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A bifunctional cationic porous organic polymer

based on a Salen-(Al) metalloligand for the
Cite this: Chem. Commun., 2016,
52, 13288 cycloaddition of carbon dioxide to produce cyclic
Received 21st September 2016,
Accepted 19th October 2016
carbonates†
DOI: 10.1039/c6cc07662a Tao-Tao Liu,ab Jun Liang,a Yuan-Biao Huang*a and Rong Cao*a
www.rsc.org/chemcomm

A bifunctional cationic porous organic polymer based on a Salen-(Al) in gas storage and separation,31,32 light-harvesting,33 and mole-
metalloligand (Al-CPOP) containing imidazolium functionality exhibited cular sensing devices.34 In particular, active functional groups
enhanced activity and good recyclability in the cycloaddition of can be easily incorporated into POPs, which showed good activity
carbon dioxide to produce cyclic carbonates without the addition and stability in heterogeneous catalysis.35–39 Herein, we design
of co-catalysts at atmospheric pressure. and prepare a new cationic porous organic polymer (Al-CPOP)
containing Salen-(Al) and imidazolium, which can be employed
In recent years, the increasing emission of greenhouse gas CO2 as a bifunctional heterogeneous catalyst for the cycloaddition
has triggered a lot of environmental problems, such as global of carbon dioxide with epoxides to produce cyclic carbonates
warming and an acceleration of sea-level rise. Therefore, develop- without the addition of co-catalysts at atmospheric pressure.
ing new techniques to reduce CO2 requires urgent attention. To the best of our knowledge, this is the first example of POP that
Besides the capture and sequestration of CO2, chemical fixation contains bifunctional groups metallosalen and imidazolium.35
of CO2 has attracted much attention of chemists around the During the catalysis process, the Salen-(Al) moiety in Al-CPOP
world.1–9 In particular, cycloaddition of carbon dioxide with epoxides (Scheme 1) acted as a Lewis acid, whereas the chloride of
to produce cyclic carbonates, which can be widely used as inter- imidazolium served as a Lewis base to synergistically promote
mediates and battery electrolytes, was proved to be an effective way the cycloaddition of carbon dioxide with epoxides to afford
for the conversion of CO2 into value-added chemicals. cyclic carbonates. As shown in Scheme 2, the epoxide could be
To date, many catalysts including ionic liquids10,11 and metal
complexes12,13 have been utilized for the cycloaddition of CO2 with
epoxides to produce cyclocarbonates. It is well known that transi-
tion metal complexes of a Schiff base, denoted as Salen-M (M = Al
and Co), are a class of effective catalysts for fixing CO2 with
epoxides.14–21 However, organic ammonium salts such as tetrabutyl
ammonium bromide acting as co-catalysts are usually required,
which increases the cost and calls for a cumbersome purification
process.5,6 Thus, combining Salen-M and an organic ammonium
salt into one complex to form a bifunctional catalyst is an alter-
native strategy to circumvent this drawback.22–30 However, these
homogeneous catalysts suffered from laborious purification pro-
cesses and cannot be recovered and reused, while the use of porous
heterogeneous catalysts could overcome this problem.
Porous organic polymers (POPs) have emerged as a class of
promising porous materials and showed potential applications

a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter University of Chinese Academy of Sciences Fujian, Fuzhou,
350002, P. R. China. E-mail: rcao@fjirsm.ac.cn, ybhuang@fjirsm.ac.cn;
Fax: +86-591-8379-6710
b
University of the Chinese Academy of Sciences, Beijing, 100049, China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6cc07662a Scheme 1 Synthesis of Al-CPOP.

13288 | Chem. Commun., 2016, 52, 13288--13291 This journal is © The Royal Society of Chemistry 2016
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which confirmed the formation of the Salen-(Al) complex. The

solid-phase 13C-NMR spectra showed that the carbon peak of
chloromethylene in Salen-(Al) at 51.48 ppm (Fig. S1, ESI†)
shifted to 50.16 ppm in Al-CPOP (Fig. 2), indicating that methylene
was connected to imidazole and imidazolium was formed.
Compared with the binding energy of Al 2p of Salen-(Al)
(74.67 eV, Fig. S2a, ESI†), the X-ray photoelectron spectroscopy
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(XPS) analysis indicated that a red shift of the Al 2p peak at

