Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Recent Advances on Imidazolium-Functionalized Organic

Cationic Polymers for CO2 Adsorption and Simultaneous
Conversion into Cyclic Carbonates

Authors: Rongchang Luo, Xiangying Liu, Min Chen, Baoyu Liu, and
Yanxiong Fang

This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.

To be cited as: ChemSusChem 10.1002/cssc.202001079

Link to VoR: https://doi.org/10.1002/cssc.202001079

01/2020
ChemSusChem 10.1002/cssc.202001079

REVIEW
Recent Advances on Imidazolium-Functionalized Organic
Cationic Polymers for CO2 Adsorption and Simultaneous
Conversion into Cyclic Carbonates

Rongchang Luo,*[a] Xiangying Liu, [a] Min Chen, [a] Baoyu Liu, [a] and Yanxiong Fang [a]

Accepted Manuscript

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ChemSusChem 10.1002/cssc.202001079

REVIEW
[a] Dr. RC Luo, XY Liu, M Chen, Dr. BY Liu, Prof. YX Fang
School of Chemical Engineering and Light Industry
Guangdong University of Technology
Guangzhou 510006, China
E-mail: luorch@gdut.edu.cn

Abstract: The cycloaddition reaction of CO2 with various epoxides to
generate cyclic carbonates is one of the most promising and efficient
approaches for CO2 fixation. Typical imidazolium-based ionic liquids
possessing the electrophilic cations and nucleophilic halogen anions,
have been identified as excellent and environment-friendly candidates
for synergistically activating epoxides to convert CO2. Therefore, the
feasible construction of a series of imidazolium-functionalized
organic cationic polymers can bridge the gap between
phosphine salts, organic bases, ionic liquids (ILs), etc.) to
heterogeneous catalysts (metal oxides, porous inorganic
materials, metal-organic frameworks (MOFs), covalent
organic frameworks (COFs), porous organic polymers
(POPs), etc.). It’s well known that heterogeneous catalysts
have significant advantages in product separation and
catalyst recycling, and sometime even exhibit higher catalytic

Accepted Manuscript
homogeneous and heterogeneous catalysis, thereby obtaining activities than homogeneous counterparts. Among them,
highly selective CO2 adsorption and simultaneous conversion imidazolium-functionalized organic cationic polymers as a
ability. This review describes the recent advancements with class of a new emerging POPs, have been developed during
regard to the design and synthesis of this type of polymeric the past several years, which are expected to bridge the gap
networks having imidazolium functionality that considered as an
between homogeneous and heterogeneous catalysis in the
eminent heterogeneous catalyst for the cycloaddition of CO 2 to
epoxides. Based on the perspective from the design of building
CO2-epoxide coupling reactions (Scheme 1).
blocks to the synthesis of cationic polymers, we mainly focus on
both how to introduce imidazole units into the material backbone
via the covalently-linked approach and how to incorporate other
active sites that may being capable of activating CO 2 and/or
epoxides into such polymeric materials.

1. Introduction
In the past several decades, excessive emission of carbon
dioxide (CO2) from the rapid combustion of fossil energy and
various human activities into the atmosphere may directly
contribute to global climate change. In order to mitigate the
energy and environmental crises caused by CO 2, immense
research efforts have been made to effectively convert the
excess CO2 into high value-added chemicals and fuels.[1]
This fundamental and efficient strategy, also known as
carbon capture and utilization (CCU) technology, can lead to
a win-win situation of carbon footprint recycling on earth and
sustainable chemical production.[2]
CO2 is indeed an abundantly available, inexpensive,
nontoxic and renewable C1 resource for synthetic chemistry.
Due to its inherent thermodynamic stability and kinetic
inertness, various reaction pathways for CO2 fixation often
require the harsh reaction temperature and/or pressure to
overcome the thermodynamic constraints, and how to
achieve the activation of inert CO2 molecule under relatively
less drastic conditions remains challenging.[3] In this context,
there are four main methods to convert CO 2 into diverse
useful chemicals: (i) to use high-energy starting materials
such as epoxides and hydrogen; (ii) to synthesize oxidized
low-energy targeted products such as organic carbonates
and carboxylic acids; (iii) to remove other by-products from
reaction system by altering the chemical equilibrium; and (iv)
to supply additional physical energy such as light and
electricity.[4] Consequently, based on the requirements of
green chemistry and sustainable development, the
production of valuable cyclic carbonates by CO 2
cycloaddition with epoxides is one of the most efficient, atom-
economic and environment benign processes to achieve
catalytic CO2 fixation.[5] To date, a large number of catalysts
have been explored, ranging from homogeneous catalysts
(such as metal complexes, quaternary ammonium or
Scheme 1. Schematic illustration of imidazolium-functionalized
organic cationic polymers
In this review, we first introduce the origin of organic
cationic polymers having imidazolium functionality and
demonstrate their superiorities in comparison to various
kinds of supported inorganic materials and inorganic-organic
hybrid materials modified by imidazolium-based ILs. Then,
these unprecedented inherent structural features of these
functional organic materials are also concluded. In the
following sections, the most recent advancements in the
design and synthesis of imidazolium-functionalized organic
cationic polymers as eminent heterogeneous catalysts for
the cycloaddition of CO 2 with epoxides are summarized, in
which excludes the preparation of porous coordination
polymers having imidazolium-based ILs. Based on the
perspective from the design of building blocks to the
synthesis of cationic polymers (Scheme 1), we mainly focus
on both how to introduce imidazole units into the material
backbone via the covalently-linked approach and how to
incorporate other active sites that may being capable of
activating CO2 and/or epoxides into such polymeric materials.
The typical examples of organic cationic polymers having
imidazolium functionality were discussed in detail. Certainly,
in order to better understand the synthetic strategies and
relevant properties of these materials, a few illustrative

