Chinese Journal of Chemical Engineering 42 (2022) 91–103

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Chinese Journal of Chemical Engineering

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

Review

Recent progress in porous organic polymers and their application for CO2
capture
Jiajia Wang, Lizhi Wang, You Wang, Du Zhang, Qin Xiao, Jianhan Huang ⇑, You-Nian Liu
College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Micro and Nano Material Interface Science, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: Carbon capture, storage, and utilization (CCSU) is recognized as an effective method to reduce the exces-
Received 30 May 2021 sive emission of CO2. Absorption by amine aqueous solutions is considered highly efficient for CO2 cap-
Received in revised form 21 August 2021 ture from the flue gas because of the large CO2 capture capacity and high selectivity. However, it is often
Accepted 23 August 2021
limited by the equipment corrosion and the high desorption energy consumption, and adsorption of CO2
Available online 13 October 2021
using solid adsorbents has been receiving more attention in recent years due to its simplicity and high
efficiency. More recently, a great number of porous organic polymers (POPs) have been designed and con-
Keywords:
structed for CO2 capture, and they are proven promising solid adsorbents for CO2 capture due to their
Porous organic polymers
Selectivity
high Brunauer-Emmett-Teller (BET) surface area (SBET), adjustable pore size and easy functionalization.
Adsorbent In particular, they usually have rigid skeleton, permanent porosity, and good physiochemical stability.
CO2 capture In this review, we have a detailed review for the different POPs developed in recent years, not only the
design strategy, but also the special structure for CO2 capture. The outlook of the opportunities and chal-
lenges of the POPs is also proposed.
Ó 2021 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All
rights reserved.

1. Introduction and high Brunauer-Emmett-Teller (BET) surface area (SBET). For

The excessive emission of CO2 has caused serious global warm-
ing, which is a great menace for the living conditions of human
beings [1,2]. How to reduce the emission of CO2 had been caught
increasing attentions. Although the development and utilization
of the clean energy has greatly improved, the fossil fuels still keep
the main position [3]. Hence, the excessive emission of CO2 would
constantly occur for the foreseeable future. Mentionable, CO2 is
considered as a kind of cheap, innoxious, abundant, and green C1
resources [4]. It is meaningful to capture the excessive CO2 from
the environment and convert CO2 into high value-added chemical
products such as CO, methane, ethanol, formic acid, etc [5,6]. For
this purpose, the enrichment of CO2 is of great importance.
The common adsorptions of CO2 were physical and chemical
adsorption [7]. As a kind of chemical adsorbent, aqueous amine
solutions have been widely used for CO2 capture from the flue
gas. However, liquid ammonia could cause equipment corrosion,
and the high desorption energy consumption would cause large
energy penalty [8]. Hence, the solid adsorbents have caught more
attentions for their low heat capacities, tunable pore structure,
⇑ Corresponding author.
E-mail address: jianhanhuang@csu.edu.cn (J. Huang).
instance, metal-organic frameworks (MOFs) [9,10], activated car-
bons [11], and porous organic polymers (POPs) [12,13] are usually
used for CO2 capture. However, in the complex conditions such as
flue gas (N2, O2, CO2, H2O, SOx and NOx), MOFs are suffered from the
chemical stability for their unsteady structure, and the release of
organic ligand and metal ions are also harmful for the environ-
ment. Activated carbons also have some disadvantages such as
poor selectivity and difficult functionalization. Among them, POPs
have attracted more and more attentions due to their easy prepa-
ration and post-functionalization, high physiochemical stability
and selectivity [14].
The POPs are constructed by the cross-linking of lighter ele-
ments (C, H, B, O, N, S, P, etc.) through covalent bonds [15]. As a
kind of good carbon capture materials, POPs have several advan-
tages: (1) POPs are constructed by rigid monomers, resulting per-
manent porosity in the polymers; (2) There are many bond
formation methods and crosslinking reactions, which will take
the polymers with various topological structures and tunable pore
structures; (3) POPs are constructed by the cross-linking of lighter
elements, which will make the polymers with high mass capacity
of CO2; (4) POPs are constructed with covalent bonds, which make
them good physiochemical stability. In this way, special POPs with
specific performance and pore structures could be designed and

https://doi.org/10.1016/j.cjche.2021.08.028
1004-9541/Ó 2021 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
92 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
synthesized to fit the need of CO2 capture, energy storage, catalysis,
etc. [16,17] Till now, the POPs could be divided to six kinds for their
different structures and construction methods: hyper-cross-linked
polymers (HCPs), conjugated microporous polymers (CMPs), poly-
mers of intrinsic microporosity (PIMs), porous aromatic frame-
works (PAFs), covalent organic frameworks (COFs), and covalent
triazine frameworks (CTFs). The HCPs, PIMs, CMPs, and PAFs are
amorphous structure, which are synthesized through irreversible
reactions under kinetic control. While the COFs and CTFs are crys-
talline structure and are synthesized by reversible reactions under
thermodynamics control [18].
As reported in the literatures, there were several factors played
key roles in CO2 capture, such as SBET, heteroatom, and microp-
orous content [19,20]. As for SBET, the higher SBET will take much
more adsorption sites. While under low pressure, SBET have little
influence on CO2 capture due to the low interaction between the
sites and CO2 moleculars. However, under high pressure, CO2
moleculars were pressed to the adsorption sites, which caused
higher CO2 uptake. Heteroatoms also have grent influence on CO2
capture. For instance, N atoms could interact with CO2 moleculars
by dipole-quadrupole interactions or hydrogen bonding, which
will obviously increase the CO2 capture of the polymers. As
reported in the literatures, O, S, P heteroatoms were also played
the positive roles in CO2 capture [21–23]. In addition, the microp-
orous structure of polymers also a key factor for CO2 capture. It was
reported that ultramicropores (d < 1.0 nm) would greatly increase
the adsorption capacity and selectivity of CO2 due to the size selec-
tion effect [24]. Hence, the design of POPs for CO2 capture should
considered three points: high SBET, heteroatom content, micropores
content.
To the best of our knowledge, there were few reviews about
POPs for CO2 capture in recent years. In 2017, Yuan’s group [25]
mainly reviewed the amorphous POPs for CO2 capture in ‘‘Journal
of Materials Chemistry A” and summarized the factors for influ-
ence on CO2 capture capacity. However, the crystalline POPs were
not mentioned. In the same year, Zhou’s group [26] also reported
POPs for CO2 capture. In this review, they mainly summarized
the strategies for POPs to enhance CO2 uptake and selectivity. Tan’s
group [16] described the synthetic strategies and principles of
HCPs, and the major applications in environmental remediation
and energy storage, such as gases capture and storage, pollutants
removal, sensing, etc. In 2020, Sun’s group [27] reported a review
on crystalline POPs (COFs) for gases capture, organics pollutants
and heavy metals adsorption. Zhang’s group [28] reviewed the
COFs for gases separation, and briefly introduced the application
of COFs in CO2 separation before 2018. Nevertheless, the compre-
hensive and detailed reviews about design and preparation of POPs
for CO2 capture were not reported. Thus, we mainly concluded and
discussed the design and preparation of the POPs for CO2 capture
and separation in the last few years. The outlook of the opportuni-
ties and challenges of POPs were also considered.
