High-temperature synthesis of magnetically active and SO 3H-functionalized ordered mesoporous carbon with good catalytic performance

Article abstract of DOI:10.1016/j.cattod.2011.11.011

Magnetically active and SO₃H-functionalized ordered mesoporous resin and carbon (MOMR-SO₃H, MOMC-SO₃H) were successfully prepared by high-temperature hydrothermal synthesis from resol, copolymer surfactant, and iron cations at 180 °C, followed by sulfonation from sulfuric acid fuming. X-ray diffraction patterns show that MOMR-SO₃H and MOMC-SO₃H have ordered hexagonal mesoporous symmetry. N ₂ isotherms indicate that these samples have uniform and opened mesopores, high surface areas (335-591 m²/g), and large pore volumes (0.34-0.35 cm³/g). Transmission electron microscopy shows that iron nanoparticles, which are superparamagnetic in nature, are highly dispersed in MOMC-SO₃H sample. Catalytic tests show that MOMC-SO₃H is highly active and excellently recyclable in esterification of acetic acid with butanol, esterification of acetic acid with cyclohexanol, and condensation of benzaldehyde with ethylene glycol. More interestingly, MOMC-SO₃H catalyst is magnetically active, showing potential applications for separating catalysts by a magnetic field in the future.

Full text of DOI:10.1016/j.cattod.2011.11.011

Catalysis Today 186 (2012) 115–120
Contents lists available at SciVerse ScienceDirect
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
High-temperature synthesis of magnetically active and SO H-functionalized
3
ordered mesoporous carbon with good catalytic performance
b
c
a
c
c
a
b
Fujian Liu , Jing Sun , Qi Sun , Longfeng Zhu , Liang Wang , Xiangju Meng , Chenze Qi ,
a,∗
Feng-Shou Xiao
a
Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University (XiXi Campus), Tianmushan Road 148, Hangzhou 310028, China
Institute of Applied Chemistry, Shaoxing University, Shaoxing 312000, China
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 May 2011
Received in revised form 7 November 2011
Accepted 11 November 2011
Available online 9 January 2012
Magnetically active and SO H-functionalized ordered mesoporous resin and carbon (MOMR-SO H,
3
3
MOMC-SO3H) were successfully prepared by high-temperature hydrothermal synthesis from resol,
◦
copolymer surfactant, and iron cations at 180 C, followed by sulfonation from sulfuric acid fuming. X-ray
diffraction patterns show that MOMR-SO3H and MOMC-SO3H have ordered hexagonal mesoporous sym-
metry. N2 isotherms indicate that these samples have uniform and opened mesopores, high surface areas
2
3
(
335–591 m /g), and large pore volumes (0.34–0.35 cm /g). Transmission electron microscopy shows
Keywords:
Magnetically active
Ordered mesoporous carbon
Heterogeneous acidic catalysts
Catalyst recyclability
that iron nanoparticles, which are superparamagnetic in nature, are highly dispersed in MOMC-SO3H
sample. Catalytic tests show that MOMC-SO3H is highly active and excellently recyclable in esterification
of acetic acid with butanol, esterification of acetic acid with cyclohexanol, and condensation of benzalde-
hyde with ethylene glycol. More interestingly, MOMC-SO3H catalyst is magnetically active, showing
potential applications for separating catalysts by a magnetic field in the future.
©
2011 Elsevier B.V. All rights reserved.
1
. Introduction
applications [21]. To overcome this problem, porous resins and car-
bons with SO H groups have been prepared [22–28]. Particularly, it
3
The replacement of liquid acids by solid acids is greatly impor-
is worth mentioning that ordered porous resins and carbons could
be prepared from self-assembly routes recently [29–32].
tant for the production of fine chemicals recently owing to the
obvious advantages of simple separation of the catalysts from the
reaction media and significant reduction of environmental pollu-
tion [1–12].
Zeolites as typical solid acids have been widely applied due to
their high surface area, adjustable framework, and product shape-
selectivity [1]. However, the conversion of bulky molecules is not
easy in relatively small micropores of zeolites due to the difficulty
for access of these bulky molecules to the catalytically active sites
To increase activities, SO H-functionalized porous carbons are
3
usually used as fine powders in catalysis. However, the separa-
tion of the fine powders from catalytic systems is a challenge.
