Dry gel conversion method for the synthesis of organic-inorganic hybrid MOR zeolites with modifiable catalytic activities

Article abstract of DOI:10.1021/cm3023538

Dry gel conversion (DGC) technique is first applied in the synthesis of organic-inorganic hybrid aluminosilicate zeolites. By using the DGC method, methylene-bridged organic-inorganic hybrid zeolites with an MOR topology are synthesized without organic additive, which are structurally characterized by powder XRD, FTIR, solid-state ²⁹Si, ¹³C, ²⁷Al MAS NMR, SEM, elemental analysis, XRF, XPS, and N₂ adsorption techniques. This work first reports that thus-synthesized methylene-bridged hybrid zeolites can be successfully bestowed with excellent catalytic activities through different modification treatments. Co²⁺-exchanged hybrid zeolites are applied in the epoxidation of alkenes with air to achieve good conversions and selectivities. Especially, methylene-bridged hybrid zeolites can be sulfonated with fuming sulfuric acid to form acidic MOR-SO₃H catalyst, which exhibits highly catalytic activity for the acid-catalyzed condensation reaction of cyclohexanone and glycol. This method will be one potential route for the fabrication of organic-inorganic hybrid zeolite or related molecular sieve catalysts.

Full text of DOI:10.1021/cm3023538

Article
pubs.acs.org/cm
Dry Gel Conversion Method for the Synthesis of Organic−Inorganic
Hybrid MOR Zeolites with Modifiable Catalytic Activities
†
†
‡
†
§
‡
,†
Dan Zhou, Xinhuan Lu, Jun Xu, Anan Yu, Jiyang Li, Feng Deng, and Qinghua Xia*
†Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei University, Wuhan
30062, P.R. China
4
‡
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Center for Magnetic Resonance, Wuhan
Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P.R. China
§
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012,
P.R. China
*
S Supporting Information
ABSTRACT: Dry gel conversion (DGC) technique is first
applied in the synthesis of organic−inorganic hybrid
aluminosilicate zeolites. By using the DGC method,
methylene-bridged organic−inorganic hybrid zeolites with an
MOR topology are synthesized without organic additive,
which are structurally characterized by powder XRD, FTIR,
29
13
27
solid-state Si, C, Al MAS NMR, SEM, elemental analysis,
XRF, XPS, and N adsorption techniques. This work first
2
reports that thus-synthesized methylene-bridged hybrid zeolites can be successfully bestowed with excellent catalytic activities
2
+
through different modification treatments. Co -exchanged hybrid zeolites are applied in the epoxidation of alkenes with air to
achieve good conversions and selectivities. Especially, methylene-bridged hybrid zeolites can be sulfonated with fuming sulfuric
acid to form acidic MOR-SO H catalyst, which exhibits highly catalytic activity for the acid-catalyzed condensation reaction of
3
cyclohexanone and glycol. This method will be one potential route for the fabrication of organic−inorganic hybrid zeolite or
related molecular sieve catalysts.
KEYWORDS: DGC method, organic−inorganic hybrid zeolite, heterogeneous catalysis, acid catalysis, epoxidation of alkenes,
hybrid mordenite
1
. INTRODUCTION
of organic Si−C bonds, hence resulting in a low content of
organic groups in the inorganic frameworks. Second, it is
almost an impossible mission to remove the organic template
molecules completely by chemical extraction or by calcination
in vacuum from the microporous channels of organic−
inorganic hybrid zeolites while maintaining the integrity of
organic−inorganic hybrid zeolite frameworks. For example, the
Organic−inorganic hybrid zeolites are one type of new
microporous crystalline materials, which are bestowed with
unique structural features and properties by incorporating
1
−9
organic groups into the frameworks of inorganic zeolites.
These crystalline materials have attracted great attention due to
the potential applications in the fields of catalysis and
separation, hopefully extending the application scope of
conventional inorganic zeolites.