2. Amorphous POPs for CO2 Adsorption
Different from the harsh synthesis conditions of crystalline
structure, amorphous POPs were more commonly seen. For
instance, the HCPs were commonly constructed by Friedel-Crafts
alkylation reaction between the aromatic rings and the cross-
linkers. Because of the multiple substitution of alkyl occurs on
the aromatic rings, the indeterminacy makes HCPs amorphous
structure. Although the amorphous structure makes the polymers
difficult to clear insight into the inner structure, the CAC bonds
make them excellent thermal and chemical stability, and they
can still maintain their original properties in very harsh chemical
environment. For POPs materials, the HCPs, CMPs, PIMs and PAFs
were belongs to amorphous polymers. The applications of these
amorphous POPs in CO2 adsorption and separation are briefly
introduce in the following.
2.1. HCPs for CO2 adsorption
The HCPs usually formed a large number of rigid cross-linking
bridges between polymer chains or aromatic monomers through
Friedel-Crafts reaction [29]. There are some permanent channels
among the molecular chains in HCPs because of the high degree
of cross-linking, which prevents the polymers chains from packing
tightly [30]. The rigidity structure of HCPs also brings the polymers
with high chemical stability, high SBET and micropore volume
(Vmicro). In addition, HCPs also have great advantages in synthesis,
such as the simple reaction procedures, cheap catalysts, and vari-
ous methods. In this way, HCPs had greatly developed in the recent
years. At present, HCPs can be produced by three ways: (1) Post-
crosslinking of precursor polymers. (2) Direct one-step condensa-
tion of multifunctional monomers (or mixtures). (3) Knitting
method with external crosslinking agents. Abundant building
monomers and synthesis strategies have produced various of HCPs,
which have become one of the most potential and valuable mate-
rials in CO2 adsorption [31].
2.1.1. Post-crosslinking of precursor polymers
Davankov’s group [32] firstly reported that a series of polymers
with permanent micropores were post-cross-linked by Friedel-
Crafts reaction. Linear polystyrene or low crosslinked polystyrene
polymers chains were swelled in suitable solvents. With the help
of Lewis acid catalysts, different external crosslinking agents were
post-crosslinked with the adjacent benzene rings of the precursor
polymers. This strategy provides a new method for synthesis the
porous polymers. Until 2002, Davankov et al. [33] firstly proposed
the concept of ultra-high crosslinked polymers, and the hyper-
cross-linked resin based on polystyrene framework was named
‘‘Davankov resin”. The formation process was mainly divided into
three stages. Firstly, the polymers chains were fully dissolved or
swelled in the solvent; then they were quickly cross-linked by
external crosslinking agents; and finally the solvents were
removed by drying to obtain HCPs with permanent micropores.
Post-crosslinking of precursor polymers for HCPs construction
had greatly developed and caught a lot of attentions. For instance,
Li and co-workers [34] synthesized the F-HCP-x by using post-
crosslinking method. Phenylmethylsilicone was chosen for the pre-
cursor polymer. Then formaldehyde dimethyl ether (FDA) was
added to crosslink the benzene rings in the polymers chains,
resulting the polymers with moderate SBET. What’s more, the
silicon-oxygen bonds of phenylmethylsilicone could be etched by
hydrofluoric acid. The resulting polymers showed great increasing
of SBET (from 440 to 1201 m2
g1) and ultramicropore volume
(Vultra) (from 0.18 to 0.49 cm3
g1), resulting the polymers with
high CO2 capture of 153.00 mg
g1 (273 K and 0.1 MPa), low isos-
teric enthalpy of adsorption (Qst) of 30.7 kJ
mol1, and good
adsorption selectivity for CO2/N2 of 36.6.
The precursor polymers for the construction of post-crosslinked
HCPs were various sources. Our group [35] synthesized a kind of
precursor polymers by Friedel-Crafts acylation reaction. Although
the polymers showed very low SBET and almost no pores, the result-
ing polymers which were post-crosslinked by the carbonyl of the
precursor polymers and amidogen of melamine through the
Schiff-base reaction, showed a great increasing of SBET (from 4 to
645 m2
g1) and Vultra (up to 0.16 cm3
g1). The post-
functionalization of melamine also takes abundant N species to
the polymers. Hence, the capture capacity of CO2 was also greatly
improved (from 48.30 to 153.00 mg
g1 at 273 K and 0.1 MPa). This
strategy was also expanded to other ketone functionalized
 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
polymers, which were constructed by aromatic monomers and acyl
chloride (or anhydride) through the Friedel-Crafts acylation reac-
tion. These precursor polymers also showed greatly improvement
of SBET, Vultra, N content, and adsorption capacity of CO2 (up to
193.00 mg
g1) after the post-crosslinked of melamine through
the Schiff-base reaction. The results indicated that the post-
crosslinked of the precursor polymers with melamine could be
widely used for ketone based precursor polymers (Fig. 1). This
strategy not only elevate the SBET and Vultra of the polymers, but
also takes abundant N species to the polymers, resulting the final
polymers with good performance in CO2 capture and selectivity
for CO2/N2 [36,37].
Although divinyl benzene (DVB) can be used for the construc-
tion of HCPs directly by free radical polymerization, the resulting
polymers have no functionalized sites. Hence, Wang and co-
workers [38] synthesized the crosslinked precursors by free radical
polymerization of DVB, 4-vinylbenzyl chloride (VBC), and 1-(30 -car
boxylpropyl)-3-vinylimidazolium bromide. Then, the functional-
ized ionic liquid crosslinking polymers of IHCPs was post-
crosslinked by the self-crosslinking of the benzene ring and chlor-
omethyl (ACH2Cl) in the precursor polymers through the Friedel-
Crafts alkylation reaction. The polymers showed good performance
for CO2 capture (94.60 mg
g1 at 273 K and 0.1 MPa).
2.1.2. Direct condensation of multifunctional monomers (or mixtures)
Different from the post-crosslinking method, the direct conden-
sation of multifunctional monomers (or mixtures) to construct the
HCPs could reduce the complexity of preparation procedures. Spe-
cial reactions were chosen for this strategy, such as the Friedel-
Crafts alkylation reaction, free radical polymerization, hydroxyl-
aldehyde condensation reaction, and Scholl coupling reaction. In
2008, Cooper’s group [39] firstly reported the HCPs were synthe-
sized by self-condensation of multifunctional monomers of
dichloroxylene (DCX) and 4,40 -bis(chloromethyl)-1,10-biphenyl
(BCMBP). The resulting polymers showed high SBET of
1307 m2
g1. Subsequently, the other multifunctional monomers
were also performed for the construction of HCPs, which had
reported in the recent review [16]. For this kind of HCPs, with
the help of Lewis acid catalysts, the chloromethyl, bromomethyl,
and benzyl alcohol groups could crosslinked with the neighboring
phenyl rings through multi-substitution, resulting the polymers
with high SBET and good performance in CO2 capture. For instance,
Tan and co-workers [40] constructed two kinds of HCPs by the self-
polycondensation of 1,4-benzenedimethanol (BDM) and benzyl
alcohol through FeCl3 catalytic Friedel-Crafts alkylation reaction.
Fig. 1. (a) Synthetic route for melamine-based HCPs; (b) CO2 isotherms at 273 K, and (c) selectivity for CO2/N2 based on IAST at 273 K.
93
The polymer of HCP-BDM showed high SBET (847 m2
g1), Vmicro
(0.21 cm3
g1), and good performance in CO2 capture
(126.00 mg
g1 at 273 K and 0.1 MPa).
