Applied Catalysis A: General 519 (2016) 146154

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Carboxymethyl cellulose supported ionic liquid as a heterogeneous

catalyst for the cycloaddition of CO2 to cyclic carbonate
Xiaohui Wu a , Mengpan Wang a , Yinzheng Xie a , Chen Chen a , Kun Li a , Mingming Yuan a ,
Xiuge Zhao a , Zhenshan Hou a,b,
a
b

Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China
Department of Chemical and Environmental Engineering, Xinjiang Institute of Engineering, Urumqi 830011, China

a r t i c l e

i n f o

Article history:
Received 21 January 2016
Received in revised form 1 April 2016
Accepted 3 April 2016
Available online 4 April 2016
Keywords:
Carboxymethyl cellulose
Ionic liquid
Heterogeneous catalysts
CO2
Cyclic carbonate

a b s t r a c t
The non-toxic biologic material carboxymethyl cellulose (CMC) supported imidazolium-based ionic
liquids (ILs), coupling with a series of Lewis acids has been prepared and used as heterogeneous
catalysts for the cycloaddition of CO2 to cyclic carbonate. The as-synthesized catalysts have been characterized by FT-IR, XRD, TGA, SEM etc. Especially, the protonated CMC (HCMC) supporting both the
hydroxyl group functionalized IL (1-hydroxypropyl-3-n-butylimidazolium chloride, HBimCl) and NbCl5
(HBimCl-NbCl5 /HCMC) exhibited the best catalytic performance. It was indicated that HBimCl on HBimClNbCl5 /HCMC catalyst was highly leaching-resistant even if it was immobilized through non-covalent
interaction. The IL and Lewis acid exhibited strong synergistic effects for the cycloaddition reaction.
Additionally, the HBimCl-NbCl5 /HCMC catalyst exhibited a high activity and excellent selectivity for a
wide scope of substrates under optimum conditions and also it was further extended to application in
the continuous xed-bed ow reactor and showed an excellent catalytic stability. No loss of catalytic
activity was observed even after 120 h on stream.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Carbon dioxide (CO2 ) is an easily available renewable carbon
resource, which has the advantages of being abundant, cheap, nontoxic, and nonammable in organic synthesis [13]. Incorporation
of CO2 into carbonates is a signicant transformation because of its
potential implications for climate change reduction and the associated economic benets [4]. Particularly, the ve-membered cyclic
carbonates are one of the most attractive synthetic protocols utilizing CO2 as shown in Scheme 1 [5,6]. These products are widely
used as monomers, aprotic polar solvents, and as intermediates in
the manufacture of ne chemicals [7,8].
Catalysts have been developed to activate CO2 for cycloaddition
in the past decades owing to its inertness [9,10]. A number of homogeneous catalysts have been reported for the synthesis of cyclic
carbonates recently, such as alkali metal or transition metal-based

Corresponding author at: Department of Chemical and Environmental Engineering, Xinjiang Institute of Engineering, Urumqi 830011, China.
E-mail addresses: wuxh2013@163.com (X. Wu), wmp2014@126.com
(M. Wang), xieyzh2013@163.com (Y. Xie), 642913643@qq.com (C. Chen),
Y30141035@mail.ecust.edu.cn (K. Li), ymmsilence@163.com (M. Yuan),
zhaoxg@ecust.edu.cn (X. Zhao), houzhenshan@ecust.edu.cn (Z. Hou).
http://dx.doi.org/10.1016/j.apcata.2016.04.002
0926-860X/ 2016 Elsevier B.V. All rights reserved.

binary systems [1113], salen complex [14,15] and ILs [1619]

etc. Among these homogeneous catalysts, ILs have attracted great
attention especially because it owns outstanding properties, like
negligible vapor pressure, good chemical and thermal stability and
tunable structure [20]. However, homogeneous catalysts have the
defects that can not be ignored. For example, it is very hard to separate homogeneous catalyst from products, resulting in the difculty
for further product purication.
Heterogeneous catalysts can avoid these problems to some
extent. Naturally, a series of inorganic or organic support immobilizing IL catalysts have been developed. These supports include
mesoporous silica [2123], polymers [24,25], graphene oxide [26],
carbon nanotubes [27], etc. It is worth noting that the presence of
hydroxyl groups on solid materials could effectively promote the
cycloaddition reaction of epoxides with CO2 . Although the great
advances of these heterogeneous catalysts have been made, it is
denitely essential to develop more effectively heterogeneous catalysts with excellent activity and catalytic stability for the xation
CO2 under mild conditions. Cellulose and related biopolymers are
becoming more and more attractive recently for their excellent
properties such as non-toxicity, biocompatibility, biodegradability, non-toxicity, natural abundance and have been employed as
supporting materials for CO2 cycloaddition [2830]. For examples,

X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

147

2.2. Preparation of catalyst

Scheme 1. The synthesis of cyclic carbonate from CO2 and epoxides.