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ChemSusChem
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earlier examples are also introduced and further elaborated.
Finally, we will highlight the effects of pore structure and
polymer matrix on catalytic performance and systematically
analyze the inherent challenges to developing novel organic
functional polymers with task-specific active sites.
2. The Origin and General Features of
Imidazolium-Functionalized Organic
Cationic Polymers
2.1 Catalyst design of CO 2 cycloaddition with epoxides
In practical industrial applications, tetrabutylammonium
bromide (TBAB) was the earliest homogeneous catalyst
used before 2000, but the harsh reaction conditions
(T>220oC, PCO2>8.0MPa) and the instability and toxicity of
catalysts eventually lead to the complicated technological
process and poor product quality as well as high chroma.
Soon afterwards, the second generation binary catalytic
system, i.e. polyethylene glycol (PEG) and potassium iodide
(KI), have been developed to moderate the reaction
conditions (T<200oC, PCO2<6.0MPa) and improve the quality
of product, especially the demand for colour.[6] However,
there are still some unavoidable problems such as the lack
of raw material sources, a sharp rise in catalyst price and the
property of easy coking as well as complexity of reaction
process.
In recent years, the third-generation catalysts including
metal complexes[7] and ILs[8] have been developing rapidly
attribute to the advantages of a succinct process, low price,
catalyst recyclability and energy savings. Academically, CO2
cycloaddition with an epoxide generally involves the
following three steps: (i) ring opening via a nucleophilic attack;
(ii) CO2 insertion into an anion reactive oxygen species; and
(iii) ring closure via an intramolecular cyclic elimination
coupling with the leaving of the nucleophile. [9] Thus it can be
seen that nucleophiles such as typical halogen anions are
used to accelerate the ring opening, which is usually
considered as the rate-determining step of the cycloaddition
reaction from epoxides and CO2.
Scheme 2. Two types of dual activation models of an epoxide
Scheme 2 shows two types of dual activation models of an
epoxide. One is metal catalyst (Lewis acid site) via the metal-
oxygen coordinative bond, the other is hydroxyl- or carboxyl-
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10.1002/cssc.202001079
containing compounds (Brønsted acid site) via the hydrogen
bond. Both of them can interact with weak basicity of oxygen
atoms in the epoxides and exhibit excellent cooperative
effect towards activating the epoxides, in turn, the generation
of reactive open-loop oxy-species presumably could facilitate
CO2 activation and conversion with increasing activity.
In general, it’s exactly based on the basic idea of catalyst
design, various homogeneous and heterogeneous catalysts
have been successfully developed for catalyzing CO2
cycloaddition with epoxides to date.[9-10] Among them, typical
ILs possessing the electrophilic cations and nucleophilic
halogen anions, have been identified as excellent and
Accepted Manuscript
environment-friendly candidates for activating epoxides to
convert CO2,[11] and yet imidazolium-based ILs and their
derivatives as the most important class of ILs, have good
solubility, high stability, favourable CO2-philic nature and
tunable acidity.[12] The acidity of the C2-proton within the
imidazolium ring is able to activate an epoxide through O⋯H
contacts called as hydrogen bond. Simultaneously, the
strong design ability can facilitate the introduction of task-
specific catalytic sites including hydroxyl-, carbonyl-, amino-
groups and metal active centers into the special structure of
catalysts, thereby improving the catalytic efficiency. [8b]
2.2 Supported inorganic materials and inorganic-
organic hybrid materials modified by imidazolium-
based ILs
As we known, homogeneous IL-derived catalysts have
excellent efficiency, but it’s difficult to separate from the
reaction mixture and has obvious drawbacks in catalyst
recovery and product purification, which seriously hinder
their large-scale practical applications. Therefore, a great
variety of heterogeneous IL-modified solid materials have
been constructed by introducing imidazolium-based IL
moieties into silica,[13] SBA-15,[14] MCM-41,[15] metal
oxides,[16] chitosan,[17] cellulose,[18] carbon nanotubes,[19]
graphene oxide,[20] polyhedral oligomeric silsesquioxanes
(POSS),[21] porous coordination polymers (PCPs), [22]
poly(ionic liquid)s (PILs),[23] POPs,[10] and even crystalline
materials such as ZIFs,[24] MOFs,[25] and COFs.[26]
Scheme 3 describes the main features of three kinds of
familiar porous solid materials modified by imidazolium-
based ILs, including supported inorganic materials,
inorganic-organic hybrid materials and functional organic
materials.[10] In this regard, typical immobilization
technologies generally include host-guest encapsulation,
covalent-binding strategy and cross-linking methods.
Unfortunately, the requirement for special groups (e.g.
hydroxyl, carboxyl, amino) on the surface of inorganic solid
materials is essential to obtain the traditional supported or
immobilized catalysts. This strategy having poor modifiability
directly leads to the low content of ILs in the catalytic
materials and the lack of multiple active sites (e.g., acid and
base sites) to synergistically promote the reaction, thus
directly resulting in the demand of relatively harsh reaction
conditions. Moreover, the rapid developments of inorganic-
organic hybrid materials including ZIFs and MOFs provide
the possibility of promoting CO2 adsorption and successive
catalytic conversion. Kinds of imidazolium-based IL
components can be expediently incorporated into the
ChemSusChem
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framework of such porous materials via either “bottom-up”
pre-synthetic approach or post-modification method ascribed
to the remarkable skeleton tunability and surface
functionalization. Notably, their rich porous structure and
higher specific surface area may ensure the accessibility
requirements of active moieties in ILs, and the controllability
of pore size can possibly enhance mass transfer rates and
the selectivity of CO2 adsorption, thus obtaining excellent
catalytic efficiency. These unique characteristics have also
made it possible to convert the diluted CO2 (ab. 15% CO2 in
N2) that is supplied as the exhaust from industrial plants such
as power stations, oil refineries and natural-gas processors.
However, instability of this kind of porous hybrid materials
connected by the coordination bond may cause the leaching
of the IL with the decreased reactivity and stability in the CO2-
involved liquid-phase reactions.
Scheme 3. The main features of three kinds of familiar functional
materials
2.3 Rapid developments of organic functional
materials
The emergence of organic functional materials reflects the
significant development of covalent chemistry and their
extended structures go beyond molecules, thereby offering
an unparalleled advantage of being able to design according
to the requirements of functional groups on a molecular
level.[27] In principle, any desired functionality can be
introduced into the porous materials through atomic-level
control over the structures and compositions. Consequently,
organic functional materials are capable of regulating the
synergistic interactions among reactant molecules for
achieving high efficiency catalysis, in which the cooperative
effect is exactly the strong demand of CO2 cycloaddition with
epoxides.
As a newly-emerging and the most versatile kind of organic
functional materials, the organic macromolecule polymers
have received more and more people's attention recently.
Most of them possess very high molecular weight, nearly-
perfect heterogeneity and fascinating architectural stability
as well as exceptional designability, which is considered as
an ideal heterogeneous catalyst. More appealingly, POPs as
the promising purely organic forms, were characterized by
low density, high surface areas, tunable pore size,
designable catalytic active sites, and satisfactory
physicochemical stability, which usually include polymers of
intrinsic microporosity (PIMs), hyper-crosslinked polymers
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(HCPs), conjugated microporous polymers (CMPs), porous
aromatic frameworks (PAFs), porous polymer networks
(PPN), covalent triazine frameworks (CTFs) and COFs. [28]
Undoubtedly, the exploitation of POPs with high activity and
sufficient stability has great potential for capturing CO 2
molecule and catalyzing the cycloaddition of CO2 to epoxides
under ambient conditions.
Inspired by the underlying principles of CO2 activation, a
combination of abundant CO2-philic moieties and tailored
pore textures as well as multiple catalytic active sites
together to develop the functionalized POPs has been an
important synergistic methodology for CO 2 capture and
Accepted Manuscript
conversion. Facts proved that a wide variety of nitrogen-
containing groups (e.g. amine, imine, triazine, carbazole,
imidazole and azo linkage) have already been validated to
enhance the CO2-philic capacity through either substantial
Lewis acid-base or dipole-quadruple interactions. It has
become a consensus of academic circles that the rational
design of heterogeneous catalysts with task-specific
nucleophiles and CO2-philic moieties is prerequisite for the
CO2 cycloaddition with epoxides. Also, this is easy to
understand that the construction of ionic POPs owning
abundant IL-based moieties in the polymeric skeletons may
provide tremendous opportunities to reach this target due to
the emergence of strong van der Waals forces and
electrostatic interactions between ILs and CO2.[29]
2.4 Overall descriptions of organic cationic polymers
having imidazolium functionality
Ionic POPs (iPOPs) also termed as porous ionic polymers
(PIPs), are a new subclass of organic functional polymers
with charged skeletons and relevant counterions, which
combines the advantages of ionic polymers and porous
materials, and showed extensive applications in many fields
such as adsorption, gas separation, energy storage, and
catalysis.[30] In sharp contrast to charge-neutral porous
polymers, various cationic or anionic moieties including
quaternary ammonium, quaternary phosphonium,
imidazolium, pyridinium, guanidinium cations and borate
anions, have been involved into the material backbones via
a considerable flexibility in monomer building design at the
molecular level.[31] Within this regard, imidazolium salts-
functionalized cationic polymers paired with appropriate
nucleophiles for the charge balance have been conferred as
the most excellent catalysts for the cycloaddition reaction of
CO2 and epoxides, in which the imidazolium cations can
activate CO2, and the customized counterions can promote
the ring opening of the epoxides through a nucleophilic
attack that was known as the rate-determining step in the
cycloaddition reaction. Furthermore, the unique cross-linked
networks would lead to the heterogeneity of polymeric
materials and presented superior stability in the CO 2-