Generally, organic−inorganic hybrid zeolites are prepared by
hydrothermal method. In 1998, Davis et al. first reported the
synthesis of β zeolite functionalized with organic groups hung
on the walls, which was sulfonated and used in the
condensation of cyclohexanone and glycol. In 2003, Tatsumi
et al. successfully synthesizd organic−inorganic hybrid zeolites
containing methylene groups as the lattice, which presented
good property for the selective adsorption. However, up to
date, only one report has approached the catalytic application
chemical extraction with CH OH/HCl solution or with
3
supercritical fluid is proven to be an effective method for the
removal of >95% organic surfactant molecules from the
mesopores of periodic mesoporous organosilica (PMO)
11
materials, which, however, can merely remove a little part
1
(
< / ) of the organic template molecules from the micropores
3
12
2
of zeolites inclusive of organic−inorganic hybrid zeolites. The
other alternative method to remove the organic template
molecules is by calcination in vacuum at high temperature
3
(
usually >350 °C), which can partially decompose organic
template molecules occluded in the microporous channels, but
will definitely destroy the majority of organic groups
10
of organic−inorganic hybrid zeolite, which may be related to
two unresolved problems. First, the syntheses of organic−
inorganic hybrid aluminosilicate zeolites containing methylene
groups as the lattice are usually performed in the strong basic
hydrothermal environments, which readily lead to the cleavage
Received: July 26, 2012
Revised: October 17, 2012
Published: October 17, 2012
©
2012 American Chemical Society
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Scheme 1. Preparation Process and Catalytic Application of Methylene-Bridged MOR Hybrid Materials
incorporated into the lattice of organic−inorganic hybrid
zeolites simultaneously. In 2007, a relatively complicated
methodology to prepare organic−inorganic hybrid zeolite
through the silylation of layered zeolitic precursor was
373 K overnight. The yield of the product was higher than 95 wt %
based on the silicon source.
MOR-2 was synthesized by using a mixture of BTESM and fumed
silica as silicon source. Typically, solution A was prepared by dissolving
1
3
0.083 g NaAlO and 0.092 g NaOH in deionized water, followed by
2
developed, by which IEZ-1 with a CDO topology was
eventually synthesized. The dilemma in the synthesis of
organic−inorganic hybrid zeolites has become a hindrance for
the extensive and deep studies of this kind of materials.
Dry gel conversion (DGC) method, allowing the trans-
formation of dry gel powder to zeolite crystals at high yield in
the presence of steam, has been regarded as a useful preparative
the addition of 1.393 g BTESM. The mixture was vigorously stirred at
room temperature for 3−4 h to complete the hydrolysis of
organosilanes. Solution B was prepared by dissolving 0.055 g
NaAlO2 and 0.067 g NaOH in deionized water, followed by the
addition of 0.49 g fumed silica at room temperature. Then, solution A
was added into solution B under stirring, and heated to 353 K in a
water bath until it turned into dry gel with the water content of ca.
0.130 g. The final gel with a molar composition of 1.0 Al O :5.8
1
4,15
technique for zeolites and related materials.
In the present
2
3
work, the DGC method is first applied in the synthesis of
organic−inorganic hybrid microporous aluminosilicate zeolite
containing methylene groups as the lattice. By using
bis(triethoxysilyl) methane (BTESM) or the mixture of
BTESM and fumed silica as the silicon source, methylene-
bridged organic−inorganic hybrid zeolites with an MOR
BTESM:11.5 SiO :3.7 Na O:10.2 H O was ground into fine powder
2 2 2
and crystallized at 453 K for 3−5 days by using the above apparatus
and procedure. The yield of the product was higher than 94 wt %
based on the silicon source. Inorganic mordenite was synthesized by
the DGC route using fumed silica as the silicon source as reported in
1
7
the literature.
.1.3. Preparation of Co -Exchanged Organic−Inorganic Hybrid
2+
2+
2
(
mordenite) topology (MOR-1 and MOR-2) are synthesized
Zeolite Catalyst. The Co cations were introduced into as-
18
in the absence of organic additive. It is noteworthy that thus-
synthesized methylene-bridged hybrid zeolites can be bestowed
with modifiable catalytic activities and directly applied in the
heterogeneous catalytic reactions. However, previous research-
ers could think that methylene-hybridized zeolite frameworks
were inert and could not be functionalized further. The
preparation process and catalytic applications of methylene-
bridged MOR hybrid materials are illustrated in Scheme 1.
synthesized hybrid materials by conventional ion-exchange method.
Typically, 5.0 g of methylene-bridged MOR was treated at 363 K
overnight with an aqueous solution (250 mL) containing 1.3 mmol of
Co(Ac) ·4H O. The solid powder was recovered by filtration, washed
2 2
several times with hot distilled water until no acidic residue was
detected, and followed by drying at 373 K for 8 h.
