Letter

pubs.acs.org/journal/ascecg

State-of-the-Art Multifunctional Heterogeneous POP Catalyst for

Cooperative Transformation of CO2 to Cyclic Carbonates
Wenlong Wang,†,∥ Yuqing Wang,†,§,∥ Cunyao Li,† Li Yan,*,† Miao Jiang,† and Yunjie Ding*,†,‡
†
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan
Road, Dalian 116023, China
‡
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian
116023, China
§
University of Chinese Academy of Sciences, 19 Yuquan Road, Shijingshan District, Beijing 100049, China
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*
S Supporting Information
Downloaded via NATL UNIV OF KAOHSIUNG on November 23, 2020 at 02:36:49 (UTC).

ABSTRACT: A single-component multifunctional catalyst (de-

noted as Mg-por/pho@POP) based on a magnesium porphyrin
and phosphonium salt-integrated porous organic polymer (POP)
was afforded via a solvothermal synthetic technique for cyclic
carbonate production which uses epoxides and CO2. In
consequence of the cooperative (or synergistic) effect of a
phosphonium salt and homogeneously dispersed magnesium
porphyrin moiety, which is possibly reinforced through the flexible
frameworks and confined microporous structure, this powerful
catalyst offered the highest activity of a heterogeneous catalyst
within the context of cyclic carbonates synthesis from epoxide and
CO2 (turnover frequencies up to 15,600 h−1) without the addition
of co-catalysts. More surprisingly, very promising turnover
numbers (TONs) of 14,400 and 4200 were realized at very mild
temperatures of 25 and 40 °C. Moreover, Mg-por/pho@POP can be simply recovered and reused at least five times.
KEYWORDS: Carbon dioxide, Polymeric catalyst, Heterogeneous catalyst, Cooperative catalysis, Cyclic carbonates

■ INTRODUCTION
Carbon dioxide, a main kind of greenhouse gas, has increased
more than 37% since preindustrial times, from 280 ppm by
volume (ppmv) to more than 400 ppmv today, and has resulted
serious environmental problems, such as global warming and
sea-level rise.1 On the other hand, CO2 is an abundant, low-
priced, nontoxic, and sustainable carbon source for the modern
chemical industry.2−4 Therefore, recently, there has been an
explosion in the growth of catalytic reactions that use CO2 as a
feedstock.5−10 In particular, the catalytic cycloaddition of CO2
with epoxides to produce cyclic carbonates, which can be
widely used as polar aprotic solvents, chemical intermediates,
and battery electrolytes, was proved to be an effective way for
the transformation of CO2 into value-added chemicals.11−14
Various homogeneous or heterogeneous catalytic systems
have been established for the cycloaddition of CO2 to
epoxide,15−19 and some catalytic systems exhibit good to
excellent activity, especially for the porphyrin, Salen metal
complexes as well as amino-phenolate-coordinated com-
plexes.20−33 However, organic ammonium salts or ionic liquids
acting as separate co-catalysts are usually required, which
increases the cost and calls for a cumbersome purification
process. As an improved catalyst model, integrating porphyrin
or a Salen-metal complex and organic ammonium into one
complex to form a bifunctional catalyst exhibits very high
efficiency.34−40 Nevertheless, these homogeneous catalysts
suffered from complicated synthesis and intricate recycling
problems, while the use of porous heterogeneous catalytic
materials could overcome this problem.41
Porous organic polymers (POPs) have attracted a lot of
attention due to their porous structures comprising various
organic functional groups which, in theory, could bring
numerous combinational structures. The combination of
numerous secondary synthons into a microporous three-
dimensional grid structure using very robust organic covalent
bonds, definitely, can afford stable polymeric materials with
exceptional chemical and thermal stability, high surface areas,
and versatile chemical functionalities.42−45 A wide range of
POPs materials have been developed for requests in many
areas, especially for catalysis and gas storage.46−48 More
recently, a few works of employing metal-functionalized porous
organic polymers which integrate valued physical and chemical
properties, for example, both of gas storage and catalytic
efficiency, have been published. For instance, biomimetic
Received: March 29, 2017
Revised: May 1, 2017
Published: May 9, 2017

© 2017 American Chemical Society 4523 DOI: 10.1021/acssuschemeng.7b00947

ACS Sustainable Chem. Eng. 2017, 5, 4523−4528
ACS Sustainable Chemistry & Engineering
catalytic metalloporphyrin-based POPs for the thiols oxidation
by using oxygen gas was developed by Jiang’s group, and this
catalyst exhibits excellent activity.49 Highly competent Rh/PPh3
POPs for the hydroformylation process have been successively
reported by Xiao’s and our group.50−52 Similar integration of
the CO2-philic group and metal−organic species in porous
organic polymers may result in this kind of catalyst possessing
both the ability of CO2 sorption and its simultaneous catalytic
conversion.