involved liquid-phase reactions. The rational building of
these advanced materials not only provides the possibility to
homogenously incorporating ionic moieties into the porous
polymer backbone with the simple control over the
catalytically active sites, but also can elaborately regulate
cooperative interactions of the functional groups in porous
materials by the task-specific design of building blocks. This
feasible strategy eventually can bridge the gap between
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homogeneous and heterogeneous catalysis, thus obtaining
highly selective CO2 adsorption and simultaneous
conversion ability as well as exhibiting excellent efficiency
(Scheme 3).[32]
Actually, a few recent fundamental researches have
already demonstrated that the high density of ionic sites is
beneficial to conduct the cycloaddition of CO 2 to epoxides
under relatively milder conditions, especially at ambient
conditions. What's more, the appearance of a large number
of micropores in material skeleton enable a high surface area
for deploying enough active sites for CO2 adsorption and
activation, and the higher-level meso- and macropores
facilitate mass transfer during the reaction. But there is plenty
of evidence that the charge interaction tends to bring
intermolecular packing, which decreases the specific surface
area and the pore volume that generate low accessibility of
active sites and the restriction of mass transport. Therefore,
the most promising approaches to construct imidazolium-
functionalized organic cationic polymers featuring large
surface areas and hierarchical pore structures as well as
versatile chemical composition and functions still remains a
great challenge.[29]
3. Design and Synthesis for Imidazolium-
Functionalized Organic Cationic Polymers
In general, imidazolium-functionalized organic cationic
polymers often include two categories of poly(ionic liquid)s
(PILs) and ionic porous organic polymers (iPOPs). Thereinto,
PILs, i.e. polymeric ILs, are a kind of the simple and easy-to-
synthesize organic polymeric materials, which are commonly
fabricated by the incorporation of repeating IL units into the
host polymeric backbone through conventional or controlled
free-radical polymerization. Both the imidazolium groups and
other active sites are located in the main chain of the polymer.
However, this method strongly depends on the types of
different alkene functional groups on the imidazolium rings
and often involved the employment of additional additives
such as azoisobutyronitrile (AIBN). Besides, other synthetic
approaches of functionalized poly(imidazolium) salts have
also been extended and carefully studied.
Thanks to the diverse and versatile building blocks and
polymerization pathways, the wide range of synthetic
methods (e.g. Schiff-base condensation, Friedel−Crafts
alkylation, click chemistry, coupling reaction, free-radical
polymerization, trimerization and quaternization) have been
successfully developed to the efficient construction of
imidazolium-functionalized ionic porous organic polymers
(IM-iPOPs) in recent years. A variety of functional monomers,
especially those rigid building blocks with diverse structures
and compositions, have already been synthesized, which are
prerequisites for maintaining the interconnected porosity.
Based on the specific structure of imidazole precursors in
recent publications, there are four main synthetic strategies
that have been developed as described in Scheme 4, that is,
(i) post-synthesis modification strategy, (ii) one-component
self-condensation strategy, (iii) multi-component co-
polymerization strategy, and (iv) one-pot quaternization
strategy, which will be discussed in detail in the following
section. All of these modular synthetic strategies allow the
imidazole units to be elegantly introduced into the highly
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10.1002/cssc.202001079
cross-linked polymeric skeletons by a wise choice of building
blocks at the molecular level. Meanwhile, the key of this
methodology for obtaining cationic networks functionalized
by imidazolium-based ILs is that the composition and
distribution of each catalytically active site should be
precisely controlled to heterogeneously promote the
occurrence of synergy in the CO2 cycloaddition reaction.
Accepted Manuscript
Scheme 4. Synthetic strategies for imidazolium-functionalized
organic cationic polymers
3.1 Post-synthesis Modification Strategy
Inspired by the traditional supported inorganic porous
materials, IL-modified organic functional materials have been
initially developed by many researchers in the immobilized
method. One of the simplest examples was a highly cross-
linked polystyrene resin modified by the hydroxyl-
functionalized imidazolium-based ILs reported by Sun et al.,
which was synthesized by using commercial
chloromethylated polystyrene as a raw material via
subsequently continuous two-step modification as shown in
Scheme 5(a).[33] Thereinto, a 98% propylene oxide (PO)
conversion could be realized in about 4 h at 120 oC and 2.5
MPa CO2 in the presence of 1.6 mol% PS-HEIMBr. However,
this synthetic method largely depends on its chloromethyl
content and internal architecture of the previously-selected
polymers. To improve the freedom of polystyrene-based
materials in the spatial structure regulation, pre-synthetic
method is a better choice. From Scheme 5(b), both Park’s
group[34] and Bordiga’s and co-workers[35] had already
reported an innovative synthesis of a series of imidazolium-
modified cationic polymers that utilizes divinylbenzene (DVB)
and vinylimidazole (VIM) to generate non-ionic co-polymers
with high surface area, and then introduced the IL
functionality into the polymeric matrix through an alkylation
step. Generally speaking, this type of post-synthesis
modification strategy can be accomplished in two steps: first,
a number of uncharged porous materials owning special
functional groups such as imidazole, chloromethyl, hydroxyl
and other active groups that can be facilitated for the
subsequent conversion are synthesized, and then either a
series of imidazole precursors or functionalized imidazolium-
based ILs are incorporated onto the pore walls of such as-
synthesized porous material through covalent attachment,
which is described in Scheme 4(i). Apparently, the
imidazolium groups are elegantly immobilized into the host
ChemSusChem
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architecture as flexible side chains that may improve the
accessibility of catalytically active sites in spite of their
uneven distributions.
Scheme 5. Post-synthetic modification for imidazolium-functionalized
organic cationic polymers.
In 2015, Zhang and co-workers first reported imidazolium
salt-modified porous hypercrosslinked polymers (HCPs) as
shown in Scheme 5(c), which was obtained by typical
Friedel–Crafts reaction with various benzyl halides and
subsequently functionalized with N-methylimidazole that
might be caused by terminal remaining chloro- or
bromomethyl groups at the end of the polymer chain. [36]
These porous materials synthesized in a simple and easily
controllable way, could endow abundant micropores along
with few meso- and macropores as well as excellent CO 2
capture capacities. Nevertheless, the specific surface area
and pore volume of the obtained imidazolium salt
functionalized porous polymers (POM-IM) were lower than
the respective non-ionic cross-linked polymers (POM),
indicating the decreased porosities after the introduction of
imidazolium-based functional groups. Unexpectedly, their
CO2 capture capacities of POM-IM still remained at the high
level (up to 14.5 wt%, 273 K), which were closely correlated
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10.1002/cssc.202001079
with the special volumes of dominant micropores and
contents of imidazolium salts. More interestingly, all of POM-
IM exhibited much higher activities than the aforementioned
IL-supported polystyrene in the CO2 cycloaddition with
epoxides into cyclic carbonates under the same reaction
conditions, and such POM3-IM having hydroxyl functionality
in its framework showed the best performance of a 92% yield
for PO within 8 h at 120oC and 1.0 MPa CO2 pressure with a
catalyst loading of 5.0 mol% (based on the imidazolium salt)
by using ethanol as solvent. These promising results
suggested a distinct synergistic effect of the nanopore
structure and the catalytic centers such as hydroxyl groups
Accepted Manuscript
and halogen anions. Additionally, these imidazolium-
modified porous materials demonstrated high stability and
recyclability for both CO2 capture and conversion. However,
these resulting materials are often amorphous, and may
acquire the low density of ionic sites (ab. 1.0 mmol/g),
thereby reducing the catalytic efficiency.
At present, COFs as a class of crystalline porous materials
have attracted widespread attention, which are easily
constructed from organic building blocks through reversible
covalent bonds. The highly crystalline structures and
accurate porosities have made it possible to provide the
required accessibility to substrate molecules for quick
diffusion. Meanwhile, some functionalized COFs possess the
highly dispersed active sites in the pore channels, which is
beneficial for the subsequent chemical modifications.[37] In
2019, the design and synthesis of imidazolium-salts-
functionalized imine-linked COFs (COF-HNU) had been
reported by Wang’s group as illustrated in Scheme 5(d).
Firstly, the phenolic-hydroxyl-group-functionalized COFs
(COF-HNU2) were readily yielded by using 2-
hydroxybenzene-1,4-dialdehyde and the triamine as a
feedstock through the Schiff-base condensation reaction,
and then the imidazolium-based ILs were anchored onto the
nanoscopic channel walls of COFs via the Williams ether
reaction.[38] COF-HNU3 obtained by the typical two-steps
post-modification method, still had the large Brunauer–
Emmett–Teller (BET) surface area of 2027 m2/g in spite of
the decreased BET value compared to COF-HNU2 (4313
m2/g). More interestingly, the presence of abundant hydroxyl
sites directly led to the high density of imidazolium cations
(ab. 2.24 mmol/g) and bromide anions, which could
effectively promote the solvent-free cycloaddition of CO2 to
epoxides with an extremely high turnover number (TON) of
up to 495000 for PO by using 0.002mol% COF-HNU3 (based
on the imidazolium salt catalytic site) at 100 oC and 2.0MPa.
The unprecedented catalytic activity might be attributed to
the highly dispersed active catalytic sites within the
nanopores of the COFs. In addition, the high crystallinity and
porosity of COF-HNU3 as well as the catalytic activity were
mostly maintained after reused for at least ten times. The
similar phenomenon was also observed in porous imine-
linked porphyrin COFs (IL@Por-COF), which was
synthesized by the successive immobilization of 1,4-
dibromobutane and further N-methylimidazole onto the
channel walls as shown in Scheme 5(e).[39] After grafting
ionic groups onto the surface of pre-synthetic polymeric
materials, the specific surface area decreased significantly
from 1123 m2/g to 513 m2/g, followed by the obvious reduced
CO2 uptake value. As expected, in the absence of any
ChemSusChem 10.1002/cssc.202001079

