Synthesis of cyclic carbonates and dimethyl carbonate using CO2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K2CO 3

Article abstract of DOI:10.1007/s11458-011-0225-x

The synthesis of cyclic carbonates or dimethyl carbonate (DMC) using CO₂ as a building block is a very interesting topic. In this work, we found that the metalorganic framework-5 (MOF-5)/KI was an active and a selective catalytic system for the synthesis of cyclic carbonates from CO ₂ and epoxides, and MOF-5/KI/K₂CO₃ was efficient for the preparation of DMC from CO₂, propylene, and methanol by a sequential route. The impacts of temperature, pressure, and reaction time length on the reactions were investigated, and the mechanism of the reactions is proposed on the basis of the experimental results.

Full text of DOI:10.1007/s11458-011-0225-x

Front. Chem. China 2011, 6(1): 21–30
DOI 10.1007/s11458-011-0225-x
RESEARCH ARTICLE
monoxide is used, which, however, is a hazardous gas.
Therefore, the development of green and safe processes for
the DMC production has been an interesting topic.
Synthesis of cyclic
In recent years, the development of green processes to
prepare DMC based on utilizing carbon dioxide (CO2) has
received much attention because CO2 is an abundant carbon
resource and a greenhouse gas and can be used as a safe and
cheap C1 building block to produce useful organic
compounds as well as a nontoxic reaction media [6–8].
There are mainly two routes for the synthesis of DMC using
CO2. The first is by means of the reaction of methanol and
CO2 [9–16]. The yield of DMC in this route is low because of
the thermodynamic limitations of the reaction. The second
route is through the two-step transesterification process
(Fig. 2). However, the main drawback of this process is that
separation of the cyclic carbonates is required. It is attractive
to integrate the coupling reaction of CO2 with epoxides and
the transesterification of cyclic carbonate with methanol into a
one-pot reaction, and some catalysts have been prepared for
the one-pot reaction [17–23]. Unfortunately, the one-pot
method could produce large amounts of by-products from the
alcoholysis of epoxides (Fig. 3). Therefore, the development
of new routes synthesizing DMC from CO2 is desirable.
Recently, a simple route, in which the coupling reaction and
the transesterification reaction took place in sequence, has
been developed by He et al. This route can avoid the
alcoholysis of epoxides and get a higher DMC yield [24]. The
development of effective catalytic systems is crucial for this
route.
carbonates and dimethyl
carbonate using CO2 as a
building block catalyzed by
MOF-5/KI and MOF-5/KI/
K2CO3
Jinliang SONG, Binbin ZHANG, Tao JIANG,
Guanying YANG and Buxing HAN (✉)
The synthesis of cyclic carbonates or dimethyl carbo-
nate (DMC) using CO2 as a building block is a very
interesting topic. In this work, we found that the metal-
organic framework-5 (MOF-5)/KI was an active and a
selective catalytic system for the synthesis of cyclic
carbonates from CO2 and epoxides, and MOF-5/KI/
K2CO3 was efficient for the preparation of DMC from
CO2, propylene, and methanol by a sequential route.
The impacts of temperature, pressure, and reaction
time length on the reactions were investigated, and the
mechanism of the reactions is proposed on the basis of
the experimental results.
In recent years, metal-organic frameworks (MOFs), which
were formed by copolymerization of organic molecules with
metal ions or metal ion clusters, have received much attention
because of their zeolite-like properties, such as high internal
surface area and microporosity, well-ordered porous struc-
tures, and high absorption capacity [25–29]. Various applica-
tions of MOFs, such as gas storage [30–32] and separation
[33,34], have been studied. Applications of MOFs in catalysis
have also been explored [35–47]. However, the exploration of
their applications in different reactions is yet interesting.