Recently, magnetically active composites have been successfully
synthesized [33–39], which offer an alternative route for separat-
ing fine powders by a magnetic field. Notably, magnetically active
nanocrystals of iron oxides are hydrothermally synthesized at the
◦
temperatures higher than 140 C [40], but conventional synthesis of
[
1
[
1,2]. Synthesis of ordered materials such as MCM-41 and SBA-
5 offers a totally new route to solve the limitation of micropores
13–15], but the amorphous nature of the mesoporous walls nor-
ordered mesoporous materials is generally fabricated at relatively
low temperatures (<140 C) [15].
◦
More recently, it is reported a successful high-temperature syn-
◦
mally has weak acidity [1,2]. To achieve strong acidic sites, SO H
thesis of ordered mesoporous resins at 150–260 C [41], which
3
groups have been functionalized on the surface of the mesoporous
walls [6,16–20], giving excellent catalytic properties in a series of
acid-catalyzed reactions. Notably, compared with zeolites, ordered
mesoporous materials including silicas and aluminosilicates have
relatively low hydrothermal stability, which strongly limit catalytic
shows a possibility for preparing magnetically active porous resins
and carbons. In this work, we show a high-temperature synthesis
of magnetically active and SO H-funcationalized ordered meso-
3
porous carbon (MOMC-SO H). Catalytic tests in esterification of
3
acetic acid with butanol, esterification of acetric acid with cyclohex-
anol, and condensation of benzaldehyde with ethylene glycol show
that MOMC-SO H has comparable activities and good recyclability,
3
compared with conventional solid acidic catalysts of Amberlyst 15
∗ Corresponding author.
E-mail addresses: fsxiao@zju.edu.cn, fsxiao@mail.jlu.edu.cn (F.-S. Xiao).
and SBA-15-SO H.
3
0
920-5861/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2011.11.011

1
16
F. Liu et al. / Catalysis Today 186 (2012) 115–120
-
Fe
2
O
3
*
1
00
-Fe
hkl
d (nm)
9.0
1
1
00
10
*
5.2
d
c
*
*
1
10
1
00
*
b
a
*
*
*
hkl
d (nm)
9.5
1
1
00
10
b
a
5.5
1
10
30
40
50
Theta (degree)
60
70
80
1
2
3
4
2
2
Theta (degree)
Fig. 2. Wide angle XRD patterns of (a) MOMR-100, (b) MOMR, (c) MOMR-SO3H, and
d) MOMC-SO3H.
Fig. 1. Small angle XRD patterns of (a) MOMR-SO3H and (b) MOMC-SO3H.
(
2
. Experimental
◦
38 wt.%). After heating at 70–80 C for 30–40 min, 20 mL of P123
(
2.1. Chemicals and preparation
(containing 1.75 g of P123) solution was added. After heating at
◦
8
0 C for 2 h, the mixture was cooled down to room tempera-
All reagents were analytical grade. Phenol, formaldehyde solu-
ture. Then, the mixture was added dropwise into 20 mL of aqueous
tion (38 wt.%), NaOH, ethanol, ferric chloride, ferrous sulfate,
sulfuric acid fuming, acetic acid, butanol, cyclohexanol, benzalde-
hyde, ethylene glycol and dodecane were obtained from Tianjin
Guangfu Chemical Company. P123 and Amberlyst 15 were pur-
chased from Sigma-Aldrich Company.
solution containing ferric chloride (FeCl ·6H O, 0.44 mmol) and
3
2
ferrous sulfate (FeSO ·7H O, 0.88 mmol) under vigorous stirring.