REVIEW
solvent and cocatalyst, the as-synthesized IL@Por-COF to obtain a large specific surface area because of the flexible
presented excellent catalytic activity in promoting the structures coupling with the high interface energy and thus
cycloaddition reactions with a 95% yield for PO within 24h at limit the further improvement of catalytic activity. Whereafter,
120 °C and 1.0MPa, and the obvious decreased activity and some more advanced strategies have been currently put
selectivity were not observed after recycled five cycles. In forward to optimized pore structure.
brief, pre-synthesis of supported solid materials having
specific functions is required for this strategy, which
determines the CO2 adsorption and catalytic activity of
subsequently synthesized IL-modified materials. Moreover,
the required catalytically active sites such as imidazole
groups and halogen anions are either inhomogeneously
distributed or selectively anchored into the pore wall, which

Accepted Manuscript
may bring about the nanopore blocking and the catalytic
material is eventually deactivated.

3.2 One-component Self-condensation Strategy

In order to avoid the above-mentioned restrictions, one-

component self-condensation strategy has also been
available to prepare them in recent years, which directly
employs charged imidazolium-based ILs with specific
functional groups as a sole polymeric monomer to synthesize
the desired iPOPs as described in Scheme 4(ii). This method
can be implemented the efficient preparation of imidazolium-
functionalized cationic polymers with extremely high ionic
site densities. Among these, main-chain PILs a very good
example. As mentioned above, a majority of PILs have been
generally obtained by a facile and template-free radical self-
polymerization process under solvothermal conditions. [40]
Hence, a number of imidazolium-based ILs containing either
vinyl groups or styrene units can be served as an ideal
monomer to directly construct the polycation matrices. For
example, Dyson’s group reported the synthesis of a class of
Scheme 6. One-component self-polymerization strategy for
PILs derived from 1,3-bis(4-vinylbenzyl)imidazolium salts
imidazolium-functionalized organic cationic polymers
[bvbim]Cl that can be easily polymerized to generate cross-
linked polymers due to its two styrene arms, which was
shown in Scheme 6(a).[41] The resultant poly[bvbim]Cl with
Except styrene-functionalized imidazolium-based salts
the tightly aggregated state exhibited the low BET value of
can be used as a polymeric monomer, vinylimidazole-type
24.18 m2/g, indicating the chloride anions probably
ILs are also good alternatives for affording a charming cross-
encapsulated inside the nanopores. Thus, the cycloaddition
linked network. As depicted in Scheme 6(b), Wang and
reaction from CO2 and epoxides would be carried out under
coworkers reported an atom-efficient and ionothermal
relatively harsh reaction conditions (140 oC, 5.0MPa) with
synthesis towards a series of meso-macroporous
unsatisfactory catalytic activity. More notably, the synthetic
hierarchical PILs that employs rigid bis-vinylimidazolium salt
strategy in a facile manner was more convenient than that of
monomer as a sole feedstock.[43] Methylene-bridged polymer
silica- and polymer-supported ILs, and the obtained
(PDMBr) presents relatively high specific surface area (205
poly[bvbim]Cl displayed almost identical catalytic activity
m2/g) and enhanced CO2 adsorption capacity (1.02 mmol/g,
compared to homogeneous analogue, which indicated that
273 K) under the optimized conditions. These polycation
incorporation of the imidazolium groups within a polymeric
matrices with abundant bromide anions PDMBr exhibited
backbone was not detrimental to catalytic performance.
unprecedented high activity at atmospheric pressure and the
Subsequently, the same group described the preparation of
low temperature of 70oC. Afterwards, greater progress had
a series of cross-linked imidazolium-derived dicationic
been made by the same group on the development of
polymers with different functionalized spacers (e.g. hydroxyl
imidazolium-based iPOPs for the CO2 capture and
and carboxyl) between the two imidazolium rings. [42] As
transforamtion. A family of hypercrosslinked mesoporous
expected, the diol-functionalized heterogeneous dicationic
imidazolium-based PILs with high ionic density (denoted as
polymer was highly active and operates under relatively
PVIm) were also synthesized by increasing their crosslinking
milder conditions. With ECH as a substrate and a 0.5mol%
degree from the imidazolium-based IL monomer with six
afore-mentioned catalyst, a 99% yield was acquired within
vinyl groups, which was prepared from the quaternization
15h at 130oC and 2.5MPa CO2. Similarly, this tpye of cross-
reaction of 1,2,3,4,5,6-hexakis(bromomethyl)benzene with
linked dicationic imidazolium-based solid-phase polymers
N-vinylimidazole.[44] The resulting sol-gel could produce
could be recycled without obvious decrease in activity.
abundant mesopores along with a large specific surface area
However, this solvothermal polymerization method is difficult
(up to 797.7 m2/g) and unprecedentedly high CO 2 adsorption