Roshan et al. [28] immobilized imidazolium-based ionic liquids on

carboxymethyl cellulose via a co-dispersing method and examined the catalytic activity in the cycloaddition of carbon dioxide
with oxides, demonstrating the synergistic role among the carboxyl moieties, the hydroxyl groups and the anions of the ionic
liquid counterparts. However, the deactivation of catalyst has been
observed after recycled 4 times. Sun et al. [29] have prepared chitosan (CS) covalently-grafted 1-ethyl-3-methyl imidazolium halide
catalysts, which exhibited good activity and selectivity for the reaction with relatively high IL loading. In addition, Tharun et al. [30]
have employed quaternized chitosan (QCHT) as a heterogeneous
catalyst for the CO2 cycloaddition. The catalyst displayed only moderate activity and gradual deactivation in catalytic recycles. All
these catalysts above have been operated under the batch-wise
condition.
On the other hand, although the promising results have been
achieved in the batch-wise process, the continuous xed-bed
mode is more preferable from the point of view of the industrial
application. In this aspect, Sakakuras group demonstrated that
phosphonium halides covalently bound to SiO2 exhibited excellent catalytic activities for CO2 cyclicaddition and was proved to be
reacted for 1000 h under xed bed operation condition [31]. However, the synthetic procedures of the catalysts were complicated
and the reaction condition was harsh. Hence, it is highly promising
to exploit a highly efcient and easily available catalyst which is
applicable for a xed-bed ow reactor under mild conditions.
As we have discussion above, the sodium salt of carboxymethyl
cellulose (CMC) is a widely applied material in industry because of
its excellent green properties [32]. The protonated CMC (HCMC) is
a derivative of the cellulose family with the carboxymethyl group
( CH2 COOH) bound, which equipped with abundance hydroxyl
groups. In this work, we attempted to immobilize imidazoliumbased ILs and Lewis acids on HCMC via a noncovalent linkage to
prepare various heterogeneous catalysts. It was found that the combination of the hydroxyl group functionalized imidazolium IL and
NbCl5 showed excellent activity and reusability in the cycloaddition
of CO2 with propylene oxide under mild and solvent free conditions.
In addition, the present catalyst can be employed in a continuous xed-bed ow reactor, where the catalyst showed promising
catalytic performance for 120 h on stream.

2.2.1. Preparation of 1- hydroxypropyl-3-n-butylimidazolium

chloride (HBimCl)
1-Buthylimidazole (1.69 g, 13.6 mmol) and 3-chloro-1-propanol
(1.29 g, 13.6 mmol) were mixed and stirred at 100 C for 20 h in
50 ml stainless autoclave equipped with a magnetic stirrer under
N2 atmosphere. The resulting mixture was washed 34 times with
ethyl acetate to remove unreacted impurities. Then product was
transferred to 50 ml glass bottle and dried at 70 C under vacuum
for 2 h to obtain slightly yellow and viscous liquid as HBimCl. The 1 H
NMR spectra was shown in Fig. 1S. 1 H NMR (400 MHZ, CDCl3 ):0.84
(t, 3H), 1.26 (m, 2H), 1.79 (M, 2H), 2.00 (m, 2H), 3.48 (m, 2H), 4.21
(t, 2H), 4.43 (t, 2H), 4.76 (s, 1H), 7.44 (t, 1H), 7.76 (t, 1H), 10.11 (s,
1H).
2.2.2. Preparation of 1, 3-dibutyl imidazolium chloride (DBimCl)
1-Buthylimidazole (1.69 g, 13.6 mmol) and 1-chlorobutane
(1.30 g, 13.6 mmol) were mixed and stirred at 100 C for 20 h in
50 ml stainless autoclave equipped with a magnetic stirrer under
N2 atmosphere. The resulting mixture was washed 34 times with
ethyl acetate to remove unreacted impurities. The product was
transferred to 50 ml glass bottle, following by drying at 70 C under
the vacuum for 2 h to obtain yellow and viscous liquid product.
The 1 H NMR spectra was shown in Fig. 2S. 1 H NMR (400 MHZ),
CDCl3 :0.94 (t, 6H), 1.39 (m, 4H), 1.89 (m, 4H), 4.35 (t, 4H), 7.46 (d,
2H), 10.82 (s, 1H).
2.2.3. Preparation of HCMC
The HCMC was prepared according to previously reported procedures [29]. NaCMC (2 g) was added to 80% ethanol aqueous
solution (200 ml), and then HCl (20 ml, 37%) was added and stirred
for 45 min. The solid was ltered and then washed with 70% ethanol
aqueous solution till the washing solution was neutral and no Cl
was detected with silver nitrate test. The solid was then dried 2 h
under the vacuum to obtain the white powder of HCMC.
2.2.4. Synthesis of HBimCl-M/HCMC catalysts
The IL HBimCl and metal chlorides (Lewis acid) were immobilized on HCMC by co-dispersing the IL (0.068 g, 0.31 mmol) and
metal halides (0.155 mmol) in DMF (5 ml) at 100 C for 5 h under
nitrogen atmosphere, and then added the HCMC (0.50 g) and stirred
overnight. After the mixture was cooled to room temperature under
nitrogen atmosphere, the solvent in the resulting mixture was
evaporated under vacuum and washed with anhydrous ethyl ether,
followed by drying under vacuum at 40 C for 2 h to obtain the catalyst HBimCl-M/HCMC, where M represented the different metal
halides. For the sake of comparison, NbCl5 /HCMC, HBimCl/HCMC,
DBimCl/HCMC and DBimCl-NbCl5 /HCMC catalysts have also been
prepared in a similar method, where the loading amounts of ILs
and metal chlorides on CMC were 0.50 mmol g1 and 0.25 mmol g1
respectively, unless otherwise described.