Considering the reported high efficiency of a porphyrin metal
complex in the reaction of epoxides and CO2 to produce cyclic
carbonates and the CO2 capture ability of N and P atom-doped
POPs,53−55 herein, in this work, we demonstrate a single-
component multifunctional catalyst based on a magnesium
porphyrin and phosphonium salt-integrated porous organic
polymer (Mg-por/pho@POP) prepared through solvothermal
technique. This kind of polymerization is a free radical-
triggered polymerization between a vinyl-functionalized
magnesium porphyrin and phosphonium salt moiety under
hydrothermal similar solvothermal conditions without stirring
(Scheme 1). This is the first example of POP that contains
multifunctional groups of metalloporphyrin and phosphonium
salt.
Scheme 1. Synthesis of Mg-por/pho@POP
■
RESULTS AND DISCUSSION
Catalyst Synthesis and Characterization. As illustrated
in Scheme 1, the target catalyst Mg-por/pho@POP can be
easily obtained from the copolymerization of a vinyl-function-
alized Mg-porphyrin complex and vinyl-functionalized phos-
phonium salt in DMF solution under solvothermal conditions
(without stirring) with quantitative yield (for details, see
Scheme S1). The vinyl-functionalized metalloligand Mg-
porphyrin monomer was synthesized from the reaction of
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porphyrin and MgBr2·OEt2 (Scheme S2), whereas vinyl-
functionalized phosphonium salt was synthesized from vinyl-
functionalized PPh3 and bromoethane (Scheme S3).54 The
synthesized Mg-por/pho@POP is stable in an air atmosphere,
and their structure and composition information were
determined through solid-state 13C, 31P nuclear magnetic
resonance (NMR), and inductively coupled plasma (ICP)
analysis.
As shown in the spectrum of solid-state 13C NMR (Figure 1),
the signals from 131 to 150 ppm show the carbon peak of
Figure 1. Solid-phase 13
C NMR spectra of Mg-por/pho@POP, “∗”
represents sidebands.
aromatic groups (including benzene and pyrrole rings), and the
peaks at 29 and 42 ppm are related to those of polymerized
vinyl groups. In addition, the peak at about 7 ppm could be
ascribed to the ethyl group of a phosphonium salt monomer.
The solid-state 31P NMR spectrum of Mg-por/pho@POP
shows a peak of 24 ppm which is attributed to the P element of
the phosphonium salt monomer (Figure S1). The inductively
coupled plasma (ICP) atomic emission spectrometer showed
that the Mg content of Mg-por/pho@POP was 0.38 wt %,
which was close to theoretic value of 0.45 wt %.
The N2 adsorption isotherm and pore width distribution
plots which were calculated from nonlocal density functional
theory (NLDFT) of Mg-por/pho@POP are shown in Figure 2.
The synthesized porous organic polymer displays a moderately
high Brunauer−Emmett−Teller (multipoint BET, P\P0 = 0.1−
0.3, Figure S2) surface area of 558 m2/g and a total pore
volume of 0.55 cm3/g. The pore width distribution plot (Figure
2B) indicates that pore sizes of the POP material are mainly
distributed in a micropore region (<2 nm), and a small portion
of mesopores (from 2 to 10 nm) were formed. A representative
field-emission scanning electron micrograph (Figure 3A, FE-
SEM) and transmission electron micrograph (Figure 3B, TEM)
images of Mg-por/pho@POP further prove that this material
possesses developed hierarchical porosities and rough surfaces,
and this porous structural property must be very positive when
the reactant and product diffuses in the pores in the reaction
process, particularly for the service of gas-involved reactions.
Elemental distribution of catalyst Mg-por/pho@POP was
tested by the energy-dispersive X-ray spectroscopy (EDX)
mapping method in SEM (Figure S3). The homogeneously
distributed character of functional elements (Mg, Br, N, and P)
exhibits the well integration of highly dispersed active
functional elements. This sort of integration in micropores
DOI: 10.1021/acssuschemeng.7b00947
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ACS Sustainable Chemistry & Engineering Letter

Figure 2. (A) N2 sorption isotherm at 77 K. (B) Pore-size distribution curves calculated by NLDFT method.