Free radical polymerization of styryl content monomers also
caught a lot of attentions. For instance, Tu and co-workers [41]
synthesized a series of sponge-like quaternary ammonium-based
mesoporous poly(ionic liquid)s (MPILs) using ionic liquids func-
tionalized styryl content monomers by free-radical polymeriza-
tion. Although the polymers showed low SBET, total pore volume
(Vtotal), and CO2 capture (54.00 mg
g1 at 273 K and 0.1 MPa), the
polymers performed good for CO2 cycloaddition reaction (yield of
99.6% at 90 °C and 0.1 MPa). Subsequently, a series of crosslinked
imidazolyl MPILs with high SBET and Vtotal were prepared by the
same method. The maximum SBET and Vtotal were 798 m2
g1 and
2.05 cm3
g1, respectively, and the adsorption capacity of CO2
was up to 158.40 mg
g1 [42]. Dai and co-worker [43] prepared
the nitrogen-functionalized POPs (PDVB-VP) with high SBET and
Vtotal by the one-step copolymerization of divinylbenzene (DVB)
with vinyl-contained monomers (e.g., 4-vinylpyridine [VP] and
1-vinylimidazole [VI]) under solvothermal conditions. It shows
good CO2 adsorption performance under low pressure conditions
(64.68 mg
g1 at 273 K and 0.015 MPa). Subsequently, a series of
P(VCB-HMTA)s were prepared by aqueous and template-free route
herein. And the adsorption capacity of CO2 was up to 69.52 mg
g1
at 273 K and 0.015 MPa [44].
Hydroxyl-aldehyde condensation reaction was also a kind of
useful reaction for the HCPs construction. For example, Han’s
group [45] prepared two hydrophobic pyrene-based hyper-
crosslinked microporous resins (ZLYs) by condensation of 1,3,6,8-
tetrakis(p-formylphenyl)pyrene (TFPPy) with phloroglucinol
(L1)/1,5-dihydroxynaphthalene (L2) (Fig. 2). The polymers showed
high SBET of 647 m2
g1, and the structure of ZLYs exist intrinsic
hydroxyl groups on the pore-walls. Hydroxyl group could enhance
the force between CO2 and ZLYs, resulting the polymers with high
CO2 uptake of 112.60 mg
g1 and Qst of 31.6 kJ
mol1. Scholl cou-
pling reaction had also widely used for the construction of HCPs.
In this strategy, phenyl rings of aromatic monomers were linked
directly by elimination of hydrogen atoms and forming a new
aryl-aryl bond by the catalysis of AlCl3. Unlike the HCPs were con-
structed by external crosslinkers, Scholl-coupled could clearly
increase the SBET. For instance, Tan and coworkers [46] firstly con-
structed a series of HCPs by Scholl coupling reaction of naph-
thalene, pyrene, triphenylphosphine (PPh3), 1,10-phenanthroline
monohydrate, benzyl amine, benzoic acid, pyrrole, thiophene,
furan, phenyl cyanide, phenylene diamines, and 2,20 -bipyridine
94 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
Fig. 2. (a) Synthetic route for ZLYs; (b) CO2 isotherms at 273 K, and (c) Qst of the ZLYs.
through self-crosslinking. The resulting polymers all showed high
SBET (as high as 1421 m2
g1) and abundant Vmicro, which made
the polymers showed high CO2 capture (202.00 mg
g1 at 273 K
and 0.1 MPa). Cui and co-workers [47] also constructed a kind of
HCPs by self-crosslinked of 3,5-diphenyl-1H-pyrazole through
Scholl coupling reaction. The resulting polymer of MOP-PZ had
high SBET of 965 m2
g1 and N content, the CO2 capture as high
as 202 mg
g1. The common HCPs have low selectivity for
CO2/N2 for the lake of heteroatoms. However, the HCPs with high
SBET and CO2 capacity were hardly got by crosslinked of heteroa-
tomic functionalized monomers directly. For this purpose, Cooper
and co-workers [48] reported a kind of Scholl-coupled microp-
orous polymers and post-functionalized by fluoride. The post-
synthetic fluorination polymers showed higher CO2 capacity
(132.00 mg
g1 at 273 K and 0.1 MPa) and selectivity for CO2/N2
(IAST: 26.0) than the direct crosslinking of fluorobenzene (CO2:
106.00 mg
g1, selectivity for CO2/N2: 10.0).
2.1.3. Knitting method with external crosslinking agent
At present, the method of knitting method with external
crosslinking agents was most commonly used for preparation of
the HCPs. This method include two kinds of external crosslinking
agents, one was the common external crosslinking agents which
were added directly for crosslinking, the other one was solvent
knitting method, for which the solvents itself were used as
crosslinking agent. For the first kind of cross-linkers, formaldehyde
dimethyl acetate (FDA), DCX, 1,4-dimethoxybenzene (DMB) and
cyanuric chloride (CC), etc. were widely used as the external
cross-linkers.
FDA was the most popular external cross-linker for HCPs con-
struction. As was firstly reported by Tan and co-workers in 2011
[49], a great amount of HCPs were prepared in this way. In recent
years, Dai and co-worked [50] used heterocyclic carbazole as raw
materials, FDA for external cross-linker, and trifluoromethanesul-
fonic acid (Brønsted acid) instead of traditional Lewis acid to
induce a ‘‘knitting”. And a series of HCPs (HC-PCz-(1-8)) were suc-
cessfully fabricated by Friedel-Crafts alkylation reaction (Fig. 3).
The highest SBET was 1688 m2
g1, the maximum CO2 uptake of
189.20 mg
g1 at 273 K and 0.1 MPa, and the selectivity for CO2/
N2 was 17.0. Lau’s group [51] also used the Brønsted acid as the
catalyst for catalyzed the Friedel-Crafts alkylation reaction, for
which triptycene and FDA were used for constructing the HCPs.
The reaction time could be greatly reduce by replacing Lewis acids
with Brønsted acids as catalyst, and the SBET was improved for 27%,
CO2 uptake increased 24% (up to 146.08 mg
g1 at 273 K and
0.1 MPa). CC and DMB were also widely used for HCPs construc-
tion. Sadak [52] reported three kinds of HCPs by crosslink of
4,40 -bis(N-carbazolyl)-1,10 -biphenyl (YBN-DMB) and three cross-
linkers of FDA, CC, and DMB. The SBET for the three HCPs were
968, 784, and 579 m2
g1, corresponding to FDA, DMB, and CC,
respectively. For FDA, the multi-substitution will greatly increase
the SBET, however, the steric effect made CC and DMB hardly
multi-substitute in one benzene ring.
The higher SBET of the polymers made them perform well in CO2
capture (88.00–127.00 mg
g1 at 273 K and 0.1 MPa). Das et al. [53]
constructed three HCPs by triptycene and three crosslinkers
(2,6-dichloropyrazine, 3,6-dichloropyridazine, and 2,4-
dichloropyrimidine) through AlCl3 catalytic Friedel-Crafts alkyla-
tion reaction. Among them, TNHCP2 showed high SBET of more than
751 m2
g1 and high N contents, resulting high CO2 capture of 127.