7
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ChemSusChem
REVIEW
(up to 3.60 mmol/g, 273 K) after the treatment of subsequent
supercritical CO2 drying, which was the key point for
increasing the BET value. Consequently, the rich
nanoporous polymers PVIm having exposed bromide anions
efficiently conduct the CO2 cycloaddition with various
epoxides at atmospheric pressure, even under relatively low
temperature (50oC, 1atm). Although this self-polymeric
strategy can obtain a high density of imidazole moieties (up
to 5.0 mmol/g), it’s difficult to introduce other catalytically
active groups to promote the reaction as well as the
monomers also have considerable limitations due to its
functional groups for polymerization.
In 2018, Cao and coworkers recently reported the
successful synthesis of the well-designed porous cationic
CTFs (CCTFs) via the ZnCl 2-catalyzed-ionothermal
trimerization reaction from cyano functionalized imidazolium
salt (i.e. 1,3-bis(4-cyanophenyl)imidazolium chloride) as a
monomer at different temperatures (350 oC, 400 oC and 500
o
C), which was shown in Scheme 6(c).[45] This charged CTFs
obtained at 500 oC (CCTF-500) possess the highest BET
surface area of 1353 m2/g and the most eminent CO2
capacity performance with 48 cm3/g at 298K and 1 bar,
whereas the densely stacked 2D layer CTFs prepared at
350oC (CCTF-350) exhibited almost no N2 adsorption
capacity yet along with high CO2 uptake capacity of 31 cm3/g,
strongly suggesting that imidazolium moieties and the
abundant triazine nitrogens are greatly benificial for obtaining
the high CO2 uptakes. Notably, CCTF-350 with the highest
density of active sites showed the best activity with a 95%
yield for ECH within 24h at 120 oC and atmospheric CO2
because of the accessiblity for CO2 and substrate through
the channel formed by layers stacking, while the other
resulting materials gained the decreased activities ascribed
to the partial decomposition at higher temperature. More
amazingly, nearly all the charged CTFs exhibited higher
yields than the corresponding homogeneous analogue,
which indicated the isolated active sites in the confined space
could be capable of conducting the synergistic effect on an
epoxide to facilitate the reaction.
Nowadays, the development of such imidazolium-modified
self-polymeric cationic materials with large surface area is
quite slow regardless of the best efforts of scientists. Besides,
the introdution of other active groups that can promote the
ring opening of an epoxide into the polymeric backbone is
also very difficult. Nonetheless, this single-component self-
polymerization method can construct imidazolium-modified
cationic skelectons with the highest ionic site density in
theory.
3.3 Multi-component Co-polymerization Strategy
As stated earlier, we know it’s quite difficult to co-immobilize
or co-integrate two different types of active sites onto one
porous solid materials via either post-synthesis modification
or one-component self-condensation method, whereas the
synergistic effect of these active sites greatly improves the
catalytic efficiency. To circumvent these drawbacks, the
advanced synthetic Friedel-Crafts reaction, Yamamoto-
Ullmann coupling reaction, Sonogashira coupling reaction,
“click chemistry” reaction and Schiff-base condensation.
Therefore, the huge numbers of customized organic
8
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10.1002/cssc.202001079
monomers have been designed to meet the requirements of
the synthetic reaction, thus endowing porous polymers with
versatile chemical compositions, unique porosities, and
multiple synergistic functionalities. As illustrated in Scheme
4(iii), the desired imidazolium-based cationic polymers often
have been prepared by co-polymerization of charged
imidazole monomers and neutral organic building blocks
through a vaiety of flexible synthetic routes.
Thereinto, dominant is the synthesis of main-chain
poly(ionic liquid) by free-radical copolymerization approach.
As early as 2007, Han’s group first prepared a kind of highly
cross-linked imidazolium-based cationic polymer (PS-IL)
Accepted Manuscript
through the copolymerization reaction of divinylbenzene
(DVB) with 3-butyl-1-vinylimidazolium chloride as described
in Scheme 7(a).[46] The corresponding IL moieties were
covalently anchored on DVB-derived polystyrene polymer
matrix to produce an active and insoluble catalytic material
for the CO2-epoxide coupling reaction. In the presence of a
certain amount of PS-IL, a 97.4% yield of PC was achieved
within 7 h at 110oC and 6.0MPa. The polymer-supported IL
was very stable and could be easily seperated and reused in
the cycloaddition of CO2 to epoxides. Inspired by this
pioneering work, many research groups introduced hydrogen
bond donors (e.g. hydroxyl[47], carboxyl[48], amino[49]) or
metal salts[50] into such polymer-supported ILs for increasing
the catalytic activity. My previous study reported a class of
novel Al(salen)-based cationic copolymers (DVB@ISA) as
depicted in Scheme 7(b), which was prepared through a
simple and one-pot free-radical copolymerization of
divinylbenzene (DVB) and charged metallosalen complexes
having vinylimidazolium-based IL moieties under the
identical conditions as above.[51] Thereinto, this well-
designed DVB@ISA endowed high surface area (up to 590
m2/g), hierarchical porous structures, and enhanced CO 2
adsorptive capacity (ab. 1.15 mmol/g, 273K). The acquire of
relatively moderate charge density in DVB@ISA (ab. 0.83
mmol/g) suggested the importance of self-polymerization of
excess neutral monomer. Certainly, that seems the rational
integration of metal centers (Lewis acid) and imidazolium-
based IL moieties (nucleophile) into the polymeric
frameworks can facilitate the cycloaddition reaction of CO2
and epoxides under relatively milder conditions (1.0MPa,
60oC). A quantitative yield of 99% for PO was obtained within
24h when increasing the catalyst loading to 0.5 mol%.
Notably, this bifunctional heterogeneous catalyst DVB@ISA
could be easily recycled and reused six times without
significant activity loss. In turn, further functionalization of this
sort of nanoporous cationic copolymers may obtain other
counterions via ion exchange reaction without changing the
main chain, which made structural modifications and
optimization very easily, obtaining high-performance in
catalytic CO2 conversion (Scheme 7(c)).[52] Hydroxyl-
exchanged nanoporous ionic copolymer PAD-3 showed high
activity, excellent stability and good substrate compatibility.
In the case of converting epichlorohydrin (ECH), high yield
can be achieved at atmospheric pressure of CO 2 with the
very low temperature of 70°C. Surely, as depicted in Scheme
7(d), other crosslinkers such as ethylene glycol
dimethacrylate (EGDMA) as an alternative of DVB, can be
also co-polymerized with a few functionalized IL to generate
a series of novel PILs.[53] In contrast with the hydrophobic
ChemSusChem
REVIEW
property of polystyrene backbones arising from its DVB
moiety, the obtained PIL-4 from ethyl ether bis(1-
vinylimidazolium) chloride and EGDMA exhibited low surface
area, and showed the improved catalytic efficiency and
accelerated mass transfer rate.
Scheme 7. Multi-component co-polymerization strategy for
imidazolium-functionalized organic cationic polymers in the presence
of a competitive polymerization.
More excitingly, both of polymeric monomers containing
carbon-carbon double bonds, i.e. allyl-functionalized
imidazolium-based ILs (charged) and vinyl-functionalized
triphenylphosphine (neutral), were introduced into POPs
featuring multifunctional sites (denoted as PPh3-
9
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10.1002/cssc.202001079
ILBr@POPs), in which had been prepared through the
solvothermal free-radical polymerization reported by Ding’s
group in 2016.[54] Subsequently these resulting POPs was
impregnated by zinc halide salts in the position of numerous
strongly coordinative phosphines to obtain the targeted
materials such as PPh3-ILBr-ZnBr2@POPs as shown in
Scheme 7(e). Notably, the slightly decreased BET surface
area of PPh3-IL-ZnBr2@POPs was observed compared with
metal-free PPh3-IL@POPs (482 m2/g vs 591 m2/g), which
was due to the additional weight of ZnBr 2 salt after the two-
steps integration. In addition, the relatively low density (ab.
0.518 mmol/g calculated by input amount) of ionic sites within
Accepted Manuscript
the porous materials was achieved due to the excessive use
of phosphine-based monomers (5.0 eq.). Very encouragingly,
owing to the outstanding cooperative effect of bromo-
substituted IL and homogeneously embedded Zn→PPh3
building blocks, PPh3-IL-ZnBr2@POPs exhibited very good
CO2 adsorption selectivity over N2 and provided the highest
activity with an initial TOF value up to 3520 h−1 for PO
(3.0MPa, 120oC) under cocatalyst- and solvent-free
conditions. The promising results indicated both the confined
micro/mesoporous architecture and the excellent mobility of
functional groups in the swelling skeletons probably
strengthened the synergistic action, and then promoted the
mass transfer behaviour. Except for the free-radical
polymerization method, some other promising synthetic
pathways have also been available in recent decades. For
example, a facile synthesis of Al(porphyrin)-derived PIPs
(denoted as Al-iPOPs) was also performed through a typical
Yamamoto–Ullmann coupling reaction of 1,3-bis(4-
bromophenyl)imidazolium bromide (charged) and
aluminium(III) 5,10,15,20-tetrakis(4’-bromophenyl)porphyine
chloride (neutral) in the following time, which was described
in Scheme 7(f).[55] We observed that the employment of
robust and rigid IL-derived monomer can effectively facilitate
the maximization of the surface area of PIPs like a BET value
of 86 m2/g for Al-iPOPs with uniform microporosity. Moreover,
the introduction of charged IL units into the skeletons of
POPs may cause the pore blocking with the decreased BET
value, whereas that of IL-free Al(porphyrin)-involved auto-
polymers was up to 219 m2/g. Considering that neutral
metalloporphyrins are more likely to undergo polymerization
than charged IL-monomers, the moderate amount of
imidazolium sites within the porous framework was obtained
with a value of 1.128 mmol/g. The acquisition of a high TOF
value of 7600 h−1 (1.0MPa and 100oC) and the excellent
activity by replacing pure CO2 with simulated flue gas (15%
CO2 and 85% N2) as a feedstock demonstrated that the
presence of an excellent cooperative effect of aluminum
center and bromide anion, the superior CO 2-philic capacity
as well as the outstanding substrate/product swelling
properties.
Alternatively, in order to avoid the potential environmental
contamination aroused from the metal leaching, several
efficient metal-free iPOPs had been designed and
synthesized recently. Scheme 7(g) illustrated a general
procedure for a one-step and efficient polymerization
towards imidazolium-functionalized HCPs bearing
adjustable surface groups (denoted as IR-HCPs) by using α'-
dibromo-p-xylene as a crosslinking agent (neutral) and a
series of benzylimidazole salts as the ionic monomers
ChemSusChem 10.1002/cssc.202001079