Figure 3. (A) SEM image of Mg-por/pho@POP. (B) TEM image of Mg-por/pho@POP.

generates a very advantageous cooperative environment for the Table 1. Mg-por/pho@POP-Catalyzed CO2 Conversion
CO2 conversion process, and this efficient process is fully with Epoxides to Cyclic Carbonatesa
discussed below. Moreover, the thermal gravimetric analysis
(TGA) result reveals that the weight loss of Mg-por/pho@POP
starts from 300 °C (Figure S4), which shows that the POP
catalyst is thermally stable under 300 °C.
It is worthwhile to notice the following: (1) The nitrogen-
and phosphine-rich backbone could increase the adsorption of
CO2, thus enhancing the “CO2 capture” ability.53−55 (2) The
substrates can be sequestered and confined by the porous
entry epoxide PCO2b [MPa] T [°C] yield [%] TOF [h−1]
organic polymers in the nanometer-sized pores, and thus, the c
concentration of substrates around the active catalytic sites is 1 1 1 120 48 9600
higher than that in homogeneous solution state.44 (3) The vinyl 2c 1 2 120 53 10600
3c 1 3 120 62 12,400
porous polymers which were synthesized via a solvothermal
4c,d 1 3 120 N. R. ―
technique display excellent swelling properties; the swollen
5c,e 1 3 120 3 600
polymers can be considered as solution in part, although
6c 1 3 100 55 11,000
actually they are flexible solids instead of liquids.51 All these
7c 1 3 140 78 15,600
favorable properties fully clarified the outstanding activity
8f 2 3 140 67 13,400
(Table 1) of the integrated multifunctional POP catalyst.
9f 3 3 140 36 7200
The catalytic activity of Mg-por/pho@POP was then
10f 4 3 140 30 6000
evaluated by the cycloaddition reaction of CO2 with propylene
11c,g 1 3 140 90 9000
oxide to produce a cyclic carbonate without the addition of any a
additive (Table 1, for experimental details, see Scheme S4). For Reaction conditions: epoxide (160 mmol), catalyst Mg-por/pho@
comparison, another control catalyst of poly(phosphonium POP (50 mg), substrate/catalyst = 20,000 (catalyst amount equal to
the amount to magnesium porphyrin complex, which is calculated
salt) was prepared (Scheme S5). First, reaction conditions such
from Mg content of ICP test). Reaction times: 1 h. The selectivities for
as the pressure of CO2 and temperature were screened. Mg- the cyclic carbonate products of all results are >98%. bPressure was
por/pho@POP showed excellent dispersion ability in propy- consistent and realized by pressure regulating valve. cYield was
lene oxide. Considering the low density of Mg-por/pho@POP, determined by GC analysis with an internal standard of n-butyl
50 mg of catalyst (0.008 mmol and 0.005% porphyrin-Mg alcohol. dNo catalyst. eCatalyst = poly(phosphonium salt). fIsolated
moieties for substrates, S/C = 20,000) for 160 mmol epoxides yields. g2 h.
was used. The carbon dioxide pressure was investigated
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between 1 and 3 MPa at 120 °C (Table 1, entry 1−3), and the
yields and turnover frequencies (TOF) were increased from
48% to 62% and 9600 to 12,400 h−1, respectively, while
increasing the CO2 pressure from 1 to 3 MPa at 120 °C. With
the optimized pressure of 3 MPa, the temperature conditions of
100 and 140 °C were further evaluated. When the temperature
was reduced from 120 to 100 °C at 3 MPa, the yields were
reduced from 62% to 55% (Table 1, entry 6). When the
reaction temperature was increased to 140 °C at 3 MPa, an
ultrahigh TOF value of 15,600 h−1 was acquired (Table 1, entry
7), which is the state-of-the-art TOF value of the heteroge-
neous catalytic system. Prolonging the reaction time to 2 h, a
high yield of 90% was achieved (Table 1, entry 11). Under
these reaction conditions, without catalysts, no cyclic
carbonates were formed (Table 1, entry 4). When the control
catalyst of poly(phosphonium salt) was used, only 3% yield of
cyclic carbonates was obtained (Table 1, entry 5), which
implies the necessity of porphyrin-Mg(II) species. The
recovered Mg-por/pho@POP showed nearly the same
reactivity as the original, and the porous polymeric catalyst
can be simply recovered and reused at least five times by simple
centrifugation (Figure 4). Also, an ICP test of the recovered
Figure 4. Recyclability test of Mg-por/pho@POP. Reaction
conditions: propylene oxide (160 mmol), 140 °C, 3 MPa, 50 mg of
catalyst, substrate/catalyst = 20,000 (catalyst amount equal to the
amount to magnesium porphyrin complex), 1 h.
catalyst of the fifth run displayed 0.37 wt % of Mg content
which is very close to the value of a fresh sample, 0.38 wt %.