MOF-5 [Zn4O(BDC)3, BDC = benzene-1,4-dicarboxylate]
is a commonly used MOF. In this work, we studied the
catalytic performance of MOF-5/KI/K2CO3 system for the
synthesis of DMC from CO2, propylene oxide, and methanol
by a sequential route. It was demonstrated that the catalyst
system could effectively catalyze both the coupling reaction
of CO2 with epoxides to the corresponding cyclic carbonates
and the transesterification reaction of propylene carbonate
with methanol to DMC and propylene glycol, achieving a
high yield of DMC. We believe that this simple and cheap
route to synthesize DMC has a great potential in industrial
application.
Keywords carbon dioxide, cyclic carbonates, dimethyl
carbonate (DMC), metal-organic framework-5 (MOF-5),
sequential route, propylene oxide
1 Introduction
Dimethyl carbonate (DMC) has attracted much interest as an
excellent solvent, a promising gasoline octane enhancer,
nontoxic carbonylation and methylation reagent in place of
virulent phosgene and dimethyl sulfate, and precursor for
polycarbonate resins [1–3]. DMC can be synthesized on an
industrial scale by the phosgene process or by the oxidative
carbonylation of methanol process (Fig. 1) [4,5]. Because
phosgene is highly toxic and the by-product HCl causes
serious corrosion, the phosgene process is gradually out of
use. For the oxidative carbonylation process, carbon
Received November 3, 2010; accepted December 6, 2010
Beijing National Laboratory for Molecular Sciences, Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, China
E-mail: Hanbx@iccas.ac.cn
©Higher Education Press and Springer-Verlag Berlin Heidelberg 2011

22
Jinliang SONG, Binbin ZHANG, Tao JIANG, Guanying YANG and Buxing HAN
Figure 1 The phosgene process (1) and the oxidative carbonylation process (2).
Figure 2 The two-step transesterification process.
Figure 3 The alcoholysis of epoxides.
infrared (FTIR) spectra were determined using a Bruker
Tensor 27 spectrometer, and the sample was prepared by KBr
pellet method.
2 Experimental
2.1 Material and apparatus
CO2 was supplied by Beijing Analytical Instrument Factory
with a purity of 99.99%. Propylene oxide (PO), methanol,
epichlorohydrin, Zn(NO3)$6H2O, KI, KCl, KBr, K2CO3,
ZnO, and triethylamine that were of analytical grade were
provided by Beijing Chemical Reagents Company. Benzene-
1, 4-dicarboxylic acid was of analytical grade and was
provided by Aldrich Chemical Company. Other epoxides
were purchased from ACROS ORGANICS. All chemicals
were used as received.
Thermogravimetric (TG) analysis of MOF-5 was per-
formed on NETZSCH STA 409 PC/PG thermogravimetric
analysis system in N2 atmosphere at a heating rate of
20°C$min–1. The X-ray diffraction (XRD) patterns were
collected on an X-ray diffractometer (D/MAX-RC) operated
at 40 kVand 200 mA with Cu Kα radiation. Fourier transform
2.2 Preparation of MOF-5
The procedures to prepare MOF-5 were similar to that
reported in Ref. [48]. Briefly, Zn(NO3)$6H2O (1.21 g,
4 mmol), benzene-1,4-dicarboxylic acid (0.32 g, 2 mmol),
and 40 mL N,N-dimethylformamide were added into a
100-mL flask equipped with a magnetic stirrer. The flask
was put into an oil bath at 60°C. Then, triethylamine (1.6 g)
were added into the mixture. The mixture was maintained at
60°C for 4 h with stirring. The formed MOF-5 was collected
by filtration, washed using N, N-dimethylformamide, and
then dried at 60°C for 12 h under a vacuum. X-ray diffraction
patterns, thermograms, and FTIR spectra of the MOF-5
prepared in this work agree well with those reported by other
authors [48].