REVIEW
(charged).[56] The fascinating structural design features,
originated from the clever connection between the phenyl
ring and the imidazolium cation, can promote the smooth
progress of hypercrosslinkage reaction through FeCl 3-
catalyzed Friedel-Crafts alkylation. In particular, these
resulting multifunctional ionic HCPs tethering the ethyl group,
termed as IC2-HCPs, endowed tunable chemical composition,
moderate content of ionic sites (up to 0.97 mmol/g), large
surface area (up to 1017 m2/g), remarkable CO2 uptakes (up
to 3.05 mmol/g, 273K) and superior CO2 adsorptive
selectivity over N2. Thus, the synthesis of cyclic carbonates
from the cycloaddition of various epoxides with the simulated
while hydroxyl groups would serve as hydrogen-bond
donors (HBDs) to simultaneously promote the ring opening
of epoxides on the basis of cooperative interactions, thereby
generating the acceleration of the rate-determining step in
the solvent- and additive-free cycloaddition reaction of CO2
with the epoxides. However, this strategy for iPOPs
synthesis often involves complicated functional monomers
and requires expensive noble-metal catalysts or additives.

Accepted Manuscript
flue gas (15% CO2 in N2, v/v) could be catalyzed by these
ionic HCPs with high yields and large TON values (up to
4800 at 120oC and 3.0MPa) as well as stable reusability
without any solvent and additive.
Through careful analysis of the structural characteristics of
each polymeric monomer, we found that all the above
examples shared a common feature, that was, both of
charged and neutral building blocks could be polymerized
under the selected conditions, which would directly cause the
rate differences in the process of polymerization.
Nevertheless, the acquired specific surface area was mainly
generated by the direct polymerization of neutral monomer.
The occurance of competitive rates and the tendency of
intermolecular accumulation derived from charge interaction
may bring about the dereased density of imidazolium-based
ionic sites. To avoid the question of the uncertainty of ion
content, more advanced synthetic methods following with the
flexible monomer designs had been developed in the past
years, which was able to precisely construct the targeted
POPs having the accurate architecture and identical
repeating units.
As early as 2001, a class of microporous organic cationic
networks bearing imidazolium salts with a high surface area
of 620 m2/g were prepared by Sonogashira coupling reaction
of diiodoimidazolium salts (charged) and tetrakis(4-
ethynylphenyl)methane (neutral), which exhibited a definite
catalytic activity in the heterogeneous conversion of CO 2 into
cyclic carbonates (Scheme 8(a)).[57] Due to its porosity and
excellent dispersion ability, the maximum yield of 92% for
ECH was achieved with a low loading of 0.065mol% T-IM at
160oC and 3.0 MPa CO2. Soon afterwards, Wang’s group
presented a facile preparation of an imidazolium- and
triazine-based POPs (IT-POPs) through the similar Pd/Cu-
catalyzed Sonogashira coupling reaction between tetrakis(4-
ethynylphenyl)methane (neutral) and functional imidazolium
salts containing triazine groups (charged), which was
described in Scheme 8(b).[58] IT-POPs possessed the high
content of the imidazolium group (2.08 mmol/g), large
Scheme 8. Multi-component co-polymerization strategy for
surface area (245 m2/g), and excellent CO2 uptake capacity imidazolium-functionalized organic cationic polymers without a
(1.70 mmol/g, 273K) with good adsorption selectivity over N 2. competitive polymerization.
Relative to the larger bromide anions, small chloride anions
in the porous frameworks were beneficial for increasing
specific surface area. The CO2-philic groups including According to above-mentioned reasons, both phenol-
imidzalium and triazine units as well as various task-specific formaldehyde condensation and Schiff-base reaction, known
components including hydroxyl groups and counter chloride as catalyst-free and eco-friendly routes, would be
anions can be periodically incorporated into POPs, which successfully applied to prepare a variety of iPOPs by using
were homogeneously distributed in the host backbone of IT- dialdehyde-functionalized imidazolium-based ILs as a
POPs. As expected, their intrinsic CO2-philicity could charge monomer in my previous works as shown in Scheme
facilitate the CO2 adsorption and subsequent activation, 8(c,d). In spite of the very low BET surface area (<10 m 2/g)