4
2
After further stirring for 30 min, the mixture was transferred to
◦
an autoclave. When the autoclave was treated at 180 C for 24 h, a
◦
black precipitate of MOMR was obtained. When heating at 600 C
Magentically active ordered mesoporous resin (MOMR) was
prepared from hydrothermal synthesis under basic conditions. As
for 2 h in flowing N for carbonization, magnetically active ordered
mesoporous carbon (MOMC) was obtained. Sulfonation of the sam-
ples was carried out in a Teflon-lined autoclave according to the
2
a typical run, 0.2 g of NaOH was dissolved in 10 mL of H O, fol-
2
lowed by addition of 2.0 g phenol and 7 mL formaldehyde solution
literature [23]. The SO H-functionalized MOMR and MOMC
3
A
1.6
1.4
B
3
3
2
2
2
1
1
60
20
80
40
00
60
20
b
a
1
1
0
0
0
0
0
.2
.0
.8
.6
.4
.2
.0
b
a
8
4
0
0
0.0
0.2
0.4
0.6
0.8
1.0
0
4
8
12
16
20
Relative pressure (p/p0)
Pore diameter (nm)
2
Fig. 3. (A) N2 isotherms and (B) pore size distributions of (a) MOMR-SO3H and (b) MOMC-SO3H. The isotherm for (b) was offset by 100 m /g along the vertical axis for clarity,
3
and the pore size distribution for (b) was offset by 1.0 cm /g along the vertical axis for clarity.

F. Liu et al. / Catalysis Today 186 (2012) 115–120
117
b
a
3
2
1
0
-1
-2
-3
-40000
-20000
0
20000
40000
H (Oe)
Fig. 5. Magnetization curves of (a) MOMR-SO3H and (b) MOMC-SO3H.
Fig. 4. TEM image of MOMC-SO3H viewed from (1 1 0) direction.
peak at 284.9 eV. Transmission electron microscopy (TEM) experi-
ments were performed on a JEM-3010 electron microscope (JEOL,
Japan) with an acceleration voltage of 300 kV.
samples were designated as MOMC-SO H and MOMR-SO H,
3
3
respectively.
.2. Characterization
X-ray diffraction (XRD) patterns were recorded on Rigaku
2
2.3. Catalytic reactions
Before catalytic reactions, all catalysts were activated by 0.1 M
D/Max-2550 (wide-angle XRD) and Siemens D5005 diffractome-
ter (small-angle XRD) using nickel-filtered Cu K␣ radiation. N2
isotherms were measured using a Micromeritics ASAP Tristar
system at the liquid nitrogen temperature. The samples were
H SO for 4 h at room temperature. Esterification of acetic acid with
2 4
butanol (EAB) and esterification of acetic acid with cyclohexanol
(EAC) as well as condensation of benzaldehyde with ethylene glycol
(CBE) were chosen as model reactions. EAB was carried out in a glass
◦
◦
outgassed for 10 h at 150 C before the measurements. The
flask under vigorous stirring at 90 C for 4 h with 0.01 g of catalyst,
pore-size distribution for mesopores was calculated using the
Barrett–Joyner–Halenda (BJH) model. The magnetization curves
were measured at 25 C under a varying magnetic field with a
Quantum Design MPMS-7 SQUID magnetometer. CHNS elemental
analysis was performed on a PerkinElmer series II CHNS analyzer
75 mmol of acetic acid, and 50 mmol of butanol. EAC was carried
out in a glass flask under vigorous stirring at 100 C for 5 h with
◦
◦
0.2 g of catalyst, 305 mmol of acetic acid, and 110 mmol of cyclo-
hexanol. CBE was carried out in a glass flask under vigorous stirring
◦
at 90 C for 1 h with 0.01 g of catalyst, 15 mmol of benzaldehyde,
2
400. XPS spectra were performed on a Thermo ESCALAB 250 with
and 15 mmol of ethylene glycol. The products in catalytic reac-
tions were analyzed by gas chromatography (Shimazu 14C) with a
Al K␣ radiation, and binding energies were calibrated using the C1s
Fig. 6. Photographs of MOMC-SO3H in ethanol without (a) and with (b) magnetic field.

1
18
F. Liu et al. / Catalysis Today 186 (2012) 115–120
a
C1s
b
1
69
O1s
Fe2p
S2p
800
700
600
500
400
300
200
100
174
172
170
168
166
Binding energy (eV)
Binding energy (eV)
c
284.7
d
712.3
725.7
286.8
290
288
286
284
282
280
740
730
720
710
700
Binding energy (eV)
Binding energy (eV)
Fig. 7. XPS measurements of (a) survey, (b) S2p, (c) C1s, (d) Fe2p spectra over MOMC-SO3H.