00–160.00 mg
g1 at 273 K and 0.1 MPa. Wang et al. [54] used DCX
as external crosslinking agent, a variety of imidazolium salts for
functional monomers, a series of imidazolium-functionalized ionic
HCPs with abundant ionic sites, large surface area, and rich micro/
mesoporosity were straightforwardly synthesized through Friedel-
Crafts alkylation. Abundant microporosity and rich ionic moieties
gave the polymers remarkably CO2 capture performance. The
adsorption capacity of CO2 was up to 134.20 mg
g1 (at 273 K
and 0.1 MPa) and selectivity for CO2/N2 was as high as 86.0
(Henry)/336.0 (IAST). Our group [55] prepared a series of
benzimidazole-based hyper-cross-linked poly(ionic liquid)s
(HPILs). In this reaction system, benzimidazole as ionic liquids
(ILs) monomers, benzyl chloride or benzyl bromide for external
crosslinking agents, the Friedel-Crafts alkylation reaction was
 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
Fig. 3. The synthesis route of nanoporous HCPs.
occurred between ILs monomers and benzyl halides. With the pro-
duction of imidazolium salts, rich ionic active sites were loaded in
HPILs. The high SBET and abundant nitrogen (N) content was bene-
ficial to CO2 adsorption, and the HPILs showed good CO2 capture
performance of 143.00 mg
g1 at 273 K and 0.1 MPa, and the selec-
tivity for CO2/N2 was 44.0.
Solvent knitting method had also caught improved attentions
for constructing of HCPs. Recently, Tan and co-workers [56] used
polycyclic aromatic hydrocarbons (PAHs) such as fluoranthene,
binaphthalene, naphthalene and phenanthrene, etc. as raw materi-
als, dichloromethane (DCM) as reaction solvent and external cross-
linker, a series of functionalized HCPs were prepared by Friedel-
Crafts alkylation reaction under the catalysis of AlCl3. Comparison
of the four PAH-based HCPs, the SBET of the four polymers ranged
from 978 to 1788 m2
g1. And the CO2 uptake capacity ranged from
181.50 to 247.90 mg
g1 at 273 K and 0.1 MPa. More importantly,
the electron-riched PAHs contain p conjugated systems were con-
sidered to be good candidates for the efficient separation of CO2
and energy storage materials. The other HCPs reported in recent
years for CO2 capture were listed in the Table 1.
In recent decades, HCPs have developed greatly. Both the syn-
thetic methods and the application fields have been greatly
expanded. However, there are still many challenges in the develop-
ment of HCPs. For example, the biggest disadvantage of the HCPs is
the randomness, and the resulting polymers networks usually do
not have regular structures, which greatly limits the performance
of polymers networks for applications.
95
2.2. CMPs for CO2 adsorption
As a kind of amorphous POPs with large conjugated skeleton,
CMPs were constructed by p-p conjugated rigid structural units.
The way of producing micropores structures in the framework
was directly connected with aromatic ring structural units or indi-
rectly connected with other aromatic ring monomers through
C@C/C„C bonds. The whole rigid framework could be completely
conjugated through the single-double/triple bonds tautomerism
[65]. A large amount of common reactions could be used for the
construction of CMPs, such as Suzuki cross coupling reaction
[66], Yamamoto coupling reaction [67], Schiff-base reaction [68],
Sonogashira-Hagihara coupling reaction [69], Friede-Crafts reac-
tion [70] and Buchwald Hartwig amination [71], etc. CMPs as typ-
ical amorphous polymers, 3D network structure could be formed
by p-p conjugated polymerized between the monomers, resulting
the polymers with high SBET and Vtotal. The covalent bonds con-
nected structures made the CMPs stable enough under high tem-
perature, therefore, CMPs were extensive used for CO2 adsorption
[72].
For example, Han et al. [73] prepared two sp2 carbon CMPs (BO-
CMP-1 and BO-CMP-2) with analogous structure through
palladium-catalyzed Suzuki-Miyaura cross-coupling reaction by
9,10-bis(dibromomethylene)-9,10-dihydroanthracene (BBMA)
and 1,4-phenylenediboronic acid. Then the CMPs were further
post-oxidated (oBO-CMP-1 and oBO-CMP-2) to enhance the rigid-
ity of CMPs structure. The adsorption performance of CMPs could
96 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103

Table 1
CO2 adsorption and separation performance of amorphous POPs

POPs SBET/m2
g1 Smicro/m2
g1 Vtotal/cm3
g1 Vmicro/cm3
g1 CO2 uptake Selectivity Qst/kJ
mol1 Ref.
capacity/mg
g1
271 K 298 K CO2/N2 CO2/CH4
CP-3 1007 0.14 76.03 47.87 [57]
TNCHP1 848 0.45 127.00 97.00 30.0 5.0 20.6 [53]
TNCHP2 766 0.40 160.00 93.00 42.0 6.0 26.0 [53]
TNCHP3 751 0.39 156.00 98.00 45.0 6.0 25.3 [53]
R/HMTA 442 0.61 83.60 65.00 56.0 [58]
PEI-PDVB 38 0.32 162.80 69.9 [59]
LKK-CMP-1 467 0.37 97.80 60.80 44.2 8.2 35.0 [60]
CMP-LS1 493 0.32 0.12 60.89 33.39 23.2 4.5 33.6 [61]
CMP-LS2 1576 1.06 0.36 170.89 92.32 27.9 5.6 36.6 [61]
CMP-LS3 643 0.37 0.17 82.50 47.14 19.8 4.5 35.3 [61]
SN@CMP-1 89 19 0.12 0.02 47.73 29.66 22.6 4.6 38.6 [62]
SN@CMP-2 590 548 0.44 0.23 67.57 46.75 27.7 7.7 44.7 [62]
SN@CMP-3 804 626 0.78 0.38 105.09 65.80 36.9 6.9 37.9 [62]
SN@CMP-4 1143 885 1.04 0.62 114.71 74.84 38.0 6.0 39.9 [62]
SN@CMP-5 1356 1030 1.42 0.85 127.48 88.00 56.5 6.5 44.4 [62]
SN@CMP-6 1172 920 1.16 0.76 169.91 104.89 61.5 4.5 59.8 [62]
SN@CMP-7 804 596 0.80 0.55 119.82 84.46 36.8 6.1 37.3 [62]
FcCMP-1 638 475 0.29 0.19 96.80 51.5 26.5 [63]
FcCMP-2 422 306 0.23 0.14 70.40 2.8 30.3 [63]
PAF-60 1094 218.04 145.36 80.4 9.8 36.9 [64]
PAF-61 793 157.14 98.21 64.2 10.5 31.6 [64]
PAF-62 701 145.36 94.29 275.0 18.7 34.2 [64]

be adjusted by adjusting the porosity of CMPs through post-
oxidation reaction. BO-CMP-1, BO-CMP-2, oBO-CMP-1 and oBO-
CMP-2 polymers displayed CO2 uptake of 79.00, 106.00, 51.00
and 75.00 mg
g1 (273 K and 0.1 MPa), respectively, and the Qst
of the four CMPs were less than 36.5 kJ
mol1, indicated that CO2
has a good affinity with aromatic micropore walls with large
porosity. Sun et al. [74] fabricated two novel CMPs (NUT-14 and
NUT-15) by Yamamoto coupling reaction and Sonogashira-
Hagihara coupling reaction. The results showed that NUT-15 with
larger SBET (415 m2
g1) and Vtotal (0.24 cm3
g1) than NUT-14
(SBET: 302 m2
g1; Vtotal: 0.18 cm3
g1). The adsorption and separa-
tion performance for CO2 of the two kinds of NUT were compared,
NUT-15 have the CO2 uptake of 127.60 mg
g1, which was the
twice of NUT-14 (74.80 mg
g1, 273 K and 0.1 MPa), and the
CO2/CH4 selectivity of NUT-14 and NUT-15 were 5.0 and 12.4,
respectively. Xu’s group [75] synthesized three CMPs with abun-
dance N and oxygen (O) by imidizing tetra-(4-aminophenyl) ethy-
lene and anhydrides (CMP@1  3). The SBET and Vtotal of the three
CMPs were calculated to be 346 m2
g1 and 0.22 cm3
g1,
325 m2
g1 and 0.60 cm3
g1, and 343 m2
g1 and 0.70 cm3
g1
for CMP@1,CMP@2, and CMP@3, respectively. The abundant N
and O contents of the three CMPs provide sufficient adsorption
sites for CO2. The maximum adsorption capacity of CO2 was
101.80 mg
g1 (273 K and 0.1 MPa) and the selectivity for CO2/
CH4 was 16.6.