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

Synthesis of cyclic carbonates and DMC using CO2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K2CO3
23
2.3 Typical procedures for DMC synthesis from propylene
oxide, CO2,and methanol
In a typical reaction, the cycloaddition reaction of CO2 and
propylene oxide was conducted in a 22 mL stainless steel
reactor equipped with a magnetic stirrer. In the reaction,
propylene oxide (20 mmol), 0.5 mmol KI, 0.5 mmol K2CO3,
and 0.1 g MOF-5 were added into the reactor. After it was
sealed, the reactor was put into a constant-temperature air bath
of 90°C. CO2 was then charged into the reactor to a pressure
of 4 MPa, and the stirrer was started. After a reaction time of
2 h, the reactor was placed into ice water, and the excess CO2
was released slowly. After that, 200 mmol methanol was
added into the reactor, and the reactor was placed into a
constant-temperature air bath of 130°C. The transesterifica-
tion reaction was carried out for 2 h. When the reactor was
cooled to room temperature, n-butanol was added into the
reactor as an internal standard. The reaction mixture was
analyzed by GC (Agilent 6820) equipped with a flame-ionized
detector and further identified by GC–MS.
3 Results and discussion
3.1 Catalyst characterization
The powder XRD pattern of the MOF-5 is given in Fig. 4,
which agreed perfectly with the result reported by Huang et al.
[48]. MOF-5 has good thermal stability, as can be learned
from the thermogram shown in Fig. 5. The weight loss below
280°C resulted from the occluded solvent DMF and water.
MOF-5 began to decompose above 380°C, which is much
higher than the reaction temperatures of the cycloaddition
reaction (90°C) and the transesterification reaction (130°C).
The FTIR spectrum of the MOF is provided in Fig. 6. IR
spectra show the expected strong characteristic adsorptions
for the symmetric and asymmetric vibrations of BDC
(1610 – 1550 cm–1and 1420 – 1335 cm–1) and adsorbed water
(3500 – 3200 cm–1). There were no absorptions of protonated
BDC (1715 – 1680 cm–1), which confirmed complete depro-
tonation of H2BDC by TEA in MOF-5.
Figure 5 Thermogram of MOF-5.
3.2 Cycloaddition of CO2 with epoxides
First, the activity of different catalysts was tested using the
reaction of PO and CO2 to produce propylene carbonate (PC),
and the results are summarized in Table 1. When we used only
KI as a catalyst, the yield of PC was low (entry 1). MOF-5
itself was not active (entry 2). In the presence of various
potassium salts, MOF-5 could catalyze the coupling reaction,
and MOF-5/KI was the most effective (entries 3–7). The
different activity of various catalyst systems could result from
Figure 6 FTIR spectra of MOF-5.
the nucleophilicity and leaving ability of the counter-anion of
different potassium salts. In addition, it can be observed that
MOF-5 has a higher activity than ZnO, and the reason may be
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

24
Jinliang SONG, Binbin ZHANG, Tao JIANG, Guanying YANG and Buxing HAN
Table 1 Coupling of CO2 and propylene oxide catalyzed by different
catalystsa)
entry
c)
catalyst
KI
yield/%
0.1
0
1
b)
2
MOF-5
b)
3
MOF-5 + KOH
MOF-5 + K2CO3
MOF-5 + KCl
MOF-5 + KBr
MOF-5 + KI
0.1
0.1
0.2
1.2
98
b)
4
b)
5
b)
6
b)
7
b)
8
ZnO + KI
5
d)
9
MOF-5 + KI + K2CO3
MOF-5(2nd) + KI(fresh)
MOF-5(3rd) + KI(fresh)
98
10
11
98
98
Figure 7 The effect of CO2 pressure on PC yield. Reaction
conditions were 20 mmol PO with 2.5 mol% KI, 0.1 g MOF-5,
reaction temperature 90°C, and reaction time 2 h.
a) Typical reaction conditions were a stainless autoclave of 22 mL,
20 mmol PO with 2.5 mol% catalyst, CO2 pressure 6 MPa, reaction
temperature 90°C, and reaction time 2 h.
b) 0.1 g MOF-5 or ZnO was added.
c) Yields were determined by GC versus an internal standard.
d) The amount of K2CO3 added was 2.5 mol%.