74.05 eV in Al-CPOP (Fig. S2b, ESI†) was observed,5 which was
ascribed to the modification of the electronic environment of
aluminum after the formation of the polymer.
A broad peak centered at 261 was observed in the powder X-ray
diffraction (PXRD) pattern, which indicated the amorphous
character of Al-CPOP (Fig. S3, ESI†). The field-emission scanning
electron microscopy (FE-SEM) image showed that Al-CPOP nano-
Scheme 2 Possible bifunctional cooperative catalysis process of Al-CPOP spheres with sizes ranging from 100 to 300 nm were formed
for CO2 fixation. (Fig. 3a). Moreover, the elemental mapping by energy-dispersive
X-ray spectroscopy (EDS) analysis displayed homogeneous distri-
butions of aluminum, chloride and nitrogen (Fig. 3b), indicating
absorbed and activated by the Salen-(Al) site and generate an
the uniform incorporation of the functional Salen-(Al) moiety
intermediate with strong d charge. At the same time, the chloride
into the polymer. Interestingly, the TGA result (Fig. S4, ESI†)
in imidazolium attacks the less steric hindrance C–O bond in the
indicates that Al-CPOP could be stable up to 250 1C.
epoxide and leads to a ring-opening reaction and achieves a new
The N2 adsorption isotherm of Al-CPOP showed a typical
zwitterion, which further reacts with the enriched CO2 to afford a
type-IV behavior and the Brunauer–Emmett–Teller (BET) surface
cyclic carbonate. More interestingly, the nitrogen-rich backbone
area is 136 m2 g 1 (Fig. S5a, ESI†), demonstrating that Al-CPOP
could increase the adsorption of CO2, thus enhancing the ‘‘CO2
is indeed a porous material. Interestingly, an obvious hysteresis
capture’’ ability, which can accelerate the CO2 reaction rate.40,41
desorption curve in the range of P/P1 = 0.4–0.8 was observed,
In addition, the bifunctional heterogeneous catalyst can be easily
indicating that mesopores were formed and the pore width is
recovered by filtration and reused at least five times without loss
centered at 2.5 nm on the basis of the density functional theory
of activity.
(DFT) model analysis and the Horvath–Kawazoe differential pore
As illustrated in Scheme 1, the target catalyst Al-CPOP can be
volume plot (Fig. S5b, ESI†). Moreover, although the porous material
easily obtained from the chloromethyl functionalized monomer
Al-CPOP containing triazine rings showed a low BET surface area,
Salen-(Al) and 2,4,6-tris(imidazol-1-yl)-1,3,5-s-triazine (TIST) in a
it exhibited moderate CO2 adsorption uptake (12 cm3 g 1) at room
mixture of DMF and ethanol. The metalloligand Salen-(Al) mono-
temperature (Fig. S5c, ESI†). Notably, an obvious hysteresis
mer was firstly synthesized from the reaction of Salen and Al salt
desorption curve was observed, indicating that a strong interaction
(Scheme S1, ESI†), whereas TIST was obtained by mixing cyanuric
exists between the triazine rings of Al-CPOP and CO2. The strong
chloride and imidazole (Scheme S2, ESI†). Compared with the
CO2 capture ability of Al-CPOP will promote the conversion of CO2.
IR spectrum of the ligand Salen (wine red line in Fig. 1), the
peak of the CQN bond at 1630 cm 1 shifted to 1649 cm 1 and a
new peak at 593 cm 1 related to the Al–O bond was observed,

Fig. 1 IR spectra of Salen (wine red line), Salen-(Al) (red line), Al-CPOP
13
(blue line) and TIST (black line). Fig. 2 Solid-phase C-NMR spectra of Al-CPOP.