CMPs always prepared by different reactions and monomers,
resulting the polymers with different CO2 adsorption properties
for different porosity and functioned groups. Hu et al. [76] prepared
three CMPs through cationic cyclization polymerization by multi-
ple enediyne moieties monomers. The SBET value of CMP1, CMP2
and CMP3 were 767, 624 and 780 m2
g1, respectively. The Smicro
(481 m2
g1) and Vmicro (0.19 cm3
g1) of CMP1 were larger than
those of CMP2 (302 m2
g1 and 0.12 cm3
g1) and CMP3
(134 m2
g1 and 0.02 cm3
g1). The higher Smicro and Vmicro endow
the good CO2 adsorption performance (129.60 mg
g1 at 273 K and
0.1 MPa) for CMP1. The porphyrin-based polymers were widely
used for their stable structure and porosity. If loaded with metal
ions, the active sites could be enhanced and the polymers could
have better performance in gas capture. Su and co-workers [77]
fabricated two porphyrin-based CMPs (Porp-TPE-CMP and
Porp-Py-CMP) through coupling reaction catalyzed by FeCl3. The
SBET of Porp-TPE-CMP (547 m2
g1) was one order of magnitude
larger than Porp-Py-CMP (31 m2
g1), indicative higher CO2 uptake
of Porp-TPE-CMP (88.75 mg
g1) than Porp-Py-CMP (54.41 mg
g1)
at 273 K and 0.1 MPa. The selectivity for CO2/N2 and CO2/CH4 of
Porp-TPE-CMP and Porp-Py-CMP were calculated to be 55.3 and
40.8, 4.1 and 5.1, respectively. The other CMPs reported in recent
years for CO2 capture were listed in the Table 1.
CMPs have emerged as a broad platform for CO2 adsorption due
to their high SBET, Vtotal and thermal stability. By changing the
structure and synthetic strategy of CMPs, the adsorption capacity
and selectivity of CO2 can be adjusted. However, the use of expen-
sive metals in some CMPs synthetic processes, which limits their
application in large-scale application.
2.3. PIMs for CO2 adsorption
The PIMs are a kind of novel materials with micropores in own
structures, they are also called intrinsic microporous polymers. The
monomers for the construction of PIMs usually have dense ring
and trapezoidal twisted molecular chain. The trapezoidal skeleton
and twisted structure limit the rotation of polymer chains, which
make the molecular chains cannot be effectively stacked. There-
fore, they have high free volume and microporous structure, which
makes them have excellent gas capture performance [78]. In 2002,
McKeown et al. [79,80] firstly used the benzodioxane to connected
diphthalonitrile units and the polymer with microporous structure
and high SBET (895 m2
g1) was obtained. Then using a similar
method, porphyrin as the monomer, they obtained a porphyrin-
based microporous polymer with SBET of up to 910 m2
g1. In
2005, Budd et al. [81] synthesized a series of linear PIMs. Different
from the above-mentioned insoluble 3D PIMs network frame-
works, linear PIMs can be dissolved in many organic solvents and
spin-coated into a membrane. Compared with other rigid struc-
tured polymers, the CO2 permeability of PIMs membranes was sig-
nificantly higher [82]. For this reason, large amount of PIMs as
separation membranes were used for selectively gases separation.
Filiz’s group [83] prepared a mixed matrix membrane (MMM)
with excellent gas transport performance based on PIM-1. The
gas transport performance of the membrane can be adjusted by
 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
controlling the loading of Potassium dodecahydrodecaborate
(K2B12H12) inorganic particles (IPs). When the loading of IPs
increased up to 10%, the CO2 permeability of PIM-1 was maximum
(12954 ± 23 Barrer, 1 Barrer=7.521018 m3 (STP)
m2
m
s1
Pa1),
which was increased for 31% by comparing with the pure PIM-1
(9896 ± 28 barrer). Fuoco’s group [84] analyzed the details of basic
transport parameters of triptycene-based ultrapermeable PIM-
TMN-Trip membrane and PIM-BTrip membrane (Fig. 4). Those
two PIMs membranes have already been reported, but without
basic parameters of gas transmission. Therefore, they obtained
the activation energy of permeation, diffusion and sorption for
PIMs membranes through theoretical calculation. They also
obtained the selectivity of diffusion, entropy and energy by calcu-
lated. The results showed that the permeability of PIMs mem-
branes was increased with the increasing of diffusion coefficient
and solubility coefficient. Meanwhile, the size of PIMs membranes
and the temperature also have greatly influence on permeability
and selectivity. This work provides a strong theoretical basis for
the gas adsorption performance of PIMs membranes and lays a
foundation for the design and development in the future.
Regen et al. [85] synthesized a series of polyelectrolyte multi-
layers containing PIMs via the layer-by-layer deposition method.
The thickness of the membranes was changed with the number
of deposition layers. The influence of membranes thickness on
gas separation had been investigated. The results indicated that
the 6 nm multilayers derived from 1 plus poly(diallyldimethylam-
monium chloride) showed exceptional permeation properties with
CO2 and N2. The CO2 permeability was 130 GPU and the selectivity
for CO2/N2 was 33.0. McKeown et al. [86] fabricated four
ethanoanthracene- (EA) and triptycene- (Trip) based polymer
membranes (TB-PIM) with/without bridgehead methyl sub-
stituents. They researched the influence of SBET and gas separation
performance of the polymer membranes by methyl substituents.
Fig. 4. (a) Molecular structures of PIM-1, PIM-TMN-Trip and PIM-BTrip; Robeson plots for the (b) CO2/CH4 and (c) CO2/N2 (1.0 Barrer = 7.521018 m3 (STP)
m2
m
s1
Pa1).
97
The results showed that the SBET and Vtotal were increased after
bridgehead methyl substituents, nevertheless, the SBET and Vtotal
were not the decisive factors for the selective permeability of
gases. It mainly depends on the size of the porosity and the inter-
connection among pores. And the types, orientation, final arrange-
ment and expansion of macromolecular groups in polymer
backbone were also played important roles in CO2 selectively sep-
aration performance.
Qin’s group [87] for the first time used the Al2O3 atomic layer
deposition (ALD) technique to modify the microporosity of PIM
(PIM-1) at the atomic level to adjust the performance of CO2 sepa-
ration. With the increasing of ALD cycle numbers, the permeability
of CO2 decreased, and the selectively significant increased. The
maximum selectivity for CO2/CH4 (56.2) and CO2/N2 (29.3) were
obtained at 6 ALD cycles. The results showed that the microporous
porosity of PIM-1 could be adjusted systematically by changing the
cycle numbers of ALD, the adsorption and separation performance
of gas were also adjusted. The method of ALD technology provides
a new way to construct PIMs membranes. The other PIMs reported
in recent years for CO2 capture were listed in the Table 1.