2
.1.4. Sulfonation of As-Synthesized Hybrid Material. The
sulfonation of as-synthesized hybrid materials was conducted
1
1
according to the method in the literature. Typically, 1.003 g of
MOR-1 was added into 10 mL of fuming sulfuric acid (30% SO3/
H SO ) and kept continuous stirring at 298 K for 2 h, then at 323 K
2. EXPERIMENTAL SECTION
2
4
for 2 h, and finally at 373 K for 4 h. After the suspension was cooled
down to room temperature, a large volume of water was added for
dilution. The solid was recovered by filtration, washed repeatedly with
boiling water until the pH value of the filtrate became neutral, and
dried at 353 K for 14 h in vacuum.
2
.1. Synthesis. 2.1.1. Synthesis of BTESM. BTESM was prepared
16
by the method reported in the literature, and the structure and purity
1
13
(
−
(
>98%) were determined by H and C NMR measurements (δ =
0.02 (s, 2H, CH ), δ = 3.82−3.86 (m, 12H, OCH ), δ = 1.20−1.24
2
2
m, 18H, CH ); δ = −7.80 (s, C, CH ), δ = 58.27−58.34 (m, 6C,
3
2
2.2. Catalytic Reactions. 2.2.1. Catalytic Epoxidation of Alkenes
OCH ), δ = 17.97−18.12 (m, 6C, CH ).
2
3
with Air. The catalytic epoxidation of alkenes with air was run on the
basis of the conditions: solvent, DMF (10 g); alkenes (styrene and α-
pinene), 3 mmol; initiator, TBHP (0.3 mmol); catalyst, 0.1 g; reaction
time, 5 h; temperature, 363 K; flow rate of air, 40 mL/min. The
reaction mixture was quantitatively analyzed by GC 9710A equipped
with an FID detector and an SE-30 capillary column (30 m × 0.25 mm
×0.25 μm), in which chlorobenzene was used as an internal standard.
The conversion and selectivity was calculated accordingly.
2
.1.2. Synthesis of Organic−Inorganic Hybrid Materials. MOR-1
was synthesized by using BTESM as unique silicon source. Typically,
.113 g NaAlO (84.2 wt %) and 0.132 g NaOH (96.0 wt %) were
0
2
dissolved in deionized water, followed by the addition of 2.013 g
BTESM. The mixture was stirred at room temperature for 3−4 h to
complete the hydrolysis of organosilanes and heated to 353 K in a
water bath until it turned into dry gel with the water content of ca.
0
.125 g. The final dry gel with a molar composition of 1.0 Al O :10.2
2 3
BTESM:3.7 Na O:12 H O was ground into fine powder and
2.2.2. Acid-Catalyzed Condensation of Cyclohexanone and
Glycol. The catalytic reaction was carried out in a 25 mL two necked
glass reactor equipped with a cryogenic-liquid condenser under
atmospheric pressure. In a typical run, 0.200 g catalyst, 7.445 g glycol,
and 7.850 g cyclohexanone were mixed and kept at 373 K for 10−180
min under stirring. The reaction mixture was quantitatively analyzed
by GC 9710A to achieve the yield of ketal product. The solid catalyst
2
2
transferred into a 30 mL Teflon beaker, which was placed in the
middle of a 130 mL stainless steel autoclave with 10 mL of deionized
water poured into the bottom of the autoclave as the steam source (as
shown in Scheme 1). The autoclave was sealed and crystallized at 453
K for 3−5 days under static conditions. The products were recovered
by filtration, washed with deionized water several times, and dried at
4
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Chemistry of Materials
Article
was recovered by filtration, washed several times with hot distilled
water, and dried at 373 K overnight for the next use.
2
.3. Characterization. Powder X-ray diffraction was performed on
a Rigaku D/MAX-IIIC diffractometer with Cu Kα radiation (λ =
.5406 Å) operating at 30 kV and 25 mA. Fourier transform infrared
FTIR) spectra were recorded on a PE2400 Fourier transform infrared
1
(
spectrophotometer. All solid-state NMR spectral experiments were
carried out at 9.4 T on a Varian Infinityplus-400 spectrometer,
equipped with a Chemagnetic triple-resonance 7.5 mm probe, with
1
13
resonance frequencies of 400.13, 100.6, and 79.5 MHz for H, C, and
2
9
Si, respectively. The magic angle spinning rate was set to 3−5 kHz.