◦
flame ionization detector (FID), and dodecane was used as an inter-
nal standard. The column was OV-1 (30 m), the initial temperature
mesoporous resin synthesized at 100 C (MOMR-100), MOMR,
MOMR-SO H, and MOMC-SO H samples. Notably, there is no peak
in MOMR-100 sample (Fig. 2a), suggesting the absence of nanocrys-
tals of iron oxides. In contrast, the MOMR and MOMC-SO H samples
synthesized at 180 C (Fig. 2b and c) show obvious peaks associated
3
3
◦
◦
was 100 C, temperature rate was 20 C/min, final temperature was
◦
◦
2
20 C, and the temperature of FID detector was 280 C.
3
◦
with crystalline ␥-Fe O3 [34,36]. After carbonization, the MOMC-
3
. Results and discussion
2
SO H (Fig. 2d) shows additional peaks associated with ␣-Fe [33].
3
The presence of both crystalline ␥-Fe O3 and ␣-Fe is very helpful
for preparation of magnetically active composites.
3.1. Preparation and characterization
2
Fig. 3 shows N isotherms and pore size distributions of MOMR-
Fig. 1 shows small-angle XRD patterns of MOMR-SO H and
2
3
SO H and MOMC-SO H samples. They show a type-IV isotherm,
MOMC-SO H samples. Both exhibit two well-resolved peaks
3
3
3
giving a sharp capillary condensation step at P/P of 0.4–0.6, which
indexed as (1 0 0) and (1 1 0) reflections associated with 2-D
hexagonal symmetry (P6mm), indicating their good ordering
of mesostructure. Fig. 2 shows wide-angle XRD patterns of
0
is due to the presence of mesoporosity [13–15]. Correspondingly,
their pore sizes are distributed at 3.6 and 3.1 nm, respectively. The
Table 1
Textural parameters, sulfur content, and acidic concentration of various solid acid catalysts.
2
Dpa (nm)
3
S contentb (mmol/g)
Acid concentrationc (mmol/g)
Run
Samples
SBET (m /g)
Vp (cm /g)
1
2
3
4
5
6
MOMR-SO3H
MOMC-SO3H
Amberlyst 15
SBA-15-SO3H
335
591
45
820
364
623
3.6
3.1
40.0
7.3
0.55
14.7
0.35
0.34
0.31
1.40
0.16
0.26
1.42
0.85
4.30
1.26
–
1.56
0.91
4.70
1.36
–
d
ZSM-5
USYe
–
–
a
Pore size distribution estimated from BJH model.
Measured by elemental analysis.
Measured by acid-base titration.
Si/Al ratio at 40.
b
c
d
e
Si/Al ratio at 7.5.

F. Liu et al. / Catalysis Today 186 (2012) 115–120
119
pore volumes and BET surface areas of MOMR-SO H and MOMC-
3
3
2
SO H are 0.35 and 0.34 cm /g and 335 and 591 m /g, as summarized
3
b
a
in Table 1. In addition, their sulfur content and acidic concentra-
tion were also measured. MOMR-SO H and MOMC-SO H show the
acidic concentration at 1.56 and 0.91 mmol/g, respectively.
3
3
Fig. 4 shows a typical TEM image of MOMC-SO H viewed
3
from (1 1 0) direction. This image clearly shows not only a good
mesostructured ordering but also uniform nanoparticles of iron
species including ␥-Fe O3 and ␣-Fe in the carbon network. The
2
particle sizes of iron nanoparticles are mainly ranged at 20–40 nm.
Fig.
MOMR-SO H and MOMC-SO H, giving the saturation value at 2.28
5 shows room-temperature magnetization curves of
3
3
and 2.88 emu/g. These results suggest that both samples are mag-
netically active. Notably, MOMR-SO H has the lower value than
3
MOMC-SO H, which is related to the formation of ␣-Fe during car-
3
bonization of MOMR (Fig. 2). Furthermore, it is found that both
samples have not hysteresis loop, suggesting their superparamag-
1
800
1600
1400
1200
1000
800
600
-
1
netic property [36]. Fig. 6 shows photographs of MOMR-SO H in
Wavebumber (cm )
3
ethanol with or without magnetic field. When the magnetic field
is absent, the powders of MOMC-SO H are highly dispersed in the
Fig. 8. IR spectra of (a) MOMC-180 and (b) MOMC-SO3H.
