as 1, 2
and 3 g of carbon source were used. Figure 2 shows the
lowangle XRD patterns of SBA-15, C/Six and C/Six
SO3H composites. The characteristic peaks assigned to
(100) (110), and (200) diffractions of 2D hexagonal mesoporous structure can be clearly observed in all samples,
which indicate that C/Six and C/SixSO3H samples still
retain the ordered mesoporous structure of SBA-15. In
addition, the (100) diffraction peak of carbon/silica composites shifts to a lower angle compared to SBA-15,
resulting in their larger d100 values (Table 1). It is well
known that the structural contraction of mesoporous silica
occurs, due to the further condensation of SiOH groups,
when organic templates are removed by calcination at high
temperature [34, 35]. The structural expansion of carbon/
silica composites could be ascribed to the partial hydrolysis
of the SiOSi framework to form SiOH groups when
calcined SBA-15 is re-hydrothermal treated [36].

Fig. 2 a Low-angle XRD patterns of SBA-15, C/Six and b C/Six

SO3H composite materials

Figure 3 a shows N2 adsorptiondesorption isotherms of

SBA-15, C/Six and C/SixSO3H composites. All these
samples show typical type IV curves with a clear hysteresis
loop at relative pressure from 0.65 to 0.85, which indicate
that the uniform cylindrical mesoporous channels are
retained. The adsorption volume of nitrogen decreasing
with the increase of carbon loading suggests the reducing
of surface area. These decreases should be caused by

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J Porous Mater
Table 1 Textural parameters and chemical properties of catalysts
Sample

SaBET (m2g-1)

VbP (cm3g-1)

Dcp (nm)

dd(100) (nm)

SBA-15

746

1.03

8.38

8.5

ae0 (nm)
9.82

Dfpw (nm)

Acidityg
(mmol H? g-1)

1.44

SBA-15SO3H

507

0.88

7.76

8.6

9.93

2.17

0.35

C/Si20 %

358

0.75

7.55

8.9

10.28

2.73

C/Si40 %

260

0.55

7.42

9.2

10.62

3.20

C/Si60 %

166

0.37

7.27

9.4

10.85

3.58

C/Si20 %SO3H

298

0.66

7.47

9.0

10.39

2.92

0.98

C/Si40 %SO3H
C/Si60 %SO3H

209
158

0.44
0.41

7.41
7.14

9.2
9.4

10.62
10.85

3.21
3.71

1.68
1.40

Specific surface area estimated using BET method

Pore volume estimated from BJH formula

Pore diameter of peak value in Fig. 3b

d-spacing of 100 diffraction

Cell parameter

Pore wall thickness

Measured by acidbase titration

Fig. 3 a N2 adsorptiondesorption isotherms and b pore diameter distributions of SBA-15, C/Six and C/SixSO3H samples

carbon species deposited on the internal surface of SBA15. The pore structure parameters are listed in Table 1. The
specific surface area and the pore volume continue to
reduce after sulfonation treating with concentrated sulfuric
acid, which may be attributed to the presence of a large
number of -SO3H groups. The pore diameter distributions
of SBA-15, C/Six and C/SixSO3H composites are
shown on Fig. 3b. The decrease in pore diameter and the
enhancement of pore wall thickness demonstrate that carbon species have successfully loaded on the pore channels
of SBA-15. In addition, the hysteresis loop of C/Si60 %
SO3H exhibits an obvious delay at relative pressure range
of 0.550.65, which implies that carbon particles accumulate to block the channels [37, 38].

123

To reveal the morphology and structure of materials,

SEM and TEM images of the C/Si40 % and C/Si60 %
particles before and after the sulfonated modification are
shown in Figs. 4 and 5. A spherical shape nanoparticle is
observed in mesoporous carbon/silica composites from
Fig. 4. The transformation of morphology may be related
to the hydrothermal treatment [39]. After sulfonation, the
spherical morphology is still maintained (Fig. 5a, b),
indicating that the process of sulfonation does not destroy
the structure of materials. Figure 5c and d show the TEM
images of single carbon/silica composite spheres of C/Si
40 %SO3H and C/Si60 %SO3H. A highly ordered
mesoporous structure is directly observed in C/Si40 %
SO3H sample, whereas, an indiscernible pore structure is

J Porous Mater

Fig. 4 SEM and TEM images of a, c C/Si40 % and b, d C/Si60 % samples samples

Fig. 5 TEM images of a C/Si

40 %SO3H and b C/Si60 %
SO3H samples. TEM images of
single carbon/silica composite
spheres of c C/Si40 %SO3H
and d C/Si60 %SO3H
samples

shown in C/Si60 %SO3H sample, which should be due

to the excess carbon particles accumulate to block the pore.
This result is in accordance with that of N2 adsorption
desorption isotherm.