2. Experimental
2.3. Characterization
2.1. Chemical reagents
Sodium
salt
of
carboxymethyl
cellulose
(NaCMC,
8001200 mPa s) was purchased from Sinopharm Chemical
Reagent Co., Ltd., Shanghai. Metal chlorides such as NbCl5 , ZnCl2 ,
InCl3 , FeCl3 and CaCl2 were all purchased from Sinopharm Chemical Reagent Co., Ltd., and used without further purication. CO2
was supplied by Shanghai Shangnong Gas Factory with a purity of
>99.95%. Epoxides were analytical grade and were used directly
without further purication. All solvents (analytical grade) were
dried by using the standard methods.

All NMR spectra were recorded on a Bruker AVANCE 400 MHz

instrument (400 MHz 1 H NMR) using CDCl3 as solvents. FT-IR
spectrum was performed from pressed KBr tablets at room temperature on a Nicolet Fourier transform infrared spectrometer
(Magna 550) by pressed KBr tablets at room temperature. The
XRD patterns were recorded from D/MAX 2550 VB/PC using CuK
radiation ( = 1.5406 ) operated at 40 kV and 200 mA. Surface
areas (BET) of the catalysts were measured by N2 adsorption at
77 K using NOVA 4200 e Analyser after the evacuation of the
sample at 100 C for 12 h. The thermal stability of catalysts was

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X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

GCMS and GC analysis. The catalyst was washed with ethyl ether
and dried in a vacuum at 60 C for recycling tests.
The cycloaddition reaction of CO2 with epoxy chloroproane
was also carried out in a vertical xed-bed stainless-steel reactor (i.d.1.1 cm, length 60 cm). The catalyst was pressed, crushed,
and sieved to 2040 mesh prior to the reaction. A constant weight
(2.0 g) of the catalyst layer was sandwiched in the middle of the
reactor with quartz wool and quartz sand for supporting the catalyst and evaporation of the reactants. In a typical procedure, epoxy
chloropropane were pumped with HPLC pumps and the CO2 pressure was tuned by a regulator, which allowed to ow through
the system at constant pressure. They met at the mixing area and
then passed through the preheater. The CO2 /epoxide mixture, after
being warmed in the preheater area, was introduced into the reactor. The efuent from the reactor was then introduced the collecting
vessel, where the pressure was reduced to atmospheric. Then collected liquid phase was analyzed by GC.
Fig. 1. The FT-IR spectra of (a) HCMC, (b) NbCl5 /HCMC, (c) DBimCl/HCMC, (d) fresh
DBimCl-NbCl5 /HCMC catalyst, (e) DBimCl-NbCl5 /HCMC catalyst after reused for
5 times, (f) HBimCl/HCMC, (g) Fresh HBimCl-NbCl5 /HCMC catalyst, (h) HBimClNbCl5 /HCMC catalyst after reused for 5 times.