1
13
For the H− C CP/MAS NMR experiments, the Hartmann−Hahn
condition was achieved using hexamethylbenzene (HMB), with a
contact time of 2.0 ms and a repetition time of 2.0 s. 29Si single pulse
experiments were performed with a 4.6 μs pulse width (π/2) and a 100
1
s recycle delay, and H decoupling with radio frequency (RF) field
strength of 35 kHz was applied during the acquisition period. The
chemical shifts of 13C, Si, and Al were referenced to HMB,
29
27
tetramethyl silane (TMS), and 1 M Al(NO ) solutions, respectively.
3
3
Elemental analyses were conducted on a vario MICRO elemental
analyzer. X-ray fluorescence (XRF) analyses (Si, Al, and Co) were
obtained on a Shimadzu XRF-1800 spectrometer. N2 adsorption/
desorption isotherms were determined by Autosorb-1 at 77.35 K. The
BET specific surface area was calculated using the BET equation in the
range of relative pressures (p/p ) between 0.05 and 0.25. The
0
morphology of crystals was observed by using a JSM6510LV scanning
electron microscope (SEM) operating at 30.0 kV. X-ray photoelectron
spectroscopy (XPS) data were acquired on a Thermol ESCALAB-250
system using Al Kα monochromatic radiation (1486.6 eV).
Figure 2. FTIR spectra of as-synthesized hybrid materials MOR-1,
MOR-2, and inorg-MOR.
the asymmetric and symmetric C−H stretching vibrations of
3. RESULTS AND DISCUSSION
3
methylene (CH ) fragments, which cannot be observed in the
2
The powder XRD patterns of as-synthesized materials are
shown in Figure 1. Obviously, all the reflection peaks are in
good agreement with those of inorganic mordenite zeolite
FTIR spectrum of inorg-MOR. The weak peaks at 2970 and
2880 cm− are attributed to trace amount of methyl groups
(CH ) originating from the cleavage of the Si−CH −Si linkage
1
3
2
(
inorg-MOR), indicating the framework type and the phase
purity.
In the FTIR spectra of MOR-1 and MOR-2 (Figure 2), two
during the hydrolysis and crystallization process.
Solid-state 29Si single pulse MAS NMR measurements were
conducted to determine the chemical environments of Si atoms
in the hybrid materials (Figure 3). The resonance peaks around
−1
clear peaks appearing at 2938 and 2862 cm are assigned to
Figure 3. Solid-state 29Si single pulse MAS NMR spectra of as-
synthesized methylene-bridged hybrid materials MOR-1, MOR-2, and
inorg-MOR.
Figure 1. Powder XRD patterns of as-synthesized hybrid materials
MOR-1, MOR-2, and inorg-MOR.
4
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Chemistry of Materials
66 ppm are contributed by T-type silicon species bonded
Article
−
3
covalently to the carbon atoms. The resonance peaks located
at ca. −102 to −110 ppm are attributable to inorganic Q-type
silicon species. According to the integrated intensity ratios of
different Si chemical environments calculated by the
deconvolution of the spectra with Gaussian lines, the ratios of
organic T-type and inorganic Q-type silicon species for MOR-1
and MOR-2 are 1:6.23 and 1:10.3, respectively. Apparently, the
introduction of many more T-type silicon species in MOR-1
than in MOR-2 is due to the use of purely organic BTESM as
silicon source in the synthesis of MOR-1. The Q-type silicon
species in MOR-1 originates totally from the cleavage of Si−
CH −Si linkage, while that in MOR-2 is contributed by both
2
the cleaved Si−CH −Si bonds and inorganic fumed silica.
2
1
13
The solid-state H− C CP/MAS NMR spectra (Figure 4,
left) of MOR-1 and MOR-2 exhibit one resonance peak around
Figure 5. SEM images of MOR-1, MOR-2, and inorg-MOR.
Supporting Information Figure S1, typical of microporous
solids. According to the elemental analysis results in Table 1,
the carbon content of MOR-1 (4.1 wt %) is higher than that of
MOR-2 (2.7 wt %), consistent with the results of solid-state
29
Si single pulse MAS NMR.
Our recent work has reported that Co -exchanged zeolites
present good catalytic activity and selectivity for the
Figure 4. Solid-state H− C CP (left) and 27Al (right) MAS NMR
spectra of as-synthesized methylene-bridged hybrid materials MOR-1
and MOR-2.