Fourier transform infrared spectroscopy spectra (Fig. 6)

are used to characterize the functional groups. In SBA-15,
the bands centered at 1,086, 800 and 470 cm-1 are attributed to asymmetric stretching, symmetric stretching and

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J Porous Mater

bending modes of SiOSi respectively and the band at

965 cm-1 is related to the characteristic stretching vibration of non-bridged SiOH groups [40, 41]. These
absorptions of SiOSi weaken in carbon/silica composite,
and the absorption of SiOH even becomes illegible, which
may be because that the SiOH group reacted with COH
group of carbon in the hydrothermal condition. Moreover,
the relative intensity of the absorption band at
*3,450 cm-1 corresponding to the stretching vibration of
OH group is significantly enhanced, indicating the plentiful oxygen-containing groups, which is favorable for the
modification of SO3H groups. In comparison with C/Si
sample, an additional peak at 1,020 cm-1 is found in the
samples with sulfonation treating. This absorption can be
ascribed to the S=O symmetric stretching vibrations [42,
43], and demonstrates that SO3H groups have been successfully modified onto the MC/silica composites. Additionally, the peak at 1,635 cm-1 is raised from the C=C
stretching vibration, suggesting the presence of polycyclic
aromatic rings, which are considered as the product of the
carbonization of organic substances [44, 45].
3.2 Catalytic performances of C/SixSO3H
composites
The solid acid catalyzed esterification is an equilibrium
limited reaction. To investigate the catalytic performances
of C/SixSO3H composite catalysts, esterification of OA
with methanol was carried out. Scheme 1 shows the
mechanistic steps during the esterification reaction [46].
The solid acid catalyst activates the esterification reaction
by affording a proton to the carboxylic acid molecule to
form a carbonium ion, which is readily attacked by an
alcohol (CH3OH) to give the corresponding ester after
losing a H2O and a proton.

3.2.1 Effect of carbon loading

Figure 7 depicts the catalytic performance of various catalysts in esterification of OA with methanol. It clearly
displayed that the catalytic activity enhanced with the
increase of carbon loading from 20 to 40 %, which was
owed to the increase of acidity of catalysts (Table 1).
Nevertheless, with higher carbon loading, the catalytic
activity declined from C/Si40 %SO3H to C/Si60 %
SO3H and the OA conversion dropped from *80 to
*65 %. This behavior could be explained that the higher
carbon loading block the pore of SBA-15 to result in the
decrease of acidity and the reduced accessibility to acid
sites. For comparison, the catalytic performance of SBA15SO3H was also tested. The observed OA conversion on
SBA-15SO3H was only *20 % and much lower than that
of C/Si40 %SO3H, and this result may be ascribed to its
low acidity.
To further estimate the catalytic activity of C/Si40 %
SO3H, the influences of reaction parameters, including
reaction time, reaction temperature and molar ratio of
MeOH/OA, were investigated as following.
3.2.2 Effect of reaction time
The reaction time is an important parameter for evaluate
catalytic activity of solid acid catalyst. Figure 8 shows the
OA conversion dependent on reaction time from 0 to 3 h
with a MeOH/OA molar ratio of 10:1 at 343 K. This catalyst exhibits a highly catalytic activity and reaction rate.
The OA conversion rapidly mounted to *70 % in the
initial 0.5 h, and reached an equilibrium value of *80 %
after 1.5 h. The connected mesoporous structure and large
surface area bearing abundant SO3H groups should be
responsible for this excellent performance, which allow
reactants to promptly transfer in the catalyst system to
reach active sites, and in the meantime products formed on
catalyst surface can quickly diffuse out of catalyst to the
solution.

Solid acid catalyst

OH

O
R C

OH

+H+

OH

C+ OH + O

Oleic acid

OCH3

O+H2
_H O
2

O
R

OCH3

Methyl oleate

123

CH3

Methanol
R= C17H33

Fig. 6 FTIR spectra of SBA-15, C/Six and C/SixSO3H samples

C
OH

CH3

OH

H
O+

H+

H3CO

OH

Scheme 1 Mechanism of solid acid catalyzed esterification of OA

with methanol

J Porous Mater

3.2.3 Effect of reaction temperature

The effect of reaction temperature on esterification was
investigated at different temperatures (323, 333, 343 and
353 K) for 3 h. Figure 9 obviously demonstrates that the
reaction rate is dependent on the reaction temperature.
Under a lower reaction temperature of 323 K, the esterification reaction got to an equilibrium state after *2 h.
With the gradual enhancement of temperature to 333 and
343 K, the times to equilibrium were shortened to *1.5
and *1 h, which was ascribed to the much faster diffusion
rate of reactants under a higher reaction temperature. As
the reaction temperature was raised up to 353 K, however,
the catalytic performance was similar to that under 343 K.
The reason may be that this temperature has greatly
exceeded the boiling temperature of methanol, and a significant portion of methanol was under refluxing to reduce
its concentration in reaction solution. Furthermore, because
the esterification reaction is a reversible endothermic process, appropriately increasing temperature is favorable for