Other substrates of epichlorohydrin, styrene oxide, and 1,2-
epoxyhexane were also examined, and epichlorohydrin could be
transformed into cyclic carbonate in high efficiency (TOF =
13,400 h−1, Table 1, entry 8). However, styrene oxide and 1,2-
epoxyhexane displayed a comparatively low reactivity (TOF =
7200 and 6000 h−1, respectively, Table 1, entries 9 and 10),
which is most probably a result of the steric hindrance effect
and electronic effect56 of styrene oxide and a big molecular size
of 1,2-epoxyhexane. Worth noting is that all the selectivities of
these reactions are greater than 98%, even for the high
temperature of 140 °C, which is probably ascribed to the high
concentration of CO2 in the micropores of POPs materials.
Although our heterogeneous POPs catalyst displays excep-
tionally high efficiency in cyclic carbonates synthesis from CO2
at high temperatures, it is very attractive that the catalyst used
in the process be capable of converting CO2 at very low
temperature with heat from the neighboring environment to
circumvent the production of extra CO2. Unfortunately, up to
now, few promising outcomes have been described. In 2013,
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Deng reported a relatively high efficient catalyst, and a TON
result around 200 was achieved at 25 °C concerning this
reaction.25 More recently, Ema and co-workers described a
bifunctional homogeneous porphyrin-Zn(II) complex, which
obtained a TON value of 1640 at 20 °C and 1 atm.57 Hereby,
our catalyst was tested in this conversion at 25 and 40 °C
(Table 2). A very high TON value of 14400 was achieved when
Table 2. Catalytic Activities of Mg-por/pho@POP in
Conversion of CO2 to Cyclic Carbonates at 25 and 40 °Ca
entry PCO2b [MPa] T [°C] yieldc [%] TOF [h−1] TON
1 1 40 72 300 14400
2 1 25 21 87.5 4200
3 0.5 40 56 233 11,200
4 0.5 25 17 71 3400
5 0.1 25 12 50 2400
a
Reaction conditions: epoxide (160 mmol), catalyst Mg-por/pho@
POP (50 mg), substrate/catalyst = 20,000 (catalyst amount equal to
the amount to magnesium porphyrin complex, which is calculated
from Mg content of ICP test). The selectivities for the cyclic carbonate
products of all results are >98%. bPressure was consistent and realized
by pressure regulating valve. cYield was determined by GC analysis
with an internal standard of n-butyl alcohol.
the conversion was performed at a very mild temperature of 40
°C (Table 2, entry 1), a TON value of 4200 was attained at an
even low temperature condition of 25 °C (Table 2, entry 2).
When the pressure was decreased from 1 to 0.5 MPa at 40 and
25 °C, the TON value were reduced to 11200 and 3400,
respectively (Table 2, entry 3 and 4). Finally, when the reaction
was carried out under ambient conditions (25 °C, 1 atm), a
TON value of 2400 was still obtained (Table 2, entry 5). These
investigations clearly show that Mg-por/pho@POP could be a
real energy-saving and CO2 alleviating catalyst.
On the basis of our experimental observations and literature
results, a mechanism of cooperative activation process was
suggested for this catalytic transformation of CO2 to cyclic
carbonates. During the catalysis process, the Mg-porphyrin
moiety in Mg-por/pho@POP acted as a Lewis acid, and the
bromine anion served as a nucleophile, whereas the P and N
atoms play a role of “CO2 catcher”. As shown in Scheme 2, an
epoxide could be activated by the Mg-porphyrin site and
generate an intermediate with a strong δ− charge in the porous
polymer’s confined micropores, thereupon a nucleophilic attack
at the less steric carbon atom (which was from the Br−)
generates an alcoholate; following one more nucleophilic attack
from the alcoholate intermediate toward CO2, another
intermediate of acyclic carbonate can be produced. Then, the
acyclic carbonate goes through an intramolecular substitution
reaction, finally producing a cyclic carbonate product, and the
integral Mg-por/pho@POP catalyst was liberated.