The PIMs have widely used for CO2 capture for their high SBET
and Vmicro. Some linear PIMs could be dissolved in many organic
solvents and spin-coated into membranes. The PIMs membrane
has already been one of the famous separation membranes for
their excellent selectivity and permeability of gases. Nevertheless,
PIMs membrane inevitably has the defect of physical aging. There-
fore, how to improve this limitation through the design of the
structure is of great important.
2.4. PAFs for CO2 adsorption
The PAFs are a kind of porous solid materials with rigid skeleton
structures and synthesize according to topology theory. PAFs are
98 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
always constructed by CAC bond coupling between the rigid
organic monomers, resulting the structure with higher SBET and
stability. In 2009, Zhu’s group [88] firstly reported the PAFs with
2D/3D periodic aromatic frameworks. The PAFs were effectively
assembled from organic building blocks through irreversible
coupling reactions (usually CAC bond coupling). This method
was based on topological orientation, which could realize the
unprecedented feasibility of synthesizing and pre-determining
the structure of POPs. In that way, porous materials could be
designed on the basis of specific uses. And diversified functions
could be designed and synthesized according to the inherent
chemical properties of the PAFs structural units, or achieved by
post-modification of the aromatic skeleton through common
organic reactions. Hence, PAFs were widely used in CO2 capture
and separation [89].
With time going on, researches on PAFs had gradually
increased. In 2011, Qiu et al. [90] synthesized two PAFs (PAF-3
and PAF-4) by using four-coordinated silicon and germanium as
raw materials by Yamamoto-Ullmann reaction. The resulting poly-
mers showed high SBET and stability. The SBET and Vtotal of PAF-3
and PAF-4 were 2932 m2
g1 and 1.54 cm3
g1, 2246 m2
g1 and
1.45 cm3
g1, respectively. The large SBET and Vtotal was conducive
for CO2 adsorption, with the value of 153.00 mg
g1 and
107.00 mg
g1 for PAF-3 and PAF-4, respectively. Hill and co-
workers [91] developed a method for the lithiated of PAN-1
(Li@PAF-1). This strategy enhanced the surface activity of PAN-1,
the adsorption enthalpy, and the gas adsorption performance.
Compared with the original PAN-1 polymer, Li@PAF-1 showed an
increasing of the adsorption capacity of CO2 for 320%
(395.50 mg
g1 at 273 K and 0.1 MPa).
With the development of PAFs, increasing interests were focus
on gas adsorption. In recent years, Bracco et al. [92] synthesized
a porous 3D fluorinated PAF (F-PAF1) by condensation of fluori-
nated tetraphenylmethane (TPM) monomer. The SBET was
2050 m2
g1. After fluorination, the C-F dipoles were partially built
on the PAFs framework. In this, the C-F dipoles were arranged in
the swellable architecture by non-centrosymmetric, giving the
entire p-phenyl groups a dipole moment. This non-
centrosymmetric way of regularly spaced fluorine substitution
made the substitution amount of fluorine atoms limited and
ensured that the skeleton as light as possible. In the PAFs structure,
the uniformly distributed C-F dipoles were exposed to the diffused
gas. Compared with the unfluorinated PAF1, the affinity of CO2 was
greatly promoted, and the selectivity for CO2/N2 was also
improved. In order to obtain a better PAFs-based CO2 adsorbent,
it is necessary to precisely adjust the pore size and Vtotal to increase
the affinity of PAFs polymers for CO2 [93]. Jiang’s group [89] made
full use of the advantages of ionic liquids and PAFs, impregnated
charged PAFs with ionic liquids. They confined cations and anions
within the polymers framework through electrostatic interaction.
The loading of the ionic liquids made the PAFs structures produced
nano-scale space, which could improve the capture of the gases.
And the ionic liquids could also promote the transmission of the
gas in the porous structure. In that way, the permeability of CO2
and the selectivity for CO2/CH4 could be adjusted by adjusting
the loading of ionic liquids. Liu et al. [94] used biphenyl and
diphenylamine as build units to prepared PAFs (PAF-45DPA) with
functional groups and high porosity. The rigid structure of biphenyl
provides a porous structure for PAFs, diphenylamine provides basic
N functional groups, and the porous structure provides channels
for gas transmission. According to the acid-base theory, basic N
functional groups can effectively adsorb CO2 and other acid gases.
Hence, PAF-45DPA showed high SBET (679 m2
g1), CO2 uptake
(88.98 mg
g1 at 298 K and 0.1 MPa), and selectivity for CO2/N2
(63.1). The other PAFs reported in recent years for CO2 capture
were listed in the Table 1.
In the past decade, the PAFs had also developed rapidly, and
PAFs showed excellent performance in CO2 adsorption and separa-
tion. However, organometallic catalysts were often used in the pro-
cess of PAFs synthesis. Those catalysts were expensive and difficult
to remove from the framework, which will block the pores and
decrease the porosity. For this reason, it is meaningful for research-
ers to develop a method for the construction of PAFs with high
porosity and low cost.
3. Crystalline POPs for CO2 Adsorption
Compared with POPs with amorphous structure, crystalline
structured POPs have adjustable structure, pore channels, and
highly ordered structures. The COFs and CTFs are belongs to crys-
talline POPs, and they are briefly introduced as followed.
3.1. COFs for CO2 adsorption
The COFs are a kind of porous organic framework polymers
with long-range ordered structure and are connected by covalent
bonds (BAO, CAC, C@H, C@N, CAN, etc.). COFs always obtained
through reversible condensation under thermodynamic control,
the resulting structure is more stable than MOFs. As a kind of
typical POPs with crystal structure, COFs have attracted a lot
of attentions in recent years [27,28,95]. Since Yaghi’s group
[96] first reported COFs in Science, COFs have received wide-
spread attention. The methods for the construction of COFs
include microwave and mechanically assisted synthesis,
solvothermal synthesis, and room temperature synthesis, etc.
Generally speaking, most of the reported COFs were synthesized
in a sealed container under solvothermal conditions. By selecting
different organic monomers, adjusting the ratio of monomers,
and controlling the reaction conditions, COFs with different
structures and morphologies could be pre-designed accurately.
Therefore, this article briefly summarizes the adsorption and
separation of CO2 by COFs with different covalent bonding
methods.
3.1.1. Imine linked
The COFs connected by imine are considered as a more
advantageous gas adsorbent for the stable structure in some
harsh conditions. Therefore imine linked strategy has been one
of the most extensive covalent bonding for COFs construction.
El-Kaderi et al. [97] prepared the ILCOF-1 with high SBET
(5070 m2
g1) by using tetrakis(p-formylphenyl)pyrene and 1,4-
p-phenylenediamine as the raw materials. And the ILCOF-1
showed good CO2 uptake (492.80 mg
g1 at 298 K and
4.0 MPa), and low Qst (18.3 kJ
mol1). Neogi et al.[98] syn-
thetized an imine linked 3D COF with the structure of nine-
fold interpenetration via tetra(p-aminophenyl)methane (TAPM)
and N-functionalized linear strut 2,20 -bipyridine-5,50 -dicarbalde
hyde (BPDCA). The COF had one-dimensional porous channels,
high SBET (5070 m2
g1) and Vtotal (1.93 cm3
g1), resulting the
COF with high CO2 adsorption capacity of 173.50 mg
g1. And
the Qst was 35.0 kJ
mol1, CO2 adsorption selectivity were as
high as 64.2 (selectivity for CO2/N2) and 10.5 (selectivity for
CO2/CH4), respectively. Thereafter, they anchored the Ru into
COF to catalyze the conversion of CO2 into cyclic carbonates.