the forward reaction. Consequently, the OA conversion

gradually increases from *68 % (323 K) to *71 %
(333 K) to *80 % (343 and 353 K).
3.2.4 Effect of MeOH/OA molar ratio
The molar ratio of methanol to OA is another most
important variable to affect the OA conversion. Because
esterification is an equilibrium reaction, the amount of
methanol is usually excessive to force the reaction towards
the formation of ester [47]. Figure 10 depicts the OA
conversion versus MeOH/OA molar ratio from 1:1 to 30:1
at 343 K for 2 h. An extremely low OA conversion of
*35 % was obtained with a MeOH/OA molar ratio of 1:1.
With the increase of the molar ratio, the OA conversion
dramatically increased. As using a 30:1 molar ratio, the OA
conversion reached above 90 %. This behavior demonstrates that the increased MeOH/OA molar ratio play an
important role in driving the equilibrium to the product
side. When the MeOH/OA molar ratio was at a low value, a

Fig. 7 Comparison of catalytic activities for conversion of OA with

various catalysts (MeOH/OA = 10:1; 2 h; 343 K; 0.1 g catalyst)

Fig. 9 Effect of reaction temperature on the conversion of OA over

C/Si40 %SO3H (MeOH/OA = 10:1; 3 h; 0.1 g catalyst)

Fig. 8 Dependence of the OA conversion on reaction time over

C/Si40 %SO3H (MeOH/OA = 10:1; 343 K; 0.1 g catalyst)

Fig. 10 Effect of MeOH/OA molar ratio on the conversion of OA

over C/Si40 %SO3H (2 h; 343 K; 0.1 g catalyst)

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J Porous Mater

large number of methanol molecules were vaporized into

reflux condenser. As a result, the methanol concentration in
reaction solution was decreased in a great degree, which
induced the low OA conversion. On the other hand, as
enhancement of the methanol concentration, the rate of
forward reaction was sharply raised, and in the meantime,
the rate of reverse reaction was restricted. Consequently,
the enhancement of MeOH/OA molar ratio contributes to
drive the equilibrium to the product side and bring a higher
OA conversion.
3.3 The reusability of catalyst
The catalyst recycling is extremely important to estimate
the efficiency of solid acid catalysts, which contributes to
reduce the cost of practical applications process. The
deactivation of solid acid catalyst occurred due to the
leaching of sulfate groups caused by the water presented in
the reaction medium [48, 49]. In order to prove the reusability of catalyst, after each catalytic reaction the solid
acid catalyst was separated by centrifugation and washed
repeatedly with ethanol and distilled water. The washed
catalyst was dried at 373 K and used for the next experiment. Figure 11 presents the reusability of C/Si40 %
SO3H catalyst through five consecutive cycles with a
MeOH/OA molar ratio of 30:1 at 343 K for 2 h. It was
noteworthy to mention that the catalyst was reusable
without any appreciable loss in activity. Meanwhile, for
checking the stability of SO3H groups, the resulting
mixture after catalytic reaction was washed with water to
extract sulfate ions possibly leached from catalyst. The
BaCl2 precipitation test demonstrates no sulfate ions exist
in the washed water, suggesting the stability of SO3H
groups on the surface of catalyst.

Fig. 11 Recyclability of C/Si40 %SO3H catalyst for the esterification of OA with MeOH (MeOH/OA = 30:1; 2 h; 343 K; 0.1 g
catalyst)

123

4 Conclusion
In conclusion, hydrothermal treatment strategy in the presence of glucose and SBA-15 was applied to prepare a
spherical mesoporous carbon/silica composite. The material
exhibits a novel spherical morphology, uniform and connected pore structure, well dispersion of acid sites and a
striking catalytic performance on esterification. Importantly,
leaching of functional groups from the hybrid catalyst in the
reaction system was inhibited and the catalyst can maintain
its initial activity after five consecutive catalytic cycles. In
addition, such a synthetic method proposes a new strategy for
controlling and preparing the different morphology of hybrid
mesoporous materials with high activities.
Acknowledgments The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China
(21001093), the Qianjiang talent project of Zhejiang Province of
China (2011R10048), the Science Foundation of Zhejiang Sci-Tech
University (0913848-Y) and the project-sponsored by SRF for ROCS,
SEM.

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