3. Results and discussion

3.1. Catalyst characterization

determined by Thermogravimetry analysis (TGA) method (heating rate: 10 C min1 ; N2 ow, 100 ml min1 ) using PerkinElmer
Pyris Diamond Analyser. The Scanning electron microscopy (SEM)
images were performed on JSM electron microscopes (JEOL JSM6360LV, Japan). ICP-AES analysis was carried out on a Varian
710-ES instrument. The content of C, H and N was checked
by element analysis, which was conducted on Elementar Vario
EL III instrument. The resulting reaction products were analyzed by gas chromatograph (Shimadzu GC-2014, KB-50 capillary
column, 30m 0.32mm 0.50 m) and GCMS (Agilent-6890 GC5973MS, HP-5MS, 30m 0.25mm 0.25 m). The concentration of
carboxyl groups on catalysts (mmol g1 ) were determined by acidbase titration method according to the reported procedures [33].
In situ diffuse reectance infrared fourier transform spectroscopy
(DRIFTS) experiments were conducted on a Nicolet 6700 FTIR tted
with a liquid nitrogen cooled mercury-cadmium-telluride detector
(MCT). The DRIFTS cell (Harrick, HVC-DRP) tted with CaF2 windows were used as the reaction chamber that allowed samples
to be heated to 150 C. All the spectra were within the range of
40001200 cm1 at the resolution of 4 cm1 and 64 scans. Prior to
the adsorption experiments, the samples were pretreated in Ar at
150 C for 4 h. Then the samples were cooled down to 25 C in order
to remove the contaminants and the PO-adsorbed FT-IR spectra of
the samples (25 mg) were recorded at 25 C. In the characterization of pyridine-adsorbed FT-IR spectra, the sample (12.5 mg) was
subjected to a standard pre-treatment involving heat treatment at
180 C in vacuum for 4 h. Pyridine was adsorbed at the partial pressure at room temperature under vacuum. All the adsorption studies
were carried out at room temperature.
2.4. Reaction of cycloaddition from CO2 and peroxides
The cycloaddition reaction of propylene oxide (PO) and CO2 to
propylene carbonate (PC) was used as a model reaction to evaluate the catalytic performance. The catalyst and PO were added
into the autoclave. The reactor was purged with CO2 for 3 times
and then charged with CO2 to the desired pressure. After the reaction, the reactor was cooled in ice-water bath immediately, and
the CO2 was slowly vented while ethyl acetate was as absorption
liquid to absorb the PO and products entrained by CO2 . Then, the
ethyl acetate in the trap was added to the reactor and washed the
catalyst to extract products and substrate. The mixture was separated by standing simply, and the liquid phase was subjected to

In this work, NaCMC was rst acidied and transformed into

its protonated form (HCMC) (Scheme 2). The HCMC was chosen
as catalyst support because it is highly thermally stable and owns
abundant hydroxyl and carboxyl groups. The IL and Lewis acid were
co-impregnated simply and thus immobilized on HCMC.
At rst, the catalysts were characterized by FT-IR spectra. As
shown in Fig. 3S, NaCMC exhibited the characteristic peaks at
3460 cm1 ( OH), 2930 cm1 (C H stretch), 1640 cm1 ( COONa),
and 10701136 cm1 ( C O ). After acidication, the new peaks
at 1757 cm1 can be assigned to the stretching vibration of
COOH, which conrmed the successful acidication of NaCMC
to HCMC [32,34]. Additionally, the imidazolium ring stretching
bands (1564 cm1 ), and the absorption bands at 3160, 3100 cm1
attributed to C H stretching vibration of imidazolium ring and
2960, 2880 cm1 were the C H stretching vibration of aliphatic
chain in IL were all observed in HCMC-supporting IL catalysts
(Fig. 1ch), which meant that the ILs were successfully grafted
on HCMC surface [27,35]. Whats more, the stretching vibration of
COOH moved from 1757 cm1 to 1750 cm1 after the HBimCl was
immobilized on the HCMC (Fig. 1a, fh), but the stretching vibration
of COOH showed no any change after the DBimCl was immobilized
on the support (Fig. 1a, ce), which could be attributed to the effect
of hydrogen bond between COOH groups of HCMC and OH of
HBimCl.
It should be noted that the numbers of carboxyl groups kept
basically unchanged even after the OH group functionalized IL
(HBimCl) was loaded in HCMC support (Table 1S), indicating clearly
that no covalent bond was formed between COOH groups of
HCMC and OH groups of HBimCl in the process of IL loading. Most
likely, there was only hydrogen bonding interaction between the
OH group of IL and COOH groups of HCMC.
The XRD patterns of catalysts were depicted in Fig. 2. The peaks
arisen from amorphous HCMC (Fig. 2a) between 10 30 were
observed. There were no obvious differences were seen between
the HCMC and the HBimCl-NbCl5 /HCMC catalyst (Fig. 2b), which
evidenced that HBimCl and NbCl5 were evenly dispersed on the
surface of the CMC support. The thermal stability of the support and the different catalysts were investigated by TGA. As
shown in Fig. 3, HCMC showed a slightly weight loss below 120 C,
which could be attributed to the removal of the adsorbed H2 O
on the surface of HCMC. The HCMC started to decompose around
220 C (Fig. 3a), which was possibly attributed to the gradual
degradation of polymer chain. It could be found that the onset

X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

149

Scheme 2. The acidication of sodium salt of carboxymethyl cellulose (NaCMC) to protonated carboxymethyl cellulose (HCMC).