In summary, a novel multifunctional porous organic polymer
Mg-por/pho@POP-integrating porphyrin-Mg moiety and
phosphonium salt was first afforded through solvothermal
synthesis of free radical polymerization. Without any co-
catalyst, the porous heterogeneous catalyst exhibited ultrahigh
activity (TOF up to 15,600 h−1 with a high yield of 78%), high
selectivity, and good recyclability for the cycloaddition of CO2
DOI: 10.1021/acssuschemeng.7b00947
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ACS Sustainable Chemistry & Engineering
Scheme 2. Possible Dual-Activation, Cooperative Reaction
Mechanism
and epoxides to produce cyclic carbonates. More importantly,
very promising turnover numbers of 14,400 and 4200 were
achieved at 25 and 40 °C, respectively. The synthetic strategy of
the multifunctional POPs material discussed in this communi-
cation holds potential for designing other multifunctional
catalysts for highly efficient catalytic processes.
■
ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.7b00947.
Synthesis of vinyl-functionalized porphyrin-Mg(II) com-
plex, synthesis of Mg-por/pho@POP, synthesis of
poly(phosphonium salt), general synthetic procedure of
cyclic carbonates and NMR of product (PDF). (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*Li Yan. Fax: +86 411-8437-9143. E-mail: yanli@dicp.ac.cn.
*Yunjie Ding. Fax: +86 411-8437-9143 E-mail: dyj@dicp.ac.cn.
ORCID
Yunjie Ding: 0000-0001-8894-9648
Author Contributions
∥ 255, 1460−1479.
Wenlong Wang and Yuqing Wang have contributed equally.
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Funding
National Science Fundation of China (21403258, 21273227,
and 21503218), Strategic Priority Research Program of the
4527
Letter
Chinese Academy of Sciences (XDB17020400), and China
Postdotoral Science Fundation (2016M590239).
Notes
The authors declare no competing financial interest.
■ REFERENCES
(1) Haszeldine, R. S. Carbon Capture and Storage: How Green Can
Black Be? Science 2009, 325, 1647−1652.
(2) Sakakura, T.; Choi, J.-C.; Yasuda, H. Transformation of Carbon
Dioxide. Chem. Rev. 2007, 107, 2365−2387.
(3) Omae, I. Aspects of carbon dioxide utilization. Catal. Today 2006,
115, 33−52.
(4) Aresta, M.; Dibenedetto, A.; Angelini, A. Catalysis for the
Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials,
and Fuels. Technological Use of CO2. Chem. Rev. 2014, 114, 1709−
1742.
(5) Banerjee, A.; Dick, G. R.; Yoshino, T.; Kanan, M. W. Carbon
dioxide utilization via carbonate-promoted C−H carboxylation. Nature
2016, 531, 215−219.
(6) Börjesson, M.; Moragas, T.; Gallego, D.; Martin, R. Metal-
Catalyzed Carboxylation of Organic (Pseudo)halides with CO2. ACS
Catal. 2016, 6, 6739−6749.
(7) Ye, J.-H.; Song, L.; Zhou, W.-J.; Ju, T.; Yin, Z.-B.; Yan, S.-S.;
Zhang, Z.; Li, J.; Yu, D.-G. Selective Oxytrifluoromethylation of
Allylamines with CO2. Angew. Chem., Int. Ed. 2016, 55, 10022−10026.
(8) Zall, C. M.; Linehan, J. C.; Appel, A. M. Triphosphine-Ligated
Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and
Thermodynamic Studies. J. Am. Chem. Soc. 2016, 138, 9968−9977.
(9) Carry, B.; Zhang, L.; Nishiura, M.; Hou, Z. Synthesis of Lithium
Boracarbonate Ion Pairs by Copper-Catalyzed Multi-Component
Coupling of Carbon Dioxide, Diboron, and Aldehydes. Angew.
Chem., Int. Ed. 2016, 55, 6257−6260.
(10) Jin, G.; Werncke, C. G.; Escudié, Y.; Sabo-Etienne, S.;
Bontemps, S. Iron-Catalyzed Reduction of CO2 into Methylene:
Formation of C−N, C−O, and C−C Bonds. J. Am. Chem. Soc. 2015,
137, 9563−9566.
(11) Schäffner, B.; Schäffner, F.; Verevkin, S. P.; Börner, A. Organic
Carbonates as Solvents in Synthesis and Catalysis. Chem. Rev. 2010,
110, 4554−4581.