10
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ChemSusChem
REVIEW
and moderate CO2 capture capacities (1.45 mmol/g, 273K)
obtained by FIP-IM, this cationic polymeric material still
exhibited high activity for metal-, solvent- and additive-free
synthesis of cyclic carbonates from CO 2 and epoxides under
mild conditions (80oC, 1.0MPa) due to the presence of
abundant phenolic hydroxyl groups and high density of
imidazolium-type ionic sites in the architectures. [59]
Analogously, the imine-linker Zn(porphyrin)-based cationic
polymer with intercalated imidazolium-based ILs (SYSU-
Zn@IL), prepared from zinc(II) tetrakis(4’-
aminophenyl)porphyin, also served as an efficient
heterogeneous catalyst for the synergistic CO 2 fixation with
epoxides to produce cyclic carbonates under mild
conditions.[60] Notably, SYSU-Zn@IL with moderate CO2
adsorptive ability (1.36 mmol/g, 273K) could directly convert
diluted CO2 (15% CO2 in N2) into cyclic carbonate with an
excellent yield at 80 °C and initial 3.0 Mpa pressure. However,
due to the flexible structures of the fabricated methylene-
bridged polymers, all of the cationic networks demonstrated
the very low BET surface areas (ab. 21 m2/g). The reason for
consensus was that the presence of charge interactions
among ionic sites tends intermolecular stacking, and thus the
higher contents of ionic active sites within IL-modified
catalytic materials often led to the relatively lower BET values.
Exactly, three-component copolymeriation process
provided an interesting pathway to yield PIPs having
imidazolium-based ILs of different contents as depicted in
Scheme 8(e).[61] The nitrogen-rich click-based CPP-ILs were
straightforwardly prepared through a typical and one-pot
alkyne-azide click reaction of 1,1,2,2-tetrakis(4-
ethynylphenyl)ethane and tetrakis(4-azidophenyl)methane
in the presence of different proportion of ethynyl-modified ILs
as charged starting units. The newly-formed triazolyl groups
had been validated to activate both CO2 and epoxides. The
experimental results verfied the BET specific surface areas
and pore volumes of these porous materials gradually
decreased as increasing the amount of ILs. The quantitative
conversion of ECH was achieved for 24h in the presence of
CPP-IL0.05 under atmosphere CO2 pressure and 100 oC.
The introduction of suitable ILs not only adjusts porous
properties, but also improves CO2 capture ability and
nucleophilic ability toward the epoxides. As a consequence,
the optimized balance between porous properties and the
imidazolium contents may facilitate the CO 2 cycloaddition
with epoxides under relatively milder conditions.
Moreover, crystalline COFs have been also constructed
from organic building blocks and displayed periodic
architectures and intrinsic nanoporosities, which meets the
multifaceted requirements of CO2 capture and subsequent
conversion. The design of multifunctional building units is
essential. As described in Scheme 8(f), a kind of novel COFs
decorated by allylimidazolium-based IL (denoted as COF-IL)
had been prepared via a reversible Schiff-base condensation
reacton from allylimidazolium-based IL derivatives (charged)
and 1,3,5-triformylphloroglucinol (neutral). The obtained
COF-IL showed good crystallinity, abundant microporous
structure, moderate BET specific surface area (291 m 2/g)
and large CO2 uptake amount (106.04 cm 3/g, 273 K).[62]
Without TBAB assistance, COF-IL showed the best catalytic
performance under the optimal conditions (3.0 mol% of
catalyst, 80oC, 24h, 1atm CO2). More importantly, the
11
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10.1002/cssc.202001079
presence of allyl groups was very convenient for further
modification or functionalization via a fascinating chemical
crosslinking.
From the above discussion, both abundant nanoporosities
and nitrogen-rich environment including imidazolium
functionality have been identified as important characteristics
for CO2 adsorption and transformation. The inherent
advantages of multicomponent copolymerization strategy
can facilitate the optimization of the pore sizes and
maximization of the surface area of porous polymers. The
advanced “bottom-up” approach had been proved to be used
for synthesizing high-performance ionic POPs. It follows that
Accepted Manuscript
the key is how to facilely design task-specific catalytic
materials with diverse structures and functions to enhance
their catalytic efficiency for the cycloaddition of CO 2 and
epoxides under mild conditions.
3.4 One-pot Quaternization Strategy
One-pot quaternization strategy to create imidazolium-based
cationic networks utilizes the formation reaction of
imidazolium-based ILs, which directly employs the
polyhalides and multidentate imidazole precursors as
starting materials via a nucleophilic substitution reaction.
This succinct strategy can not only circumvent these
problems such as complicated functional monomers and the
use of expensive/toxic catalysts or additives, but also
promote the maximization of ionic sites density within the
polymeric backbone, enhancing their heterogeneous
catalytic performance.
As early as in 2014, due to the CO2-philic properties of
fluorine-containing compounds or materials, Liu and co-
workers first reported a series of main-chain fluoro-
functionalized PILs, which were constructed through a two-
step alkylation (Scheme 9(a)).[63] Obviously, fluorine linkages
were directly involved into the backbone of the PILs. It had
been discovered the catalytic activity in CO2 cycloaddition to
epoxides increased with the fluorine content in the main-
chain cations, and the resulting F-PIL-Br showed the highest
efficiency and stability as well as easy recyclability,
producing a series of cyclic carbonates with excellent yields
at 120oC under 1.0 MPa CO2 pressure. Simultaneously, as
described in Scheme 9(b), Zhang’s group also developed
silicon-based main chain poly-imidazolium salts from
bisimidazole and silicon tetrachloride (SiCl4),[23] which was
served as an efficient metal-free heterogeneous catalysts for
the fixation of CO2 into cyclic carbonates (110oC, 1.0MPa).
The unreacted Si–Cl groups in the polymer chain would be
transformed into Si–OH groups via hydrolysis reaction.
These results from the density functional theory study
demonstrated that the silanol groups of the polymeric chain
backbone was the key factor to activating an epoxide for
obtaining high activity. Likewise, Dyson’s group explored a
simple preparation of a series of heterogeneous
imidazolium-based cationic polymers from inexpensive and
commercial starting materials, which was obtained from the
direct reaction of different benzyl halides with
trimethylsilylimidazole in near-quantitative yields as shown in
Scheme 9(c).[64] The arene-bridged polyimidazolium salt PIM
synthesized from 4,4'-bis(chloromethyl)-1,1'-biphenyl had
larger spacers that might form more porous structures with a
ChemSusChem
REVIEW
higher BET value of 91.56 m2/g. Moreover, the robust
heterogeneous polymers having a pure imidazolium-based
platform were considered as excellent organocatalysts for
the solvent-free cycloaddition of CO2 to epoxides to afford
cyclic carbonates at atmospheric pressure (100 oC, 1atm).
Thus it can be seen that all sorts of the facile synthesis of
main-chain imidazolium-based cationic polymers could be
recovered and reused multiple times without a significant
loss of activity.
Scheme 9. One-pot quarterisation strategy for imidazolium-
functionalized organic cationic polymers.
12
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10.1002/cssc.202001079
As illustrated in Scheme 9(d), Cao’s group first reported a
kind of metalloligand-derived cationic polymer (denoted as
Al-CPOP) can be easily prepared by a one-pot
quaternization strategy from the 5,5’-dichloromethyl-
functionalized Al(salen) complex and 2,4,6-tris(imidazol-1-
yl)-1,3,5-s-triazine.[65] Despite of a relatively low BET specific
surface area obtained by porous Al-CPOP (ab. 136 m2/g),
yet it exhibited moderate CO 2 adsorption uptake (12 cm 3/g,
298K) due to abundant nitrogen-rich sites including triazine
rings and imidazolium cations. On the basis of structural
characteristics of Al-CPOP having repeating aluminium
centers and chloride anions, it can be employed as an
Accepted Manuscript
eminent bifunctional catalyst in the cocatalyst- and solvent-
free cycloaddition of CO2 with epoxides to produce cyclic
carbonates, and presented high activity and selectivity at
atmospheric pressure (120oC, 1atm).
Similarly, a series of the crosslinked polyimidazolium salts
containing three-dimensional contorted adamantane groups
and imidazolium functionality (denoted as PIM) were
constructed from 1,3,5,7-tetrakis(4-(imidazole-1-
yl)phenyl)adamantane and a variety of benzyl bromides
without any additive and catalyst, which was reported by
Wang et. al. in 2020 as depicted in Scheme 9(e).[66] The as-
prepared material PIM2 exhibited a low BET value of 24.2
m2/g, and thus the flexibility of the benzyl linkage may cause
pore collapse within the networks. Due to the lack of other
active groups that synergistically activating epoxides, the
polymeric imidazolium salts showed moderate activity for
catalyzing the CO2 cycloaddition with a variety of epoxides
without any solvent or co-catalyst (130oC, 1.0MPa)
compared with the reported heterogeneous imidazolium-
derived polymers.
Thereafter, a succinct and “two-in-one” strategy was
demonstrated for constructing an imidazolium-functionalized
cationic network bearing abundant hydroxyl groups via an
one-pot quaternization, which can achieve the simultaneous
polymerization and ionization between multi-imidazole
precursor (tetrakis[4-(1-imidazolyl)phenyl]methane) and a
special linker (1,3-dibromo-2-propanol) as shown in Scheme
9(f).[67] Although the bifunctional cationic polymer IMIN-Br-
OH have a low BET surface area of 20 m2/g, these enriched
multi-active sites with definite spatial positions may enhance
the cooperative catalytic activity in the CO 2 cycloaddition with
various epoxides. As a result of their low mass-transfer
resistance, the IMIN-Br-OH still provided a high yield of 99%
for ECH at 40°C and 1 atm in spite of the requirement of the
exceptionally long reaction time (72h). Additionally, hot
filtration and leaching tests demonstrated that the robust
heterogeneous catalyst exhibited good recyclability.
Through the systematic analysis from the above examples,
it is easy to find that the imidazolium-functionalized cationic
polymers prepared by a one-pot quaternization method often
acquire the superior activity due to their high densities of
ionic active sites. However, higher imidazolium-based
cationic centers can also cause the decreased specific
surface area because the strong polarity of imidazolium salts
may lead to charge interactions and tendency of
intermolecular stacking. Recently, a series of porous
metallosalen-derived hypercrosslinked ionic polymers as
shown in Scheme 9(g) were also synthesized through a
simple three-component Friedel–Crafts alkylation that
 ChemSusChem 10.1002/cssc.202001079