Table 1
Effect of different Lewis acids on the synthesis of propylene carbonate by HBimClM/HCMC catalystsa .
Entry

Con. (%)

Sel. (%)

1b
2
3
4
5
6

none
CaCl2
FeCl3
ZnCl2
InCl3
NbCl5

37.5
51.1
54.5
70.7
75.3
88.1

99.1
98.7
98.8
97.9
98.8
99.0

a
Reaction condition: PO (10 mmol), catalyst (0.1 g), temperature: 110 C, CO2
pressure: 1.5 MPa, time: 3 h.
b
HBimCl/HCMC was used as catalyst.

Table 2
The synthesis of propylene carbonate over various catalystsa .

Fig. 2. XRD patters of (a) HCMC, (b) HBimCl-NbCl5 /HCMC, (c) HBimCl- NbCl5 /HCMC
catalyst after reused for 5 times.

Entry

Catalyst

Con.%

Sel.%

1
2b
3
4c
5c
6
7
8
9d
10e
11

HCMC
NbCl5
NbCl5 /HCMC
HBimCl
DBimCl
HBimCl/HCMC
DBimCl/HCMC
HBimCl-NbCl5 /HCMC
HBimCl-NbCl5 /HCMC
HBimCl-NbCl5 /HCMC
DBimCl-NbCl5 /HCMC

0
3.2
41.7
62.1
54.2
69.6
62.2
98.1
95.2
97.8
89.9

96.9
98.7
99.1
93.3
98.3
95.9
98.3
99.1
98.9
90.0

a
Reaction condition: PO (10 mmol), catalyst (0.1 g), temperature: 130 C, CO2
pressure: 1.5 MPa, time: 3 h.
b
NbCl5 : 6.8 mg (0.025 mmol).
c
HBimCl or DBimCl: 10.9 mg (0.05 mmol).
d
0.075 g catalyst.
e
0.175 g catalyst.

3.2. Catalytic performances

Fig. 3. The thermal gravity analysis of (a) HCMC, (b) The fresh HBimCl-NbCl5 /HCMC
catalyst, (c) The spent HBimCl-NbCl5 /HCMC catalyst after 5 catalytic recycles.

decomposing temperature of fresh HBimCl-NbCl5 /HCMC (Fig. 3b)

decrease slightly, as comparing with that of the parent HCMC,
revealing the interaction between support and IL.
Moreover, the low porosity of the present catalysts were
reected by rather small BET surface area (BET area < 10 m2 g1 ),
which indicated all catalytically active species would be mainly dispersed over the outside surface of HCMC. As shown in Fig. 4, the SEM
images showed further that the bulk structure of HCMC is brous
in texture with about 160 m length and 14 m width (Fig. 4a and
d), while the HBimCl-NbCl5 /HCMC catalyst had a slightly rougher
surface and shorter ber due to the addition of IL and NbCl5 components but still showed brous texture (Fig. 4b and e).

The effects of different Lewis acids on catalytic activity were

rst investigated for the cycloaddition reaction of CO2 with epoxides. Lewis acids were used as promoter in this work and all of
them were listed on Table 1. It was found that HBimCl/HCMC catalyst only afforded conversion of PO of 37.5% (Table 1, entry 1).
However, when these metal chlorides as Lewis acids were added,
the activity of catalysts were greatly improved (Table 1, entries 1
vs. 26). Among various Lewis acids, NbCl5 was proved to be the
most active for the cycloaddition reaction. These results indicated
that Lewis acid could play an important role in enhancing the activity of IL catalyst by interacting with the oxygen of the epoxide to
form the Lewis acid-epoxide adduct [36]. Especially, the strength
of Lewis acid had also a crucial effect on the activity. The stronger
Lewis acids like InCl3 and NbCl5 seemed to offer more signicant
role in improving catalytic performance (Table 1, entries 24 vs. 5
and 6).
Sequentially, the activities of NbCl5 -derived catalysts for the
cycloaddition reaction of PO and CO2 were examined further
under the optimized reaction conditions. As shown in Table 2,
either the support material HCMC or NbCl5 could catalyze scarcely
the cycloaddition reaction (Table 2, entries 1 and 2), but their

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X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

Fig. 4. The SEM images of HCMC (a, d), the fresh HBimCl-NbCl5 /HCMC catalyst (b, e) and HBimCl-NbCl5 /HCMC catalyst after reused for 5 times (c, f).