This journal is © The Royal Society of Chemistry 2016 Chem. Commun., 2016, 52, 13288--13291 | 13289
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Table 2 Cycloaddition of CO2 with various epoxidesa

Entry Substrate Product Conv.b/% Selec.b/%

1 499 95
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2 91 74

Fig. 3 (a) FE-SEM image of Al-CPOP and (b) EDS elemental-mapping

image of Al-CPOP.
3 61 95

Thus, the bifunctional catalyst Al-CPOP containing the Salen-(Al)

metalloligand and imidazolium was then employed for the 4 15 499
cycloaddition of carbon dioxide with epoxide to produce a
cyclic carbonate without the addition of any additive at atmo- a
Reaction conditions: epoxide (10 mmol), Al-CPOP (0.1 mmol, 1 mol%),
spheric pressure. The substrate epichlorohydrin (10 mmol) was CO2 (0.1 MPa), 393 K, 24 hours. b Determined by GC.
firstly selected for the screening of the optimized reaction
conditions. Interestingly, 77% epichlorohydrin can be trans-
We next examined the scope of the reactions with a variety of
formed to the corresponding cyclic carbonate 4-(chloromethyl)-
substituted epoxides (Table 2). As for propylene oxide, Al-CPOP
1,3-dioxolan-2-one with high selectivity (94%, Table 1, entry 1)
gave excellent conversions (91%) and satisfactory selectivity (74%).
using only 1 mol% catalyst based on Al at 100 1C. When the
The epoxide allyl glycidyl ether gave moderate conversion (61%)
temperature was increased to 120 1C, nearly all of the substrate
and outstanding selectivity (95%, Table 2, entry 3). Although only
was consumed and 95% selectivity was afforded (Table 1,
15% cyclohexane oxide was converted to the corresponding cyclic
entry 3). Therefore, the following optimal conditions, i.e., 1 mol%
carbonate 4-butyl-1,3-dioxolan-2-one, it exhibited nearly 100%
catalyst, 0.1 MPa CO2, 120 1C and 24 h, were chosen for the sub-
selectivity (Table 2, entry 4).
sequent catalysis.
Compared with the homogeneous catalyst, the bifunctional
For comparison, different catalysts were examined under the
porous heterogeneous catalyst Al-CPOP can be easily recovered
optimal conditions. It should be noted that without the catalyst,
by centrifugation and reused for the next run. As shown in Fig. 4,
no product was obtained (Table 1, entry 4). Compared with the
after being recycled for five runs of the cycloaddition of carbon
bifunctional catalyst Al-CPOP (Table 1, entry 3), although the
dioxide with epichlorohydrin to produce the cyclic carbonate
homogeneous catalyst Salen-(Al) showed a high comparable
4-(chloromethyl)-1,3-dioxolan-2-one, the Al-CPOP catalyst still
conversion (97%), it exhibited much lower selectivity under the
exhibited high activity and selectivity, indicating that the porous
same conditions (86%, Table 1, entry 5). As shown in entry 6,
catalyst is stable.
Table 1, only 11% conversion and 86% selectivity were obtained
In summary, a new bifunctional cationic porous organic
when the industrial catalyst KI was used under the same conditions.
polymer Al-CPOP combining Salen-(Al) and imidazolium was firstly
These control experiments demonstrated that the bifunctional
synthesized. Without any co-catalyst, the porous heterogeneous
POP Al-CPOP is an effective catalyst for the promotion of this
reaction.

Table 1 Cycloaddition of CO2 with epichlorohydrina

Entry Catalyst T/1C Conv.b/% Selec.b/%

1 Al-CPOP 100 77 94
2 Al-CPOP 110 92 96
3 Al-CPOP 120 499 95
4c Blank 120 0 —
5 Salen-(Al) 120 97 86
6 KI 120 11 86
a Fig. 4 Recycled experiment of Al-CPOP for the cycloaddition of CO2
Reaction conditions: 0.1 MPa CO2, 10 mmol epichlorohydrin, 1 mol%
catalyst, 24 hours. b Determined by GC. c No catalyst was used. with epichlorohydrin.

13290 | Chem. Commun., 2016, 52, 13288--13291 This journal is © The Royal Society of Chemistry 2016

Communication
catalyst exhibited high activity, high selectivity and good recycl-
ability for the cycloaddition of carbon dioxide to produce cyclic
carbonates at atmospheric pressure.
The authors gratefully acknowledge the financial support
from the 973 Program (2014CB845605 and 2013CB933200),
the NSFC (21671188, 21273238, 21521061, and 21331006), the
Strategic Priority Research Program of the Chinese Academy of
Published on 19 October 2016. Downloaded by National University of Kaohsiung on 11/23/2020 2:42:31 AM.
Sciences (XDB20000000), the Youth Innovation Promotion
Association, CAS (2014265), and the Chunmiao Project of the Haixi
Institute of the Chinese Academy of Sciences (CMZX-2014-004).
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