REVIEW
integrating the superiority of self-condensation and one-pot
quaternization. Among these, the ionic Co-HIP possessing
metalloligand and imidazolium functionality endowed open
micro/mesoporous channels and a large surface area (541
m2/g). The relatively high CO 2 capacities for Co-HIP (2.10
mmol/g, 273K) can promote the CO2 cycloaddition with
epoxides to perform at ambient conditions, displaying an
enhanced yield of 99% for ECH within 20h at 80 oC. The
promising reason was strongly associated with the
bifunctional active sites (cobalt center and bromide anion) in
the porous structure.
Finally, Table 1 illustrates the important results of the CO2
difficult to find crystalline COF-IL prepared from advanced bi-
component co-polymerization approach presents the largest
CO2 uptake capacity and unsaturated double bonds-derived
PDMBr obtained from self-condensation method has the
highest density of imidazole groups. Besides, several ionic
POPs with hierarchical structures such as PPh3-ILBr-
ZnBr2@POPs and Al-iPOPs-2 show excellent catalytic
performance and superior diffusive properties with the
highest TOF values. Although the specific surface area
values of some ionic polymers are not very high, their
acquired catalytic activities are not very poor in the CO 2-
involved liquid-phase reactions, probably suggesting the

cycloaddition reaction by using ECH as a representative
substrate over a variety of imidazolium-functionalized
organic cationic polymers. Some parameters that affect
catalytic performance including the specific surface areas,
CO2 uptake and the contents of imidazolium units as well as
the TOF values are also listed for comparison. It is not
Accepted Manuscript
pore structure is not the most crucial factor despite of the
convenience of mass transfer. Consequently, we should
carefully evaluate the various parameters that may affect
catalytic performance to achieve the expected equilibrium so
as to acquiring the ideal heterogeneous catalytic materials.

Table 1 Listed results of the CO2 cycloaddition with ECH over various imidazolium-functionalized organic cationic polymers discussed here. a

BET CO2 uptake Imidazoleb Loadingc t T PCO2 Yield TOFd

Entry Method Polymeric materials 2 o
Ref.
/m /g /mmol/g(273K) /mmol/g /mol% /h / C /MPa /% /h-1
1 post-modification PS-HEIMBr n.d. n.d. 3.2 1.6 3 115 2.5 92 19.2 [33]
2 post-modification POM3-IM 575 3.23 1.01 5.0 8 120 1.0 90 2.25 [36]
3 post-modification COF-HNU3 2027 n.d. 2.24 0.002 36 100 2.0 96 1333 [38]
4 post-modification IL@Por-COFs 513 1.41 0.6 8.17 24 120 1.0 91 0.46 [39]
5 Self-condensation poly[bvbim]Cl 24.18 n.d. 2.53 1.0 3 140 5.0 98 32.7 [41]
6 Self-condensation p5b 34.7 n.d. 3.15 0.5 15 130 2.5 99 13.2 [42]
7 Self-condensation PDMBr 205 1.02 5.2 2.6 48 70 0.1 99 0.79 [43]
8 Self-condensation PVIm-6-SCD 797.7 3.6 5.0 0.5 24 50 0.1 99 8.25 [44]
9 Self-condensation CCTF-350 n.d. 1.27e 2.11 0.2 24 120 0.1 95 19.8 [45]
10 Co-polymerization PS-IL n.d. n.d. 1.0 1.0 3 110 6 96 32 [46]
11 Co-polymerization DVB@ISA 590 1.15 0.87 0.25 24 60 1.0 98 16.3 [51]
12 Co-polymerization PAD-3 156 1.4 2.32 4.64 24 70 0.1 98 0.88 [52]
13 Co-polymerization PIL-4 1.97 n.d. 2.5 1.0 12 100 1.0 99 8.3 [53]
14 Co-polymerization PPh3-ILBr-ZnBr2@POPs 482 n.d. 0.43 0.0125 1 120 3.0 37 2960 [54]
15 Co-polymerization Al-iPOPs-2 86 1.32 1.14 0.1 6 40 1.0 99 165 [55]
16 Co-polymerization IC2-HCPs-5b 1017 3.05 0.8 0.02 20 120 3.0f 92 230 [56]
17 Co-polymerization T-IM 620 n.d. 1.33 0.065 10 150 1.0 85 131 [57]
18 Co-polymerization IT-POP-1 245 1.70 2.08 0.1 10 120 1.0 99 99 [58]
19 Co-polymerization FIP-Im <10 1.45 2.51 5.0 10 80 1.0 99 1.98 [59]
20 Co-polymerization SYSU-Zn@IL2 21 1.36 1.6 0.16 12 80 1.0 99 51.6 [60]
21 Co-polymerization CPP-IL0.05 994 3.21 0.7 1.0 24 100 0.1 99 4 [61]
22 Co-polymerization COF-IL 291 4.73 1.7 3.0 48 80 0.1 98 0.68 [62]
23 One-pot quaternization IP3 91.56 n.d. 3.36 5.0 4 100 0.1 99 4.95 [64]
24 One-pot quaternization Al-CPOP 136 0.54e 3.7 1.0 24 120 0.1 95 3.96 [65]
25 One-pot quaternization PIM2 24.2 n.d. 3.06 0.2 4 130 1.0 92 115 [66]
26 One-pot quaternization IMIN-Br-OH 20 n.d. 4.02 8.0 72 40 0.1 99 0.17 [67]
27 One-pot quaternization Co-HIP 541 2.10 0.49 0.21 20 80 0.1 99 23.6 [68]
[a]
n.d.=not detected; [b] Denoted as the content of imidazolium units within polymers; [c] Calculated by the content of ILs; [d]
Equal to
mole of synthesized AGC per mole of catalyst per hour; [e] Measured at 298K; [f] Using 15% CO2 in N2.

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ChemSusChem 10.1002/cssc.202001079

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ChemSusChem 10.1002/cssc.202001079

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Entry for the Table of Contents

Accepted Manuscript
Recent advancements in the cycloaddition reaction of captured
CO2 with epoxides over a variety of imidazolium-functionalized
organic cationic polymers as a class of eminent heterogeneous
catalysts are reviewed.

16
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