1
13
2+
17
epoxidation of alkenes with air. In order to test the ion-
exchangeability and catalytic activity of as-synthesized methyl-
ene-bridged hybrid zeolite, hybrid MOR-1 is ion-exchanged by
−
5 ppm, which is assignable to the carbon species bonded
directly to silicon atoms, indicative of the presence of organic−
inorganic hybrid structure. Al MAS NMR spectra of two
2+
Co cations and used in the epoxidation of styrene and α-
2
7
pinene with air (Table 3). According to the XRF analysis, the
2+
hybrid materials present only one kind of AlO chemical
contents of Co species in the Co -exchanged MOR-1 and
inorg-MOR samples are 2.98 and 4.75 wt %, respectively. The
4
environment located at about 55 ppm (Figure 4, right). SEM
images exhibit irregular morphologies of as-synthesized hybrid
materials, different from uniform crystals of inorg-MOR
shown in Figure 5).
Table 1 summarizes the synthesis conditions and physical
properties of various methylene-bridged hybrid zeolites
reported in the literature and in this work. It is clearly shown
that the C content in MOR-1 (this work) crystallized in a short
time of only 3 days is a little higher than those of other hybrid
materials synthesized by a conventional hydrothermal method,
which generally requires a long time for the crystallization,
indicative of the effectiveness of the synthesis route by DGC
method.
2+
majority of Co species in the Co -exchanged samples exists in
the form of Co2+ cations, as characterized by the appearance of
only one peak with the binding energy of ca. 782 eV in the X-
(
2
+
ray photoelectron spectra, which is characteristic of Co -
1
9−21
2+
exchanged zeolites.
The conversions over hybrid Co -
MOR-1 are 89.2 mol % for styrene and 74.9 mol % for α-
pinene, comparable to 90.1 mol % for styrene and 75.7 mol %
2+
for α-pinene achieved over inorganic Co -inorg-MOR. The
2+
epoxidation selectivities over hybrid Co -MOR-1 are 89.4% for
styrene and 87.4% for α-pinene.
Very importantly, thus-synthesized methylene-bridged hybrid
zeolite can be directly sulfonated and applied in the acid-
catalyzed condensation of cyclohexanone and glycol. The
powder XRD pattern and FTIR spectrum of sulfonated MOR-1
On the basis of the XRF analysis, the Si/Al ratios of MOR-1
and MOR-2 are calculated and listed in Table 2. BET surface
areas of organic−inorganic hybrid MOR zeolites were
(MOR-SO H) are shown in Figure 6. After being sulfonated by
3
2
determined to be 198.0 and 210.1 m /g, slightly lower than
fuming sulfuric acid, the MOR framework is still preserved, and
2
−1
2
49.3 m /g of purely inorganic mordenite, which reflects the
the peak emerging at 1080 cm in the FTIR spectrum can be
negative impact of Si−CH −Si substituting for lattice Si−O−Si
attributed to the symmetric stretching vibration of OSO.
As compared with the FTIR spectrum of inorg-MOR, two clear
splitting peaks at around 800 cm− may be attributable to the
symmetric stretching vibrations induced by the sulfonation. As
2
on the microporous adsorption surface areas of thus-
1
synthesized materials. Type-I N adsorption/desorption iso-
2
therms of MOR-1 and MOR-2 at 77.35 K are shown in
4
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Table 1. Synthesis Conditions and Physical Properties of Various Methylene-Bridged Hybrid Zeolites Reported in the
Literature and in This Work
a
b
sample
dry gel composition (molar ratio)
1.0Al O :10.2BTESM: 3.7Na O:12H O
T (K) time (days)
phase
C content (wt %)
ref
MOR-1
453
453
413
463
373
413
423
423
413
413
366
366
3
MOR
MOR
MFI
MFI
LTA
BEA
MFI
MFI
BEA
BEA
FAU
FAU
4.1
2.7
1.9
3.2
2.2
2.7
2.0
3.6
2.0
4.9
1.3
1.5
this work
2
3
2
2
a
MOR-2
ZOL-2
ZOL-5
ZOL-A
ZOL-B
1.0Al O :5.8BTESM:11.5SiO :3.7Na O:10.2H O
3
this work
2
3
2
2
2
1.0BTESM:0.5TEMABr:0.26Na O:40H O
20
7
3
3
3
3
8
8
8
8
9
9
2
2
1.0Al O :27.8BTESM:2.33Na O:3222H O
2
3
2
2
1.0Al O :0.96BTESM:3.15Na O:127.9H O
14
21
7
2
3
2
2
1.0TEOS:0.5BTESM:1.08TEAF:15.3H O
2
a
ZSM-5
ZSM-5
1.0BTESM:4.0SiO :2.5TPAOH:2.5HF:35H O
2 2
a
1.0BTESM:1.0SiO :1.0TPAOH:1.0HF:14H O
26
31
60
13
13
2
2
a
β
a
1.0BTESM:4.0SiO :2.5TPAOH:2.5HF:35H O
2 2
β
1.0BTESM:1.0SiO :1.0TPAOH:1.0HF:14H O
2 2
ZOF-1
ZOF-9
1.0Al O :7.7−8BTESM:4.96−5.32Na O:0.46−0.48K O:101.5−105.5H O
2 3 2 2 2
1.0Al O :6−6.44BTESM:4.2−4.6Na O:0.36−0.39K O:80.2−85.4H O
2
3
2
2
2
a
b
SiO represents inorganic silicon source. Elemental analysis results.