the temperature at CO2 pressure of 6 MPa within the
temperature range of 60°C–110°C, and the reaction lasted
for 2 h. It was shown that the activity of the catalyst was
strongly affected by the reaction temperature. The yield of PC
increased with increasing temperature, and it reached 98% at
90°C. Then, the PC yield was kept almost constant with the
further increase of the temperature, hinting that 90°C is the
optimal temperature for the reaction under our reaction
conditions.
that MOF-5 is a porous material with high surface area [48],
which makes for the access of reactants to the active sites
(Zn4O) of MOF-5. To examine the effect of K2CO3 on the
coupling reaction catalyzed by MOF-5/KI, we used MOF-5/
KI/K2CO3 to conduct the cycloaddition of CO2 and PO (entry
9). The result showed that K2CO3 did not affect the activity of
MOF-5/KI.
The reusability of the MOF-5 was also studied at the
reaction condition used in entry 7, and the results are also
summarized in Table 1 (entries 10, 11). Obviously, the activity
and selectivity of the MOF-5 remained after reusing for three
times.
The pressure of CO2 is an important reaction parameter for
the coupling reaction of CO2 with epoxides. To study the
effect of CO2 pressure on PC yield, the reaction was
conducted with MOF-5/KI catalyst system at 90°C within
the pressure range of 2–12 MPa for 2 h, and the results are
shown in Fig. 7. It can be learned in Fig. 7 that CO2 pressure
had little effect on the PC yield at low CO2 pressure (2–
6 MPa), and then, the yield of the PC decreased with the
pressure increase (from 6 MPa to 12 MPa). The main reason
for this may be that MOF-5 is a good absorbent, and
concentrations of PO and CO2 in the vicinity of the catalyst
were high enough at low pressure. However, more PO was
extracted into the CO2-rich phase at higher pressures because
the solvent power of CO2 increases with pressure, which
Figure 8 The effect of reaction temperature on PC yield.
Reaction conditions were 20 mmol PO with 2.5 mol% KI, 0.1 g
MOF-5, CO2 pressure 6 MPa, and reaction time 2 h.
The influence of reaction time on PC yield is given in
reduced the concentration of PO in the vicinity of the catalyst. Fig. 9. The coupling reaction was conducted at 90°C and
Therefore, the yield decreased with increasing pressure at 6 MPa of CO2. It can be seen in Fig. 6 that the conversion of
higher pressures.
PO was incomplete, and the PC yield was low at short reaction
Figure 8 demonstrates the dependence of the yield of PC on time. The yield of PC could reach 98% at 2 h. No obvious
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

Synthesis of cyclic carbonates and DMC using CO2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K2CO3
25
increase in the PC yield was observed with prolonged reaction required a longer time (4 h) for obtaining high yield (94%) of
time, indicating that the reaction time of 2 h was suitable for the desired product, which may result from the reduced
our catalyst system.
electron density of the epoxide oxygen atom caused by the
Under the catalyst system of MOF-5/KI, coupling reactions electron-withdrawing CH2Cl group. A much longer reaction
of CO2 with different epoxides (Fig. 10) were also studied at time (7 h) was needed to get a high product yield (95%) when
6 MPa without using any solvent, and the results are styrene oxide (Table 2, Entry 3) was used as substrate, which
summarized in Table 2. The results showed that the catalyst is probably due to the low reactivity of its β-carbon center.
system was active for all epoxides studied. PO (Table 1, entry Among the substrates used, cyclohexene oxide (Table 2,
7) and glycidyl phenyl ether (Table 2, Entry 1) were the most Entry 4) showed the lowest activity for coupling with CO2
active substrates and yielded a large amount of the among the substrates used. Only 20% yield of product was
corresponding cyclic carbonates in a short reaction time. achieved when the reaction was carried out at 90°C for 24 h.
Epichlorohydrin (Table 2, Entry 2) showed less activity and The poor reactivity results mainly from the high steric
hindrance.