combination afforded some activity (Table 2, entry 3). It can be seen

that the single imidazolium-based IL showed moderate to high catalytic activities, and the IL with hydroxyl group had higher activities
than that of IL without hydroxyl group (Table 2, entries 4 and 5).
This indicated that the OH group in IL was responsible for the
enhancing activity [25]. Whats more, the ILs supported on HCMC
showed slightly higher activity than the corresponding homogeneous analogue (Table 2, entries 4 vs. 6; entries 5 vs. 7), suggesting
the functional groups of HCMC would facilitated the ring opening of the epoxide and nucleophilic attack of the cycloaddition of
CO2 with epoxides, and thus distinctly enhanced the activity for
cycloaddition [28,35]. Obviously, the loading of both ILs and NbCl5
on HCMC afforded excellent activity (Table 2, entries 811), while
the OH group functionalized IL HBimCl was proved to be the more
efcient for the reaction, as compared with that of DBimCl (Table 2,
entries 8 vs. 11). In other words, there was the strongest synergistic interaction between HBimCl and NbCl5 . Additionally, the loading
amount of catalyst also affected activity. The constant activity could
be achieved when the loading amount of catalyst increased to 0.1 g
(Table 2, entries 810).
The effects of reaction condition (temperature, CO2 pressure
and reaction time) were investigated over this catalyst. Firstly, we
investigated the effect of the reaction temperature and the results
are shown in Fig. 5a, the reaction temperature had a signicant
effect on the reaction. With the increment of temperature from
100 C to 130 C, the conversion of PO increased apparently. At
higher temperature, the activity did not further increase. The higher
temperature might result in the decomposition of the catalyst and
needed more energy. Consequently, the appropriate temperature
was chosen at 130 C for the cycloaddition reaction.
Then we investigated the inuence of CO2 pressure on the reaction of PO was studied at 130 C for 3 h as shown in Fig. 5b, the
conversion of PO was increased obviously when the reaction pressure increased from 0.6 MPa to 1.5 MPa. A possible explanation was
that more CO2 can be dissolved in PO as increasing reaction pressure [17], which was favorable for the CO2 cyclicaddition reaction.
However, at higher pressure range, the conversion of PO had a
slight decrease while selectivity showed no obvious changes. This
might be related to a dilution effect occurring that the excess CO2

reduced the concentration of CO2 in the vicinity of the catalyst or

hinder the active mass transport [37,38]. Thus, it was apparent that
the appropriate reaction pressure was 1.5 MPa for the synthesis of
cyclic carbonate.
The effect of reaction time was obtained from Fig. 5c. Under the
condition of 130 C and 1.5 MPa, the conversion of PO had a brightly
increasing within the rst 2.5 h and then remained almost invariant
with high selectivity. The substrate was almost completely converted to PC within 3 h with high selectivity.
Sequentially, the kinetic studies of the cyclic addition of CO2
and PO were investigated. The synthesis of PC using the HBimClNbCl5 /HCMC catalyst was undertaken as a function of temperature
and the activation energies were obtained accordingly, where the
reaction rate constants under different reaction temperature were
determined from the experimental data assuming pseudo-rst
order reaction kinetics. The kinetic parameters were studied over a
temperature range from 110 to 140 C. Since the concentrations of
catalysts were constant and the presence of CO2 was excess, thus
the rate laws for this process were tted to Eq. (1).
Rate = k[epoxide][CO2 ][cat.] = kobs [epoxide] = d[epoxide]/dt (1)
Integrating Eq. (1), then
Ln [1 con.] = kobs t

(2)

where k is the rate constant; [epoxide], [CO2 ], [cat.] represents PO,

CO2 and catalyst concentration; while t is the reaction time; con.
the conversion of PO and [con.] the observed pseudo-rst order rate
constant, respectively.
The kobs was thus obtained from the slope of the natural
logarithm of remaining PO conversion versus time at different
temperatures based on Eq. (2). The plots were linear as shown
in Fig. 4S, the tted values of correlation coefcient R2 were all
approximately equal to 1, which indicated that the reaction followes rst-order kinetics [3941]. Ultimately, as shown in Fig. 6,
the activation energy (Ea) for the process was calculated using the
Arrhenius equation, where Ea was 29.0 kJ mol1 . The Ea obtained
under the present condition was similar to that reported over other
catalytic systems [42,43].

X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

151

Fig. 5. Dependence of PC conversion and selectivity on the reaction condition over HBimCl-NbCl5 /HCMC catalyst.

Fig. 6. Arrhenius plots for the CO2 cycloaddition to PC catalyzed by HBimClNbCl5 /HCMC.