2
Table 2. Physical Properties of As-Synthesized Hybrid
Materials MOR-1, MOR-2, and inorg-MOR
2
a
sample
BET surface area (m /g)
Si/Al ratios
MOR-1
198.0
210.1
249.3
8.8
MOR-2
11.7
10.3
inorg-MOR
a
XRF analysis.
Table 3. Catalytic Epoxidation of Styrene and α-Pinene with
Air
styrene
α-pinene
catalyst
conversion
selectivity
conversion
selectivity
2
+
Co -MOR-1
89.2
90.1
89.4
85.4
74.9
75.7
87.4
85.3
2+
Co -inorg-MOR
Figure 7. Comparison of different catalysts for the condensation
reaction of cyclohexanone and glycol.
Information Figure S2, the pyridine-adsorption IR spectrum
shows that the sulfonated hybrid MOR-1 contains strong
Bro
̈
nsted acid and weak Lewis acid. The recycling studies
(
Figure 8) show the reusability of the catalyst MOR-SO H as a
3
Figure 6. Powder XRD patterns and FTIR spectra of MOR-1 and
sulfonated MOR-1.
expected, for the condensation reaction of cyclohexanone and
glycol, the MOR-SO H catalyst shows excellent catalytic
3
activity (with the yield of 71.6 mol %), much higher than
+
those of H -MOR and the blank reaction (depicted in Figure
7
), which clearly shows the advantage of sulfonated hybrid
MOR as the acid catalyst. As illustrated in Supporting
Figure 8. Recycling studies of MOR-SO H catalyst.
3
4
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Chemistry of Materials
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heterogeneous catalyst, in which six recycles of this catalyst did
not appreciably decrease the yield of ketal, indicating that the
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3
(
MOR-1. The in-depth investigations on the further applications
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4
(
(
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(
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methylene-bridged mordenite zeolite in the absence of organic
additive by the DGC method, which will be one potential route
for the fabrication of other organic−inorganic hybrid zeolite or
related molecular sieve catalysts. More importantly, as-
synthesized methylene-bridged mordenite can be bestowed
with modifiable catalytic activities and applied in the
heterogeneous catalytic reactions.
1
(
(
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(
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ASSOCIATED CONTENT
■
20) Verberckmoes, A. A.; Weckhuysen, B. M.; Schoonheydt, R. A.
*
S
Supporting Information
N adsorption/desorption isotherms and pyridine-adsorption
IR spectrum of sulfonated hybrid MOR-1. This material is
available free of charge via the Internet at http://pubs.acs.org.
Microporous Mesopoprous Mater. 1998, 22, 165−178.
(21) Gutierrez, L.; Mirο
2008, 114, 281−292.
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, E.; Irusta, S. Microporous Mesoporous Mater.
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AUTHOR INFORMATION
■
*
Corresponding Author
E-mail: xiaqh518@yahoo.com.cn. Phone: +86-27-50865387.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (20901023, 21173073, 21273064), the
project sponsored by SRF for ROCS, SEM of China ([2009]
1
001), the Chen Guang Scheme for Young Scientists of Wuhan
City (201050231087).
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