Based on the results discussed above, we propose a
plausible mechanism for this chemical fixation reaction
(Fig. 11). The coupling reaction is initiated by coordination
of Zn4O clusters in MOF-5 as a Lewis acidic site with the
oxygen atom of epoxide. Second, the I– generated from KI
attacks the less-hindered carbon atom of the coordinated
epoxides, followed by ring opening step. Then, the interaction
occurred between the oxygen anion of the opened epoxy ring
Figure 9 The influence of reaction time on PC yield. Reaction
conditions were 20 mmol PO with 2.5 mol% KI, 0.1 g MOF-5,
CO2 pressure 6 MPa, and reaction temperature 90°C.
Figure 10 Coupling of CO2 with different epoxides.
Table 2 Various carbonates synthesis catalyzed by MOF-5 in the presence of KI a)
entry
1
epoxides
products
time/h
2
yield/%
97
1b
1c
2b
2c
2
4
94
3
4
7
95
20
1d
1e
2d
2e
24
a) Reaction conditions were epoxide 20 mmol with 2.5 mol% KI, 0.1 g MOF-5, CO2 pressure 6 MPa, and reaction temperature 90°C.
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

26
Jinliang SONG, Binbin ZHANG, Tao JIANG, Guanying YANG and Buxing HAN
and CO2, and this can form an alkylcarbonate anion, which is K2CO3 system is shown in Fig. 12. The yields of DMC and
converted into the corresponding cyclic carbonate through the propylene glycol (PG) increased with increasing reaction time
ring close step.
in the beginning and became constant after 2 h. This implies
that the transesterification reaction reached an equilibrium
after 2 h under the reaction conditions. We also studied the
effect of reaction temperature on the DMC and PG yields, and
the results are shown in Fig. 13. As reaction temperature was
increased, the DMC and PG yields increased within the
temperature range studied.
The molar ratio of methanol to PC is an important reaction
parameter as transesterification is a reversible reaction. The
yield of the reaction at different methanol to PC molar ratios is
summarized in Table 4. As expected, the yield increased with
increasing methanol to PC ratio.
3.3 Transesterification of PC with methanol
Transesterification of cyclic carbonate with methanol, the
second step reaction in Fig. 2, is one of the important routes to
produce DMC. We examined the activity of various catalysts
for the reaction of PC with methanol, and the results are
summarized in Table 3. All the catalyst systems with K2CO3
showed good activity. We chose the MOF-5/K2CO3 system to
study the influence of other conditions on DMC yield. The
effect of reaction time on the DMC yield using MOF-5/
Figure 11 A plausible reaction mechanism for the coupling reaction of CO2 with epoxide catalyzed by MOF-5 and KI.
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

Synthesis of cyclic carbonates and DMC using CO2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K2CO3
27
Table 3 Transesterification of PC and methanola)
b)
entry
catalyst
PC conversion/%
yield/%
DMC
17
PG
17
63
16
7
c)
1
c)
2
d)
3
KI
K2CO3
17
63
16
7
60
MOF-5
15
c), d)
4
MOF-5 + KI
MOF-5 + K2CO3
MOF-5 + K2CO3 + KI
6
c), d)
5
c), d)
6
64
63
60
63
62
60
a) The typical reaction conditions were a stainless autoclave of 22 mL, 20 mmol PC, 0.2 mol methanol, reaction temperature 130°C, and reaction time
2 h.
b) Yields were determined by GC versus an internal standard.
c) 2.5 mol% KI or/and K2CO3 was added.
d) The amount of MOF-5 was 0.1 g.
Figure 12 Influence of reaction time on the transesterification
reaction of PC and methanol. Reaction conditions are 20 mmol PC
with 2.5 mol% K2CO3, 200 mmol methanol, 0.1 g MOF-5, and
reaction temperature 130°C.
Figure 13 Influence of reaction time on the transesterification
reaction of PC and methanol. Reaction conditions are 20 mmol PC
with 2.5 mol% K2CO3, 200 mmol methanol, 0.1 g MOF-5, and
reaction time 2 h.
coupling reaction CO2 and propylene oxide catalyzed by
MOF-5/KI. Then, the formed PC reacted with methanol in the
presence of K2CO3 to form DMC.