(12) Darensbourg, D. J. Making Plastics from Carbon Dioxide: Salen
Metal Complexes as Catalysts for the Production of Polycarbonates
from Epoxides and CO2. Chem. Rev. 2007, 107, 2388−2410.
(13) Shaikh, A.-A. G.; Sivaram, S. Organic Carbonates. Chem. Rev.
1996, 96, 951−976.
(14) Clements, J. H. Reactive Applications of Cyclic Alkylene
Carbonates. Ind. Eng. Chem. Res. 2003, 42, 663−674.
(15) North, M.; Pasquale, R.; Young, C. Synthesis of cyclic
carbonates from epoxides and CO2. Green Chem. 2010, 12, 1514−
1539.
(16) Martín, C.; Fiorani, G.; Kleij, A. W. Recent Advances in the
Catalytic Preparation of Cyclic Organic Carbonates. ACS Catal. 2015,
5, 1353−1370.
(17) Lu, X.-B.; Darensbourg, D. J. Cobalt catalysts for the coupling of
CO2 and epoxides to provide polycarbonates and cyclic carbonates.
Chem. Soc. Rev. 2012, 41, 1462−1484.
(18) Kember, M. R.; Buchard, A.; Williams, C. K. Catalysts for CO2/
epoxide copolymerisation. Chem. Commun. 2011, 47, 141−163.
(19) Klaus, S.; Lehenmeier, M. W.; Anderson, C. E.; Rieger, B.
Catalysts for CO2/epoxide copolymerisation. Coord. Chem. Rev. 2011,
(20) Castro-Osma, J. A.; North, M.; Wu, X. Development of a
Halide-Free Aluminium-Based Catalyst for the Synthesis of Cyclic
Carbonates from Epoxides and Carbon Dioxide. Chem. - Eur. J. 2014,
20, 15005−15008.
(21) Paddock, R. L.; Nguyen, S. T. Chemical CO2 Fixation: Cr(III)
Salen Complexes as Highly Efficient Catalysts for the Coupling of CO2
and Epoxides. J. Am. Chem. Soc. 2001, 123, 11498−11499.
DOI: 10.1021/acssuschemeng.7b00947
ACS Sustainable Chem. Eng. 2017, 5, 4523−4528
ACS Sustainable Chemistry & Engineering
(22) Paddock, R. L.; Hiyama, Y.; Mckay, J. M.; Nguyen, S. T. Co(III)
porphyrin/DMAP: an efficient catalyst system for the synthesis of
cyclic carbonates from CO2 and epoxides. Tetrahedron Lett. 2004, 45,
2023−2026.
(23) Jin, L.; Jing, H.; Chang, T.; Bu, X.; Wang, L.; Liu, Z. Metal
porphyrin/phenyltrimethylammonium tribromide: High efficient
catalysts for coupling reaction of CO2 and epoxides. J. Mol. Catal. A:
Chem. 2007, 261, 262−266.
(24) Qin, Y.; Guo, H.; Sheng, X.; Wang, X.; Wang, F. An aluminum
porphyrin complex with high activity and selectivity for cyclic
carbonate synthesis. Green Chem. 2015, 17, 2853−2858.
(25) Xie, Y.; Wang, T.-T.; Liu, X.-H.; Zou, K.; Deng, W.-Q. Capture
and conversion of CO2 at ambient conditions by a conjugated
microporous polymer. Nat. Commun. 2013, 4, 1960.
(26) Chun, J.; Kang, S.; Kang, N.; Lee, S. M.; Kim, H. J.; Son, S. U.
Microporous organic networks bearing metal-salen species for mild
CO2 fixation to cyclic carbonates. J. Mater. Chem. A 2013, 1, 5517−
5523.
(27) Castro-Osma, J. A.; North, M.; Offermans, W. K.; Leitner, W.;
Müller, T. E. Unprecedented Carbonato Intermediates in Cyclic
Carbonate Synthesis Catalysed by Bimetallic Aluminium(Salen)
Complexes. ChemSusChem 2016, 9, 791−794.
(28) Dai, Z.; Sun, Q.; Liu, X.; Bian, C.; Wu, Q.; Pan, S.; Wang, L.;
Meng, X.; Deng, F.; Xiao, F.-S. Metalated porous porphyrin polymers
as efficient heterogeneous catalysts for cycloaddition of epoxides with
CO2 under ambient conditions. J. Catal. 2016, 338, 202−209.