3
solution. After introduction of a magnetic filed, the sample powders
are easily manipulated by a magnet.
Fig. 7 shows XPS measurement of MOMC-SO H, exhibiting the
of 5318, Run 2) is more active than SBA-15-SO3H (TON of 3316, Run
6) and Amberlyst 15 (TON of 959, Run 4). The higher activity over
MOMC-SO3H than over SBA-15-SO3H could be related to the differ-
ence in the mesoporous walls that the carbon is more hydrophobic
3
signals of S, C, O, and Fe. The S2p peak at 169.1 eV is assigned to S–O
bond, C1s peaks at 284.7 and 286.8 eV are associated with C–C and
C–S bonds, and Fe2p3/2 and Fe2p peaks at 725.7 and 712.3 eV are
1/2
mainly attributed to Fe3 species. Fig. 8 shows IR spectra of MOMC
+
than silica [24], and the higher activity over MOMC-SO H than
3
and MOMC-SO H samples. Interestingly, after sulfonation, MOMC-
over Amberlyst 15 is reasonably assigned to larger surface area of
3
−1
MOMC-SO H than of Amberlyst 15 (Table 1).
SO H shows additional band at 1032 cm , which is characteristic
3
3
of sulfonic groups in the sample [22]. Both XPS and IR results con-
firm that sulfonic groups have been successfully functionalized on
It is worth noting that MOMC-SO3H shows excellent recycla-
bility (Table 2, Run 3), compared with Amberlyst 15 (Run 5). For
example, in the EAB, after recycles for four times, the activity over
the surface of ordered mesoporous walls of MOMC-SO H.
3
MOMC-SO H is reduced from 96.8% to 92.4%, while the activity over
3
Amberlyst 15 is changed from 99.1% to 90.1% by the same recy-
cling; in the EAC, after recycles for four times, the activity over
3.2. Catalytic results
MOMC-SO H is reduced from 60.1% to 54.7%, while the activity
over Amberlyst 15 is changed from 59.7% to 35.2% by the same
recycling. These results suggest that the sulfonic groups of MOMC-
Table 2 presents catalytic data in esterification of acetic acid
with butanol (EAB), esterification of acetric acid with cyclohex-
anol (EAC), and condensation of benzaldehyde with ethylene glycol
3
SO H are more stable than those of Amberlyst 15 under the same
(
CBE). In these reactions, MOMC-SO H exhibits much higher activ-
3
3
reaction conditions. The analysis of the sample acidic concentration
ities than zeolites (ZSM-5 and USY) and SO H-functionalized on
3
shows MOMC-SO H shows that the S element are basically stable
mesoporous silica (SBA-15-SO H). Particularly, its activity is even
3
3
after recycles for 4 times (the S content at 0.85 and 0.80 mmol/g for
the fresh and recycled sample), in good agreement with those of
catalytic results in Table 2.
comparable that of Amberlyst 15, one of conventional acidic resins
with superior activities. For example, MOMC-SO H gives butanol
3
conversion at 96.8% in the EAC (Run 2), which is obviously higher
It is particularly emphasized that MOMC-SO H is magnetically
than SBA-15-SO H (90.2%, Run 6), ZSM-5 (68.4%, Run 7), and USY
3
3
active. The combination of high activity, good recyclability, and
magnetic movement together would be potentially important for
preparing efficient solid acid catalysts for industrial applications.
(
45.8%, Run 8). Because the quite distinguishable acidic sites over
various catalysts (Table 1), the turnover numbers of these catalysts
are calculated (Table 2). The results show that MOMC-SO H (TON
3
Table 2
Catalytic data in esterification of acetic acid with butanol (EAB), esterification of acetic acid with cyclohexanol (EAC), and condensation of benzaldehyde with ethylene glycol
CBE) over various solid acid catalysts.