3.4 DMC synthesis from CO2, propylene oxide and
methanol by a sequential route
To select a suitable route for our catalyst system MOF-5/KI/
K2CO3, we conducted the reaction under various routes, and
the results are shown in Table 5. The one-pot route (entries 1–
7) produced a large amount of by-products, and the DMC
yield was low. When the reaction was conducted under a
sequential route (Fig. 14), there were no by-products
produced, and the DMC yield was high (entry 8).
4 Conclusion
MOF-5/KI system could catalyze the cycloaddition of CO2
and PO to produce PC effectively, and a yield of 98% can be
achieved at 90°C within the pressure range of 2–6 MPa with a
reaction time of 2 h. The catalytic system is also efficient for
the cycloaddition of CO2 and epoxides, and high yields can be
obtained under suitable conditions. MOF-5/KI/K2CO3 system
is efficient for the preparation of DMC from CO2, propylene,
and methanol by a sequential route, and the selectivity for the
desired products can be 100% under suitable conditions. We
believed that the highly efficient catalytic systems have a
3.5 Reaction mechanism by a sequential route
Based on the above results, we proposed a plausible
mechanism for the DMC synthesis by a sequential route
(Fig. 15). First, propylene carbonate was formed from the
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

28
Jinliang SONG, Binbin ZHANG, Tao JIANG, Guanying YANG and Buxing HAN
Table 4 The effect of molar ratio of methanol to PC on the yield of DMC and PGa)
b)
entry
molar ratio of methanol to PC
PC conversion/%
yield/%
DMC
43
PG
45
63
68
76
1
2
3
4
5
47
64
71
76
10
15
20
60
67
75
a) Typical reaction conditions were a stainless autoclave of 22 mL, 4.9 wt% MOF-5 of PC, 2.5 mol% K2CO3, reaction temperature 130°C, and
reaction time 2 h.
b) Yields were determined by GC versus an internal standard.
Figure 14 DMC synthesis from CO2, propylene oxide, and methanol by a sequential route.
Table 5 Different reaction routes
a)
b)
entry
yields/%
PC
94
93
90
89
70
71
85
40
PG
0.3
DMC
0.4
5 + 6
3
c), d)
c), e)
c), f)
c), g)
c), h)
c), i)
j)
1
2
3
4
5
6
7
8
1.3
1.1
3.4
3.5
3.7
9.8
4.4
3.3
0
2.5
2.6
5.0
5.5
17.3
22.4
10
15.3
21.3
9.8
k)
57.6
57
a) All reactions were conducted under the conditions as follows: a stainless autoclave of 22 mL, 2.5 mol% K2CO3, 2.5 mol% KI, and CO2 pressure
4 MPa.
b) Yields were determined by GC versus an internal standard.
c) The conditions used were 0.05 g MOF-5, reaction time 4 h, 10 mmol PO, and 100 mmol CH3OH.
d) Reaction temperature was 90°C.
e) Reaction temperature was 100°C.
f) Reaction temperature was 110°C.
g) Reaction temperature was 120°C.
h) Reaction temperature was 130°C.
i) Reaction temperature was 140°C.
j) The conditions used were 0.05 g MOF-5, 10 mmol PO, 100 mmol CH3OH, 2 h at 90°C, and then 2 h at 130°C.
k) The conditions used were 0.1 g MOF-5, 20 mmol PO and 2 h at 90°C, and after depressurization, 200 mmol CH3OH was added into the autoclave
and then reacted at 130°C for 2 h.
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

Synthesis of cyclic carbonates and DMC using CO2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K2CO3
29
Figure 15 A plausible reaction mechanism by a sequential route.
2001, 3, 87–91
potential application in the synthesis of the corresponding
chemicals.
15. Choi, J. C.; Sakakura, T.; Sako, T., J. Am. Chem. Soc. 1999, 121,
3793–3794
Acknowledgements The authors are grateful to the National
Natural Science Foundation of China (Nos. 21003133 and
20932002), Ministry of Science and Technology of China (Grant
No. 2009CB930802), and Chinese Academy of Sciences (Grant No.