3.3. Catalyst stability

At rst, the reusability of the HBimCl-NbCl5 /HCMC and DBimClNbCl5 /HCMC catalysts was examined under the optimal conditions
(Fig. 7). After reaction, ethyl ether was added to the reaction
mixture. The solid catalyst was recovered conveniently by simple centrifugation, followed by washing with ethyl ether 3 times
and then vacuum drying at 60 C. Then the recovered catalyst was

reused for the next recycle. The reusability of HBimCl-NbCl5 /HCMC

catalyst was shown in Fig. 7a. It was found that the catalyst could
be reusable for at least up to ve times with high conversion, while
the selectivity of the product remained the same. On the other
hand, although DBimCl-NbCl5 /HCMC catalyst showed high activity
at the rst run, it became deactivated gradually in the consecutive
catalytic recycles (Fig. 7b).
Subsequently, the FT-IR of the reused HBimCl-NbCl5 /HCMC catalyst was displayed in Fig. 1g, which revealed that the typical
absorption peaks of the HBimCl remained unchanged, and also the
XRD pattern of the reused catalyst was also in agreement with that
of fresh one (Fig. 2b and c). In addition, The TGA curves of the reused
catalyst displayed a pattern similar to that of the fresh one (Fig. 3b
and c), which thus proved that the present catalyst system was
thermally stable. The surface morphology of the reused catalysts
was shown in Fig. 4c and f, which indicated that the catalyst was
still brous in texture although the surface of the catalyst became
rougher and the ber of that shorter. All these results suggested
that no signicant difference occurred between the fresh and the
reused HBimCl-NbCl5 /HCMC catalysts.
These results strongly implied that the HBimCl-NbCl5 /HCMC
catalyst not only afforded the better catalytic activity but also
showed higher catalytic stability in the recycling test, as compared
with that of DBimCl-NbCl5 /HCMC catalyst. Because the HCMC
support is highly stable and DBimCl showed actually no structural changes from FT-IR spectra after catalytic recycles (Fig. 1d
and e), therefore the poorer recycliability of DBimCl-NbCl5 /HCMC
catalyst could be attributed to IL leaching during the catalytic

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X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

Fig. 7. Recyclability of (a) HBimCl-NbCl5 /HCMC and (b) DBimCl-NbCl5 /HCMC catalysts.

recycles. Thus in the next step, the contents of active species of

the HBimCl-NbCl5 /HCMC and DBimCl-NbCl5 /HCMC catalysts have
been determined before and after reaction (Table 2S), respectively.
It was found that the mass percentage of N (1.32 wt.%) and Nb
(2.23 wt.%) of the HBimCl-NbCl5 /HCMC catalyst after the fth runs
had no obvious decrease, as compared with the fresh catalyst (N:
1.41 wt.%, Nb: 2.33 wt.%), while the mass percentage of C had a
slightly increase, possibly due to the propylene carbonate adsorbed
on the surface of the catalyst. However, the mass percentage of N of
the spent DBimCl-NbCl5 /HCMC catalyst (1.13 wt.%) had an obvious
loss, as compared with the fresh catalyst (N: 1.42 wt.%), although
the mass percentage of Nb had no obvious reduction (Table 2S).
Surface acidity properties of the catalysts were also analyzed by
FT-IR using pyridine as probe molecule and the data were collected
in Fig. 5S. The bands at 1594.4 cm1 can be associated with the formation of a H-bonded pyridine adduct, as an index of the presence
of weak Bronsted acid site [44,45]. The band at 1450.4 cm1 was
attributed to pyridine-adsorbed on Lewis sites (coordinated unsaturated Nb sites) on the catalyst. The quantication of acid sites was
performed using the same expressions as those in the research article of Lanzafame et al. [45]. The density of Brnsted and Lewis acid
sites was found to be 2.65 and 0.24 mmol g1 , respectively.
In order to gain a deeper insight into the reaction mechanism, DRIFT of in situ PO adsorption was performed over HCMC,
HBimCl/HCMC and HBimCl-NbCl5 /HCMC catalysts. After PO was
introduced into the different solid samples, as shown in Fig. 8a, the
bands at 1423.2, 1409.7 and 1398.1 cm1 can be assigned to C H
bending vibration of gas-phase PO molecules. After purging with
Ar, it was observed that PO molecules absorbed very weakly on
HCMC. However, PO molecules gave the most favorable adsorption
on HBimCl-NbCl5 /HCMC catalyst (Fig. 8b). Furthermore, C H bending vibration of PO molecules at 1423.2, 1409.7 cm1 was shifted to
lower wavenumbers owning to PO adsorption. These results suggested strongly that both IL and Lewis acid sites played a crucial
role in activating PO molecules.
On the basis of the results above, the reaction mechanism can
be demonstrated as Scheme 3. The ionic liquid showed excellent
resistance to leaching, indicating that the ionic liquid HBimCl can be
immobilized robustly through non-covalent interactions including
electrostatic interaction and hydrogen bond. Additionally, NbCl5
was dispersed on HCMC as a Lewis acid site. Firstly, the strong
Lewis acid site (Nb sites) and the hydroxyl groups in HBimCl coordinated with the oxygen of the epoxide, resulting in activation of
an epoxide molecule [41]. Meantime, the nucleophilic attack using
Cl on the less sterically hindered -carbon atom of the epoxide
furnishes the ring-opened intermediate, by which the ring of the
epoxide was opened easily. This is followed by the CO2 insertion
into the Nboxo bond, which is predicted to be the rate determining step [4648]. Thereafter, the intermediate made a subsequent