(29) Xie, Y.; Wang, T.-T.; Yang, R.-X.; Huang, N.-Y.; Zou, K.; Deng,
W.-Q. Efficient Fixation of CO2 by a Zinc-Coordinated Conjugated
Microporous Polymer. ChemSusChem 2014, 7, 2110−2114.
(30) Alkordi, M. H.; Weseliński, Ł. J.; D’Elia, V.; Barman, S.; Cadiau,
A.; Hedhili, M. N.; Cairns, A. J.; AbdulHalim, R. G.; Basset, J.-M.;
Eddaoudi, M. CO2 conversion: the potential of porous-organic
polymers (POPs) for catalytic CO2−epoxide insertion. J. Mater.
Chem. A 2016, 4, 7453−7460.
(31) Wu, X.; North, M. A Bimetallic Aluminium(Salphen) Complex
for the Synthesis of Cyclic Carbonates from Epoxides and Carbon
Dioxide. ChemSusChem 2017, 10, 74−78.
(32) Maeda, C.; Taniguchi, T.; Ogawa, K.; Ema, T. Bifunctional
Catalysts Based on m-Phenylene-Bridged Porphyrin Dimer and
Trimer Platforms: Synthesis of Cyclic Carbonates from Carbon
Dioxide and Epoxides. Angew. Chem., Int. Ed. 2015, 54, 134−138.
(33) Kleij, A. W.; Rintjema, J. Aluminum-Mediated Formation of
Cyclic Carbonates: Benchmarking Catalytic Performance Metrics.
ChemSusChem 2017, 10, 1274−1282.
(34) Whiteoak, C. J.; Kielland, N.; Laserna, V.; Escudero-Adán, E. C.;
Martin, E.; Kleij, A. W. A Powerful Aluminum Catalyst for the
Synthesis of Highly Functional Organic Carbonates. J. Am. Chem. Soc.
2013, 135, 1228−1231.
(35) North, M.; Young, C. Reducing the Cost of Production of
Bimetallic Aluminium Catalysts for the Synthesis of Cyclic Carbonates.
ChemSusChem 2011, 4, 1685−1693.
(36) Castro-Osma, J. A.; North, M.; Wu, X. Synthesis of Cyclic
Carbonates Catalysed by Chromium and Aluminium Salphen
Complexes. Chem. - Eur. J. 2016, 22, 2100−2107.
(37) Ema, T.; Miyazaki, Y.; Shimonishi, J.; Maeda, C.; Hasegawa, J.
Bifunctional Porphyrin Catalysts for the Synthesis of Cyclic
Carbonates from Epoxides and CO2: Structural Optimization and
Mechanistic Study. J. Am. Chem. Soc. 2014, 136, 15270−15279.
(38) Tian, D.; Liu, B.; Gan, Q.; Li, H.; Darensbourg, D. J. Formation
of Cyclic Carbonates from Carbon Dioxide and Epoxides Coupling
Reactions Efficiently Catalyzed by Robust, Recyclable One-Compo-
nent Aluminum-Salen Complexes. ACS Catal. 2012, 2, 2029−2035.
(39) Duan, S.; Jing, X.; Li, D.; Jing, H. Catalytic asymmetric
cycloaddition of CO2 to epoxides via chiral bifunctional ionic liquids. J.
Mol. Catal. A: Chem. 2016, 411, 34−39.
(40) Meléndez, J.; North, M.; Villuendas, P. One-component
catalysts for cyclic carbonate synthesis. Chem. Commun. 2009,
2577−2579.
4528
Letter
(41) Luo, R.; Chen, Y.; He, Q.; Lin, X.; Xu, Q.; He, X.; Zhang, W.;
Zhou, X.; Ji, H. Metallosalen-Based Ionic Porous Polymers as
Bifunctional Catalysts for the Conversion of CO2 into Valuable
Chemicals. ChemSusChem 2017, 10, 1526.
(42) Kaur, P.; Hupp, J. T.; Nguyen, S. T. Porous Organic Polymers in
Catalysis: Opportunities and Challenges. ACS Catal. 2011, 1, 819−
835.
(43) Zhang, Y.; Ying, J. Y. Main-Chain Organic Frameworks with
Advanced Catalytic Functionalities. ACS Catal. 2015, 5, 2681−2691.
(44) Sun, Q.; Dai, Z.; Meng, X.; Wang, L.; Xiao, F.-S. Task-Specific
Design of Porous Polymer Heterogeneous Catalysts beyond
Homogeneous Counterparts. ACS Catal. 2015, 5, 4556−4567.