KJCX2.YW.H16).
16. Ikeda, Y.; Sakaihori, T.; Tomishige, K.; Fujimoto, K., Catal.
Lett. 2000, 66, 59–62
17. Kishimoto, Y.; Ogawa, I., Ind. Eng. Chem. Res. 2004, 43, 8155–
8162
18. Bhanage, B. M.; Fujita, S. I.; Ikushima, Y.; Torii, K.; Arai, M.,
Green Chem. 2003, 5, 71–75
19. Cui, H. Y.; Wang, T.; Wang, F. J.; Gu, C. R.; Wang, P. L.; Dai, Y.
Y., Ind. Eng. Chem. Res. 2003, 42, 3865–3870
20. Chang, Y. H.; Jiang, T.; Han, B. X.; Liu, Z. M.; Wu, W. Z.; Gao,
L.; Li, J. C.; Gao, H. X.; Zhao, G. Y.; Huang, J., Appl. Catal. A
Gen. 2004, 263, 179–186
References
1. Tundo, P., Pure Appl. Chem. 2001, 73, 1117–1124
2. Tundo, P.; Selva, M., Acc. Chem. Res. 2002, 35, 706–716
3. Pacheco, M. A.; Marshall, C. L., Energy Fuels 1997, 11, 2–
29
21. Bhanage, B. M.; Fujita, S. I.; Ikushima, Y.; Arai, M., Appl.
Catal. A Gen. 2001, 219, 259–266
4. Romano, U.; Tesei, R.; Mauri, M. M.; Rebora, P., Ind. Eng.
Chem. Prod. Res. Dev. 1980, 19, 396–403
5. King, S. T., Catal. Today 1997, 33, 173–182
22. Li, Y.; Zhao, X. Q.; Wang, Y. J., Appl. Catal. A Gen. 2005, 279,
205–208
23. Jagtap, S. R.; Bhor, M. D.; Bhanage, B. M., Catal. Commun.
2008, 9, 1928–1931
6. Sakakura, T.; Choi, J. C.; Yasuda, H., Chem. Rev. 2007, 107,
2365–2387
24. Tian, J. S.; Miao, C. X.; Wang, J. Q.; Cai, F.; Du, Y.; Zhao, Y.;
He, L. N., Green Chem. 2007, 9, 566–571
25. Moulton, B.; Zaworotko, M. J., Chem. Rev. 2001, 101, 1629–
1658
7. Song, C. S., Catal. Today 2006, 115, 2–32
8. Gibson, D. H., Chem. Rev. 1996, 96, 2063–2096
9. Fang, S.; Fujimoto, K., Appl. Catal. A Gen. 1996, 142, L1–L3
26. Kitagawa, S.; Kitaura, R.; Noro, S., Angew. Chem. Int. Ed. 2004,
43, 2334–2375
10. Tomishige, K.; Sakaihori, S.; Ikeda, Y.; Fujimoto, K., Catal.
Lett. 1999, 58, 225–229
27. Wang, Z.; Cohen, S. M., J. Am. Chem. Soc. 2007, 129, 12368–
12369
11. Choi, J. C.; He, L. N.; Yasuda, H.; Sakakura, T., Green Chem.
2002, 4, 230–234
28. Song, Y. F.; Cronin, L., Angew. Chem. Int. Ed. 2008, 47, 4635–
4637
12. Sakakura, T.; Saito, Y.; Okano, M.; Choi, J. C.; Sako, T., J. Org.
Chem. 1998, 63, 7095–7096
29. Natarajan, S.; Mandal, S., Angew. Chem. Int. Ed. 2008, 47,
4798–4828
13. Sakakura, T.; Choi, J. C.; Saito, Y.; Masuda, T.; Sako, T.;
Oriyama, T., J. Org. Chem. 1999, 64, 4506–4508
14. Fujita, S.; Bhanage, B. M.; Ikushima, Y.; Arai, M., Green Chem.
30. Li, Y.; Yang, R. T., Langmuir 2007, 23, 12937–12944