Nagaraja et al. [99] prepared a N-riched COF with high SBET
(736 m2
g1) by Schiff-base condensation reaction between
4,40 -azodianiline (AZO) and benzene-1,3,5-tricarboxaldehyde
(BTA). The COF exhibits CO2 adsorption capacity of 52.25 mg
g1
at 273 K, 134.55 mg
g1 at 195 K, and 31.23 mg
g1 at 298 K,
and the Qst was 32.3 kJ
mol1.
 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
3.1.2. b-ketoenamine linked
The synthesis of b-ketoenamine linked COFs are based on the
reversible Schiff base reaction between trialdehyde phloroglucinol
and amino monomers to form an eno-limine structure, which is
then irreversibly convert to a stable structure of ketoenamine.
Compared with eno-limine isomers, the ketoenamine isomers are
dominated (Fig. 5) [100]. Wei’s group [101] synthetized a 2D b-
ketoenamine TpTa-COF under lower temperatures and shorter
reaction time via rapid microwave assisted solvothermal method.
The TpTa-COF had high stability and SBET (725 m2
g1) and showed
a good performance of CO2 capture (224.40 mg
g1 at 273 K and
0.1 MPa), Qst of TpTa-COF was 34.1 kJ
mol1 and the selectivity
for CO2/N2 was as high as 32.0. Triformylphloroglucinol and azo
substituted 4,40 -biphenyl diamine were also used to prepared azo
functionalized b-ketoenamine-linked AzoCOFs (Tg-AzoCOF, C10-
AzoCOF and H-AzoCOF) by the Schiff base reaction. Among them,
H-AzoCOF showed good adsorption effect on CO2 for its higher SBET
and Vmicro [102]. Lai and co-workers [103] synthetized chlorine-
functionalized b-ketoenamine-based CAA-COF-1 and CAA-COF-2
by solvothermal method between triformylphloroglucinol and
2,5-dichloro-1,4-phenylene diamine/3,30 -dichlorobenzidine dihy-
drochloride. The CO2 uptake of CAA-COF-1 and CAA-COF-2 were
251.68 and 119.68 mg
g1 at 273 K and 0.1 MPa, respectively.
And the Qst of CAA-COF-1 and CAA-COF-2 were 29.9 and
29.5 kJ
mol1, respectively. The selectivity under dry and humid
mixed gas conditions was investigated, CAA-COF-1 showed better
selectivity for CO2/N2 and CO2/CH4 than CAA-COF-2. The selectivity
for CO2/N2 and CO2/CH4 of CAA-COF-1 in dry and humid mixed gas
conditions were 95 and 29, 87 and 26, respectively. The dipole
interaction between the electron-riched chlorine in CAA-COF
structure, the electron-deficient carbon in the CO2 molecule, and
the N-riched environment in the structure significantly all
improved the CO2/N2 selective separation performance.
3.1.3. Other linked
Thanks to the abundant monomers and multitudinous connec-
tion methods, a large amount of COFs with different linked types
had constructed. In addition to the above two connection methods,
there were boronate ester-linked, hydrazone-linked, azine-linked
and boroxine-linked, etc. El-Kaderi et al. [104] used 1,4-
benzenediboronic acid and hexahydroxytriptycene as raw materi-
als, the boronate ester-linked TDCOF-5 with high SBET
(2497 m2
g1) was synthetized. The adsorption capacity of CO2
was 92 mg
g1 (273 K and 0.1 MPa) and the Qst was 21.8 kJ
mol1.
Fig. 5. Illustration of (a) formation of b-ketoenamine linkage in COFs and (b) aldimine via an iminium ion intermediate.
99
At present, there are short of new boronate ester-linked COFs for
CO2 capture due to the boronate ester-linked COFs structure not
stable enough under acidic or basic conditions. Mothé Esteves
et al. [105] prepared a series of hydroxylated and azine-based
microporous COFs by condensation of hydrazine hydrate and
hydroxylated-1,3,5-triformylbenzenes. The SBET of COFs with dif-
ferent hydroxyl contents was quite different, large SBET always
have more hydroxyl. And the SBET was ranged from 242 to
1205 m2
g1. Therefore, the CO2 adsorption capacity were obvi-
ously different, and the CO2 adsorption capacity was ranged from
5.98 to 24.99 mg
g1 at 273 K and 0.1 MPa.
The present 2D hydrazine-linked COFs were demonstrated good
chemical stability in boiling water and strong acidic media. There-
fore, Karimi et al. [106] used 2,4,6-tris(p-formylphenoxy)-1,3,5-
triazine and oxalyl dihydrazide as raw materials, synthesized a
stable 2D hydrazine-linked COF (TPT/OH COF) with high SBET and
N-riched porous structure. The synthetic COFs showed the CO2
uptake of 39.60 mg
g1 under 0.1 MPa and 298 K. The other COFs
reported in recent years for CO2 capture were listed in the Table 2.
Membrane separation technology was already a mature technol-
ogy for CO2 separation. As a novel porous open framework materi-
als, COFs have already widely prepared into membranes for their
high porosity, SBET, and regular pore size, which endowed them
excellent CO2 separation performance [107]. For instance, Tan’s
group [108] reported a strategy of 3D MOF-mediated COF-based
membrane, in which MOF film provides the binding sites, and
the 2D COF structural building units were anchored along the ver-
tical direction. The 2D COF-based composite membrane H2P-DHPh
COF-UiO-66 was prepared by strong chemical bonding between 2D
COF and 3D MOF. The composite membrane showed ultra-high
CO2 permeability.
As a kind of crystalline structure POPs, COFs have adjustable
structure and pore channels. Although the pore size can be
adjusted through the design of the structure, it is difficult to con-
struct COFs with ultramicropores due to the limit of the size of
the construction units. Therefore, building a COFs with abundant
ultramicropores to achieve high selective CO2 adsorption and sep-
aration is an urgent problem.
3.2. CTFs for CO2 adsorption
The CTFs are a kind of high-performance organic porous mate-
rials which were widely developed in recent years. They are a new
type of polymers based on the cyano ring trimerization (formation
100 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103

Table 2
CO2 adsorption and separation performance of crystalline POPs

POPs SBET/m2
g1 Smicro/m2
g1 Vtotal/cm3
g1 Vmicro/cm3
g1 CO2 uptake Selectivity Qst/kJ
mol1 Ref.