(45) Slater, A. G.; Cooper, A. I. Function-led design of new porous
materials. Science 2015, 348, aaa8075.
(46) Liu, G.; Wang, Y.; Shen, C.; Ju, Z.; Yuan, D. A facile synthesis of
microporous organic polymers for efficient gas storage and separation.
J. Mater. Chem. A 2015, 3, 3051−3058.
(47) Ullah, R.; Atilhan, M.; Anaya, B.; Al-Muhtaseb, S.; Aparicio, S.;
Patel, H.; Thirion, D.; Yavuz, C. T. Investigation of Ester- and Amide-
Linker-Based Porous Organic Polymers for Carbon Dioxide Capture
and Separation at Wide Temperatures and Pressures. ACS Appl. Mater.
Interfaces 2016, 8, 20772−20785.
(48) Arab, P.; Parrish, E.; islamoglu, T.; El-Kaderi, H. M. Synthesis
and evaluation of porous azo-linked polymers for carbon dioxide
capture and separation. J. Mater. Chem. A 2015, 3, 20586−20594.
(49) Chen, L.; Yang, Y.; Jiang, D. CMPs as Scaffolds for Constructing
Porous Catalytic Frameworks: A Built-in Heterogeneous Catalyst with
High Activity and Selectivity Based on Nanoporous Metalloporphyrin
Polymers. J. Am. Chem. Soc. 2010, 132, 9138−9143.
(50) Sun, Q.; Jiang, M.; Shen, Z.; Jin, Y.; Pan, S.; Wang, L.; Meng, X.;
Chen, W.; Ding, Y.; Li, J.; Xiao, F.-S. Porous organic ligands (POLs)
for synthesizing highly efficient heterogeneous catalysts. Chem.
Commun. 2014, 50, 11844−11847.
(51) Sun, Q.; Dai, Z.; Liu, X.; Sheng, N.; Deng, F.; Meng, X.; Xiao,
F.-S. Highly Efficient Heterogeneous Hydroformylation over Rh-
Metalated Porous Organic Polymers: Synergistic Effect of High Ligand
Concentration and Flexible Framework. J. Am. Chem. Soc. 2015, 137,
5204−5209.
(52) Li, C.; Yan, L.; Lu, L.; Xiong, K.; Wang, W.; Jiang, M.; Liu, J.;
Song, X.; Zhan, Z.; Jiang, Z.; Ding, Y. Single atom dispersed Rh-
biphephos&PPh3@porous organic copolymers: highly efficient cata-
lysts for continuous fixed-bed hydroformylation of propene. Green
Chem. 2016, 18, 2995−3005.
(53) Wang, J.; Yang, J. G. W.; Yi, G.; Zhang, Y. Phosphonium salt
incorporated hypercrosslinked porous polymers for CO2 capture and
conversion. Chem. Commun. 2015, 51, 15708−15711.
(54) Li, C.; Wang, W.; Yan, L.; Wang, Y.; Jiang, M.; Ding, Y.
Phosphonium salt and ZnX2−PPh3 integrated hierarchical POPs:
tailorable synthesis and highly efficient cooperative catalysis in CO2
utilization. J. Mater. Chem. A 2016, 4, 16017−16027.
(55) Wang, W.; Li, C.; Yan, L.; Wang, Y.; Jiang, M.; Ding, Y. Ionic
Liquid/Zn-PPh3 Integrated Porous Organic Polymers Featuring
Multifunctional Sites: Highly Active Heterogeneous Catalyst for
Cooperative Conversion of CO2 to Cyclic Carbonates. ACS Catal.
2016, 6, 6091−6100.
(56) Castro-Gómez; Salassa, G.; Kleij, A. W.; Bo, C. A DFT Study on
the Mechanism of the Cycloaddition Reaction of CO2 to Epoxides
Catalyzed by Zn(Salphen) Complexes. Chem. - Eur. J. 2013, 19, 6298−
6289.
(57) Maeda, C.; Shimonishi, J.; Miyazaki, R.; Hasegawa, J.-y.; Ema, T.
Highly Active and Robust Metalloporphyrin Catalysts for the
Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and
Carbon Dioxide. Chem. - Eur. J. 2016, 22, 6556−6563.
DOI: 10.1021/acssuschemeng.7b00947
ACS Sustainable Chem. Eng. 2017, 5, 4523−4528