Scheme 3. The proposed reaction mechanism for cycloaddition of epoxide and CO2
catalyzed by HBimCl-NbCl5 /HCMC catalyst.

intramolecular ring-closure, cyclic carbonate could be formed and

the catalyst was regenerated. It should be worth noticing that cellulose might act as an additional activator for the ring-opening of
epoxide by its hydrogen bonding [28]. The synergetic catalysis role
of the above two allowed the reaction to proceed smoothly.
As we were encouraged by the promising results obtained from
batchwise recycling, the synthesis of cyclic carbonates from epoxides and CO2 was carried out as a continuous-ow process, which
would be more favorable for the practical application. Here, we
tested the activity and stability of the HBimCl-NbCl5 /HCMC catalyst in the continuous xed bed ow mode under mild conditions
(2 MPa CO2 pressure, 120 C). As shown in Fig. 9, the conversion of
epoxy chloropropane was nearly 92% with a ow rate of 2.4 ml h1
for epoxy chloropropane and 32 ml min1 for gas CO2 for more than
100 h on stream while the selectivity to chloromethyl ethylene carbonate was normally over 96% when the continuous ow reached
to stability, which indicated that the life time of catalyst was excellent under a continuous-ow condition. Because the IL and Lewis
acid were loaded on HCMC through a non-covalent approach, thus
the catalyst preparation is very easy from cheap, non-toxic and biocompatible materials, and thus it can be more potential application
for industrial production.
3.4. Cycloaddition of CO2 with other epoxides
The results above demonstrated that supporting ILs with the
OH group, promoted with Lewis acid NbCl5 was a very efcient
catalyst for the cycloaddition of CO2 and PO in the absence of any

X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

153

Fig. 8. DRIFT spectra of (a) gas-phase PO and (b) in situ PO adsorbed on HCMC, HBimCl/HCMC and HBimCl-NbCl5 /HCMC samples.
Table 3
Different epoxides as substrates for the cycloaddition reaction with CO2 catalyzed
by HBimCl-NbCl5 /HCMCa .

Fig. 9. The conversion of epichlorohydrin in a xed-bed continuous ow reactor. Reaction conditions: HBimCl-NbCl5 /HCMC (2.0 g); epoxy chloroproane ow:
0.04 ml min1 ; CO2 ow: 32 ml min1 ; the pressure of CO2 : 2 MPa; temperature:
120 C.

other solvent. Thus the catalyst was extended to other epoxides as

substrates for synthesis of cyclic carbonates under the optimized
reaction conditions and the results were summarized in Table 3.
It could be found that the catalyst was applicable to the cycloaddition reaction of CO2 with various terminal epoxides (Table 3,
entries 16), indicating a variety of epoxides produced corresponding cyclic carbonates with high conversions and selectivities within
the rst 5 h (Table 3, entries 14). Compared with other epoxides,
epoxycyclohexane and cyclohexene needed a longer reaction time
to produce corresponding cyclic carbonates because of the steric
hindrance (Table 3, entries 5 and 6) [38].
4. Conclusion
In summary, CMC-supporting imidazolium-based ILs, combining with Lewis acid promoter, especially like niobium chloride,
have been demonstrated as an effective catalysts for the synthesis of various cyclic carbonates via epoxide and CO2 under
solvent-free condition. It was demonstrated that HBimCl on
HBimCl-NbCl5 /HCMC catalyst showed excellent resistance to
leaching. There was a strong synergistic effect between HBimCl
and Lewis acid promoter like niobium chloride, which afforded
the best catalytic performance. The HBimCl-NbCl5 /HCMC catalyst
could be recovered by simple centrifugation after the reaction
and reused ve times without any loss of activity in batch

a
Reaction conditions: epoxides (10 mmol), catalyst (0.1 g), temperature: 130 C,
CO2 pressure: 1.5 MPa.

reactor. Furthermore, the catalyst showed high activity and catalytic stability in continuous xed bed reactor for more than 100 h
on stream, which demonstrated the applicability of the catalyst
system for synthesizing cyclic carbonates from CO2 and epoxides.
The results of this work provided an example of the applications of
HCMC-supported IL catalysts as environmentally benign efcient
alternatives in organic synthesis and catalysis.
Acknowledgements
The authors are grateful for support from the National Natural
Science Foundation of China (21373082) and innovation Program
of Shanghai Municipal Education Commission (15ZZ031), and the
Fundamental Research Funds for the Central Universities.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.apcata.2016.04.
002.

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X. Wu et al. / Applied Catalysis A: General 519 (2016) 146154

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