(
Run
Catalysts
EABa
EACb
CBEc
Conv. (%)
TONd
Conv. (%)
TONd
218
363
331
70
Conv. (%)
TONd
1
2
3
4
5
6
7
8
MOMR-SO3H
MOMC-SO3H
MOMC-SO3He
Amberlyst 15
Amberlyst 15e
SBA-15-SO3H
ZSM-5
97.6
96.8
92.4
99.1
90.1
90.2
68.4
45.8
3128
5319
5077
1054
959
3316
8340
996
61.7
60.1
54.7
59.7
35.2
45.7
19.5
39.8
67.8
65.9
807
1086
64.2
207
41
185
255
95
46.7
43.9
39.1
515
1568
255
USY
a
The activities in EAB were evaluated by butanol conversion, and the product was butyl acetate with the selectivity higher than 99.9%.
b
c
The activities in EAC were evaluated by cyclohexanol conversion, and the product was cyclohexyl acetate with the selectivity higher than 99.9%.
The activities in CBE were evaluated by benzaldehyde conversion, and the product was 2-phenyl-1,3-dioxolane with the selectivity higher than 99.9%.
Number of converted reactant per acidic site in the catalysis.
d
e
Recycles for four times.

1
20
F. Liu et al. / Catalysis Today 186 (2012) 115–120
4
. Conclusions
Magnetically active and SO H-functionalized ordered meso-
[16] V. Dufaud, M. Davis, J. Am. Chem. Soc. 125 (2003) 9403–9413.
[
17] D. Margolese, J.A. Melero, S.C. Christiansen, B.F. Chmelka, G.D. Stucky, Chem.
Mater. 12 (2000) 2448–2459.
3
[18] I. Díaz, C. Márquez-Alvarez, F. Mohino, J. Pérez-Pariente, E. Sastre, J. Catal. 193
(2000) 283–294.
porous carbon (MOMC-SO H) has been hydrothermally synthe-
sized by self-assembly of resol with triblock polymer (P123) in the
presence of iron species at 180 C, followed by calcination in flowing
nitrogen at 600 C and sulfonation by fuming sulfuric acid. Catalytic
tests in esterification and condensation show that MOMC-SO H is
highly active and excellently recyclable. Particularly, the combina-
tion of superior catalytic performance with magnetic activity over
3
[
19] I. Díaz, C. Márquez-Alvarez, F. Mohino, J. Pérez-Pariente, E. Sastre, J. Catal. 193
2000) 295–302.
(
◦
[
20] Q.H. Yang, J. Liu, J. Yang, M.P. Kapoor, S. Inagaki, C. Li, J. Catal. 228 (2004)
265–272.
◦
[21] Z.T. Zhang, Y. Han, L. Zhu, R.W. Wang, Y. Yu, S.L. Qiu, D.Y. Zhao, F.-S. Xiao, Angew.
Chem. Int. Ed. 40 (2001) 1258–1262.
3
[
22] R. Xing, N. Liu, Y.M. Liu, H.H. Wu, Y.W. Jiang, L. Chen, M.Y. He, P. Wu, Adv. Funct.
Mater. 17 (2007) 2455–2461.
MOMC-SO H might open an alternative route for designing novel
solid acid catalysts for production of fine chemicals by green or
sustainable routes.
[23] F.-J. Liu, X.-J. Meng, Y.L. Zhang, L.M. Ren, F. Nawaz, F.-S. Xiao, J. Catal. 271 (2010)
2–58.
3
5
[
[
[
24] M. Hara, T. Yoshida, A. Takagaki, T. Takata, J.N. Kondo, S. Hayashi, K. Domen,
Angew. Chem. Int. Ed. 43 (2004) 2955–2958.
25] X.Q. Wang, R. Liu, M.M. Waje, Z.W. Chen, Y.S. Yan, K.N. Bozhilov, P.Y. Feng,
Chem. Mater. 19 (2007) 2395–2397.
26] R. Xing, Y.M. Liu, Y. Wang, L. Chen, H.H. Wu, Y.W. Jiang, M.Y. He, P. Wu, Micro-
porous Mesoporous Mater. 105 (2007) 41–48.
Acknowledgements
This work is supported by the State Basic Research Project of
China (2009CB623507) and National Natural Science Foundation
of China (20973079).
[27] Y.J. Xu, W.Q. Gu, D.L. Gin, J. Am. Chem. Soc. 126 (2004) 1616–1617.
[
[
[
[
28] J. Janaun, N. Ellis, Appl. Catal. A 394 (2011) 25–31.