capacity/mg
g1
273 K 298 K CO2/N2 CO2/CH4
ACOF-1 1176 0.91 177.00 55.00 40.0 37 27.6 [114]
TpPa-COF (MW) 725 218.00 32.0 34.1 [101]
[HO]25% 1054 0.89 54.00 31.00 32.2 [115]
[HO]50% 1089 0.91 46.00 34.00 29.4 [115]
[HO]75% 1153 0.96 52.00 32.00 31.5 [115]
[HO]100% 1284 1.02 63.00 35.00 8.0 36.4 [115]
[HO2C]25% 786 0.78 96.00 58.00 38.2 [115]
[HO2C]50% 673 0.66 134.00 67.00 39.6 [115]
[HO2C]75% 482 0.54 157.00 72.00 41.2 [115]
[HO2C]100% 364 0.43 174.00 76.00 77.0 43.5 [115]
COF-JLU2 415 0.56 217.00 77.0 31.0 [116]
3D-IL-COF-1 517 0.36 53.40 24.6 23.1 [117]
3D-IL-COF-2 653 0.53 76.10 24.0 22.3 [117]
3D-IL-COF-3 870 0.56 49.30 24.4 21.5 [117]
ICTFs-Cl 751 0.34 103.97 62.08 119.1 [118]
ICTFs-SCN 1010 0.46 109.24 61.49 39.3 [118]
ICTFs-Cl-SCN 885 0.44 92.19 61.73 44.2 [118]
HATN-CTF-1 926 0.35 173.80 120.12 53.0 9.8 26.8 [119]
HATN-CTF-2 1994 0.95 245.08 155.32 46.0 9.6 32.6 [119]
df-TzCTF600 1720 1.12 0.75 298.76 202.40 30.0 35.0 [120]
TzCTF600 1582 1.02 0.64 193.60 110.44 21.0 28.0 [120]

of triazine ring) of aromatic nitrile compounds, and was firstly pro-
posed by Thomas et al. in 2008 [109]. As a sub-category of COFs,
the pore size, SBET, pore structure and functional groups of CTFs
can be adjusted by selecting different monomers, and CTFs have
permanent open and stable pores. CTFs with different structures
(2D/3D), pore structures and different N contents can be obtained
by selecting different polymerization reactions (ionothermal reac-
tion, Friedel-Crafts reaction and Schiff base reaction, etc.). CTFs
polymers usually have large SBET, uniform porous structure, high
thermal/chemical stability, and rich N content, making them
widely used in CO2 capture.
As an important CO2 capture and storage adsorbent, CTFs have
received extensive attentions. Dai’s group [110] synthesized a ser-
ies of fluorine-functionalized CTFs-derived polymers of F12CTF-3-T
by using fluorinated trinitrile monomer through ionothermal
under different temperatures. The SBET was 2085 m2
g1 for
F12CTF-3-T and the pore size was about 0.7 nm which matches well
with the twice size of CO2. Therefore, F12CTF-3-T had high-
efficiency CO2 capture performance (289.52 mg
g1 at 273 K and
0.1 MPa). Kuo and co-workers [111] synthesized a series of
bicarbazole-based CTFs (Car-CTFs) by the same method through
the self-condensation of [9,90 -bicarbazole]-3,30 ,6,60 -tetracarboni
trile (Car-4CN). The Car-CTFs showed high SBET of 1400 m2
g1,
resulting very high CO2 adsorption capacity of 334.40 mg
g1
(273 K and 0.1 MPa) and 172.04 mg
g1 (298 K and 0.1 MPa),
respectively. The triazine structure has abundant N contents,
which were conducive to the adsorption of CO2. TCNQ-derived
CTFs (TCNQ-CTF) was prepared by 7,7,8,8-tetracyquinodimethane
(TCNQ). The SBET was as high as 4000 m2
g1, CO2 uptake was
263.56 mg
g1 at 273 K and 0.1 MPa, and the Qst was 29.2 kJ
mol1

Fig. 6. (a-c) Structural units; (d, e) CO2 adsorption isotherms and (f) Qst of CTFs (1 bar = 0.1 MPa).
 J. Wang et al. / Chinese Journal of Chemical Engineering 42 (2022) 91–103
[112]. Chen’s group [22] synthesized three CTFs (CTFs-N4, CTFs-O4
CTFs-S4) by using 2,4,6-tris(4-cyanophenylamino)-1,3,5-triazine
(TAT), 2,4,6-tris(4-cyanophenoxy)-1,3,5-triazine (TOT), and 2,4,6-t
ris(4-cyanobenzenesulfenyl)-1,3,5-triazine (TST) as building units
through ZnCl2-mediated heating cyclotrimerization method. The
maximum SBET was 758 m2
g1 and Vtotal was 0.29 cm3
g1. The
abundance N heteroatoms were extremely improved the CO2 cap-
ture. Adsorption capacity for CO2 were 149.60 mg
g1 (273 K) and
96.80 mg
g1 (298 K) under 0.1 MPa, the Qst was 44.0 kJ
mol1 and
selectivity for CO2/N2 was 45.0 (Fig. 6). Mukhtar and co-workers
[113] prepared high pressure selective CO2/CH4 adsorption CTF-
NH by using cyanuric chloride and 1,4-phenylenediamine. They
researched the CO2 selectivity adsorption performance under dif-
ferent temperatures (298 to 348 K) and pressures (1.0 to
2.0 MPa). The results showed that the CO2 adsorption capacity
was decreased with the increasing of temperature, while the selec-
tivity for CO2/CH4 obviously improved (2.7 to 5.1). After amine
functionalization the adsorption capacity of CO2 improved for
94.99% and the maximum CO2 uptake was 342.32 mg
g1. The
other CTFs reported in recent years for CO2 capture were listed in
the Table 2.
As an emerging porous material, CTFs has been widely used in
CO2 adsorption and separation. However, there were few CTFs with
crystalline structure, and amorphous CTFs are limited by CO2
adsorption sites, resulting unsatisfactory adsorption performance.
The common methods for the construction of CTFs were ther-
mosynthesis under 400 °C, the structure of CTFs could be partly
carbonized. The high energy consumption and uncertain structure
would limit the application of the CTFs for CO2 capture.
4. Conclusion and Prospect
We systematically reviewed the construction of different POPs
for CO2 capture. As a kind of promising polymers, the POPs were
constructed by lighter elements, rigid monomers, many chemical
bond formation methods, crosslinking reactions, and rigid covalent
bonds. Therefore, a large amount of POPs was constructed. The
high SBET and Vmicro, abundant heteroatoms, high physiochemical
stability, and unique porosity endowed the POPs excellent perfor-
mance for CO2. By comparing with other porous materials, the pore
structure, SBET, and function groups of POPs could be adjusted. In
this way, POPs with high SBET, heteroatoms contents, and ultrami-
cropore contents could be designed and constructed.
However, the application of POPs in CO2 capture was limited by
the adsorption capacity. As was reported by the literature, SBET, Vul-
tra, and heteroatoms play the key role in CO2 capture. Take HCPs for
example, aromatic rings were always multi-substituted and hyper-
cross-linked through Friedel-Crafts reaction, resulting the HCPs
with high SBET and abundant ultramicropores. However, the
hyper-cross-linking would create quite a few closed pores or even
solid structures, which were useless for CO2 capture. Hence, high
temperature carbonization was a promising way to create much
more micropores for the polymers. Although activated carbons
showed good CO2 capture, they were limited by the low selectivity
for CO2/N2 for the lack of functionalized groups and heteroatoms,
which were considered useful for the selectivity for CO2/N2. The
porous carbons derived from the POPs always showed good CO2
capture and selectivity for CO2/N2 for the abundant heteroatom
content of the POPs.
The utilization of the captured CO2 was also a promising strat-
egy for the reduction of CO2 excessive emissions. As a kind of C1
source, CO2 could be used for the preparation of cyclic carbonates
through cycloaddition reaction between CO2 and the epoxide. With
the functionalization of ionic liquids or metal ions, POPs could be
used for the catalysts of cycloaddition reaction for CO2 fixation.
101
POPs could be constructed with photo-responsive monomers
(porphyrin, carbazole, phthalocyanine, etc.), and the polymers
exhibit good performance for photocatalysis. In this way, CO2 could
be converted into high value-added chemical products (CO,
methane, ethanol, formic acid, etc.) through the photocatalysis.
The excessive emissions of CO2 have caused serious extreme cli-
mate. The reduction of CO2 has caused increasing attentions.
Hence, as a kind of promising materials, more and more POPs with
new functionalities would be designed and constructed. We hope
this work will provide guidance for the design and synthesis of
functional POPs for the development of advanced adsorption and
other performance.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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