Frontiers of Chemistry in China Vol. 6, No. 1, 2011

30
Jinliang SONG, Binbin ZHANG, Tao JIANG, Guanying YANG and Buxing HAN
31. Morris, R. E.; Wheatley, P. S., Angew. Chem. Int. Ed. 2008, 47, 40. Wu, C. D.; Hu, A.; Zhang, L.; Lin, W., J. Am. Chem. Soc. 2005,
4966–4981
127, 8940–8941
32. Zlotea, C.; Campesi, R.; Cuevas, F.; Leroy, E.; Dibandjo, P.; 41. Xamena, F. X. L. i.; Casanova, O.; Tailleyr, R. G.; Garcia, H.;
Volkringer, C.; Loiseau, T.; Férey, G.; Latroche, M., J. Am.
Chem. Soc. 2010, 132, 2991–2997
Corma, A., J. Catal. 2008, 255, 220–227
42. Dewa, T.; Saiki, T.; Aoyama, Y., J. Am. Chem. Soc. 2001, 123,
502–503
33. Chen, B.; Liang, C.; Yang, J.; Contreras, D. S.; Clancy, Y. L.;
Lobkovsky, E. B.; Yaghi, O. M.; Dai, S., Angew. Chem. Int. Ed.
2006, 45, 1390–1393
43. Hasegawa, S.; Horike, S.; Matsuda, R.; Furukawa, S.;
Mochizuki, K.; Kinoshita, Y.; Kitagawa, S., J. Am. Chem. Soc.
2007, 129, 2607–2614
34. Procopio, E. Q.; Linares, F.; Montoro, C.; Colombo, V.;
Maspero, A.; Barea, E.; Navarro, J. A. R., Angew. Chem. Int.
Ed. 2010, 49, 1–5
44. Horcajada, P.; Surblé, S.; Serre, C.; Hong, D. Y.; Seo, Y. K.;
Chang, J. S.; Grenéche, J. M.; Margiolaki, I.; Férey, G., Chem.
Comm. 2007, 2820–2822
35. Lor, B. G.; Puebla, G.; Iglesias, M.; Monge, M. A.; Valero, C.
R.; Snejko, N., Chem. Mater. 2005, 17, 2568–2573
36. Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim,
K., Nature 2000, 404, 982–986
45. Liu, H.; Liu, Y.; Li, Y.; Tang, Z.; Jiang, H., J. Phys. Chem. C
2010, 114, 13362–13369
46. Park, Y. K.; Choi, S. B.; Nam, H. J.; Jung, D. Y.; Ahn, H. C.;
Choi, K.; Furukawa, H.; Kim, J., Chem. Commun. 2010, 46,
3086–3088
37. Pan, L.; Liu, H.; Lei, X.; Huang, X.; Olson, D. H.; Turro, N. J.;
Li, J., Angew. Chem. Int. Ed. 2003, 42, 542–546
38. Alaerts, L.; Séguin, E.; Poelman, H.; Thibault-Starzyk, F.; 47. Leus, K.; Muylaert, I.; Vandichel, M.; Marin, G. B.; Waroquier,
Jacobs, P. A.; De Vos, D. E., Chemistry 2006, 12, 7353–7363
M.; Van Speybroeck, V.; Van der Voort, P., Chem. Commun.
2010, 46, 5085–5087
39. Gándara, F.; Gomez-Lor, B.; Gutiérrez-Puebla, E.; Iglesias, M.;
Monge, M. A.; Proserpio, D. M.; Snejko, N., Chem. Mater. 48. Huang, L.; Wang, H.; Chen, J.; Wang, Z.; Sun, J.; Zhao, D.; Yan,
2008, 20, 72–76 Y., Microporous Mesoporous Mater. 2003, 58, 105–114
Frontiers of Chemistry in China Vol. 6, No. 1, 2011