29] C.D. Liang, Z.J. Li, S. Dai, Angew. Chem. Int. Ed. 47 (2008) 3696–3717.
30] C. Liang, S. Dai, J. Am. Chem. Soc. 128 (2006) 5316–5317.
31] Y. Meng, D. Gu, F.Q. Zhang, Y.F. Shi, H.F. Yang, Z. Li, C.Z. Yu, B. Tu, D.Y. Zhao,
Angew. Chem. Int. Ed. 44 (2005) 7053–7059.
References
[
[
[
[
32] F.Q. Zhang, Y. Meng, D. Gu, Y. Yan, C.Z. Yu, B. Tu, D.Y. Zhao, J. Am. Chem. Soc.
1
27 (2005) 13508–13509.
33] Z.H. Sun, L.F. Wang, P.P. Liu, S.C. Wang, B. Sun, D.Z. Jiang, F.-S. Xiao, Adv. Mater.
8 (2006) 1968–1971.
34] Y.P. Zhai, Y.Q. Dou, X.X. Liu, B. Tu, D.Y. Zhao, J. Mater. Chem. 19 (2009)
000–3292.
[
[
[
[
[
[
1] A. Corma, Chem. Rev. 97 (1997) 2373–2420.
2] M.E. Davis, Nature 417 (2002) 813–821.
3] J.H. Clark, D.J. Macquarrie, Chem. Soc. Rev. 25 (1996) 303–310.
4] A. Corma, Chem. Rev. 95 (1995) 559.
5] T. Okuhara, Chem. Rev. 102 (2002) 3641–3666.
6] J.A. Melero, G.D. Stucky, R.V. Griekena, G. Morales, J. Mater. Chem. 12 (2002)
1
3
35] A.H. Lu, W. Schmidt, N. Matoussevitch, H. B oˇ nnemann, B. Spliethoff, B. Tesche,
E. Bill, W. Kiefer, F. Schüth, Angew. Chem. Int. Ed. 43 (2004) 4303–4306.
36] W. Zhao, J. Gu, L. Zhang, H. Chen, J. Shi, J. Am. Chem. Soc. 127 (2005) 8916–8917.
37] Y. Li, H.Y. Tan, X.Y. Yang, B. Goris, J. Verbeeck, S. Bals, P. Colson, R. Cloots, G.
Tendeloo, B.L. Su, Small 7 (2011) 475–483.
1
664–1670.
[
[
[7] M.A. Harmer, Q. Sun, Catal. Appl. A 275 (2004) 247–255.
[8] J.A. Dias, J.P. Osegovic, R.S. Drago, J. Catal. 183 (1999) 83–90.
[9] G. Busca, Chem. Rev. 107 (2007) 5366–5410.
[
[
[
[
38] R. Xiang, G.H. Luo, W.Z. Qian, Q. Zhang, Y. Wang, F. Wei, Q. Li, A.Y. Cao, Adv.
Mater. 19 (2007) 2360–2363.
39] W. Chen, X.L. Pan, M.G. Willinger, D.S. Su, X.H. Bao, J. Am. Chem. Soc. 128 (2006)
[
[
[
10] T. Welton, Chem. Rev. 99 (1999) 2071–2083.
11] A. Corma, H. Garcia, Chem. Rev. 103 (2003) 4307–4365.
12] Y.X. Wei, Y.L. He, D.Z. Zhang, L. Xu, S.H. Meng, Z.M. Liu, B.L. Su, Microporous
Mesoporous Mater. 90 (2006) 188–197.
3136–3137.
40] M.H. Cao, T.F. Liu, S. Gao, G.B. Sun, X.L. Wu, C.W. Hu, Z.L. Wang, Angew. Chem.
Int. Ed. 44 (2005) 4197–4201.
41] F.J. Liu, C.J. Li, L.M. Ren, X.J. Meng, H. Zhang, F.-S. Xiao, J. Mater. Chem. 19 (2009)
[
[
[
13] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
7
10–712.
14] D.Y. Zhao, J.L. Feng, Q.S. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D.
Stucky, Science 279 (1998) 548–552.
15] D.Y. Zhao, Q.S. Huo, J.L. Feng, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 120
7921–7928.
(
1998) 6024–6036.