d2cs00727d CO2 Pop

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Porous organic polymers for CO2 capture,

separation and conversion
Open Access Article. Published on 14 November 2022. Downloaded on 6/26/2023 12:24:49 PM.
Cite this: Chem. Soc. Rev., 2022,

51, 9831
Kyung Seob Song,† Patrick W. Fritz† and Ali Coskun *
Porous organic polymers (POPs) have long been considered as prime candidates for carbon dioxide
(CO2) capture, separation, and conversion. Especially their permanent porosity, structural tunability,
stability and relatively low cost are key factors in such considerations. Whereas heteratom-rich micro-
porous networks as well as their amine impregnation/functionalization have been actively exploited to
boost the CO2 affinity of POPs, recently, the focus has shifted to engineering the pore environment,
Received 26th August 2022 resulting in a new generation of highly microporous POPs rich in heteroatoms and featuring abundant
DOI: 10.1039/d2cs00727d catalytic sites for the capture and conversion of CO2 into value-added products. In this review, we aim
to provide key insights into structure–property relationships governing the separation, capture and con-
rsc.li/chem-soc-rev version of CO2 using POPs and highlight recent advances in the field.
Introduction in the coming years. Since CO2 is one of the main culprits of
global warming, research into remediation technologies is
Humankinds’ reliance on fossil fuels as a key energy source has booming. As a result, porous materials have gained consider-
resulted in a continuous rise in the atmospheric concentration able interest during the last two decades and various strategies
of carbon dioxide (CO2), reaching record levels of 419 ppm towards inorganic, organic and hybrid porous materials for CO2
(National Oceanic and Atmospheric Administration, Mauna capture have been investigated with the common goal to reduce
Loa station, Feb 2022)1 and expected to increase even further new CO2 emissions and to decrease the overall CO2 concen-
tration in the atmosphere.
Department of Chemistry, University of Fribourg, Chemin du Musée 9,
The main idea behind carbon capture and sequestration/
1700 Fribourg, Switzerland. E-mail: [email protected] storage (CCS) is to remove CO2 directly at their point sources or
† These authors contributed equally to this manuscript. to reduce existing emissions from the atmosphere through
Kyung Seob Song received his BSc Patrick W. Fritz obtained his BSc
degree in chemical engineering in technical chemistry from
from Chung Nam National Technische Universität Wien (TU
University (CNU), Republic of Wien) in 2018 and received his
Korea in 2014. He joined the MSc from the institute of
research group of Prof. Ali materials chemistry and the
Coskun in the Graduate School institute of applied synthetic
of EEWS at the Korea Advanced chemistry (IMC and IAS) under
Institute of Science and the supervision of Prof. Miriam
Technology (KAIST) in 2014 and M. Unterlass in 2019. In 2020 he
received his MSc degree in 2016. joined the group of Prof. Ali
In 2017, He moved to University Coskun at University of
Kyung Seob Song of Fribourg, Switzerland with Patrick W. Fritz Fribourg, where he works on
Prof. Ali Coskun and received porous organic polymers and
his PhD degree in chemistry in 2022. He works on design and covalent organic frameworks for separation and energy
synthesis of porous organic polymers (POPs) for environmental applications.
applications such as CO2 capture, separation and conversion,
precious metal recovery. Currently, he is a postdoctoral fellow
developing POPs for heterogenous catalysis.
This journal is © The Royal Society of Chemistry 2022 Chem. Soc. Rev., 2022, 51, 9831–9852 | 9831
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Review Article Chem Soc Rev
direct air capture (DAC) and store the captured CO2 under- concentrations of 5–15%. Gases are adsorbed within the pores
ground in deep geological formations. Although the concept of of the sorbent either through physical interactions and/or weak
CCS was first introduced in 1977,2 industrial technologies to chemical bonds at high pressure and desorbed once the
separate CO2 have been used since the 1920s in the purification pressure is lowered. Whereas adsorbents such as silica and
of methane from natural gas. The major difference between zeolites have been used in the past, recently, the scope has been
DAC and CCS lies in the CO2 concentration. Whereas the DAC extended to porous (metal–)organic materials such as porous
process needs to operate at low CO2 concentrations of around organic polymers (POPs) or metal–organic frameworks
400 ppm, CO2 capture from point sources via CCS operate at (MOFs).4,5 Although similar to PSA, VSA operates at near-
significantly higher CO2 concentrations. Depending on the ambient temperatures and pressures. The main difference is
source, CO2 concentration in various emission sources can vary that a pre-adsorption compression step can be avoided,
significantly from few percent to over 50%. Three main sources although some studies have shown that gas pressures slightly
namely pre-combustion, post-combustion and oxyfuel combus- above atmospheric pressure are favorable towards the uptake
tion are targeted with CCS. Whereas post-combustion CO2 capacity. In the VSA process, the desorption of CO2 and sorbent
capture from flue gas operates at low CO2 concentrations in regeneration operates by applying vacuum, which is considered
the range of 5–15% and requires the separation of CO2/N2 to be the most energy-demanding step of the process.6–8 TSA on
mixtures at 1 bar, pre-combustion (CO2/H2) and oxyfuel com- the other hand employs a thermal regeneration process, which
bustion (CO2 and water vapor) involve much higher CO2 is attractive for locations with low-grade thermal energy
concentrations.3 Industrially, aqueous amine solutions (often resources.8–10 Each of these three technologies have their own
monoethanol amine, MEA) have been employed in such pro- advantages and disadvantages and have also been used in
cesses. While these solutions are low-cost and offer very high combination to obtain better overall tradeoffs. Another alter-
selectivity towards CO2 over other gases, they suffer from low native to obtain high-purity CO2 is cryogenic distillation
uptake capacities and require a significant amount of energy dubbed cryogenic carbon capture (CCC). Cryogenic carbon
for their regeneration. Furthermore, MEA poses environmental capture revolves around the physical separation of different
and human health risks that have to be considered for such gases based on their boiling and re-sublimation temperatures
large-scale applications. and is commonly used in natural gas purification.11 CCCs
In this direction, the use of solid sorbents has emerged as a biggest advantage lies in the high purity of CO2 that can be
promising alternative as they offer higher thermal stability and obtained and used for several applications including, but not
potentially higher CO2 capacity, while regeneration can be limited to chemical transformations and enhanced oil
performed at significantly lower temperatures. For the recovery recovery,12 however, the immense energy cost due to cooling
of the captured CO2 and the regeneration of the sorbents, is a major drawback.
three main technologies have been established, namely, (i) Despite the lack of policies and insufficient financial incen-
pressure swing adsorption (PSA), (ii) vacuum swing adsorption tives to reduce carbon emissions and to retrofit existing facil-
(VSA), and (iii) temperature swing adsorption (TSA). PSA is ities with CCS technologies, the rising public awareness about
commonly applied for treating flue gas, which is comprised climate change resulted in new technologies being pioneered
of SO2, Hg, CO, H2O, CO2 and N2, and operates well with CO2 by upcoming small businesses. Among them, the combination
of CCS/DAC technologies with renewable energy has gained
substantial interest. An interesting example of such a technol-
ogy was brought to the market by ‘‘Climeworks’’ who are using
Ali Coskun received his PhD solid sorbents to directly capture CO2 from the air and CO2 is
degree in chemistry from Middle stored till the capacity is reached. Then, CO2 is concentrated by
East Technical University, heating the filters using renewable energy sources and subse-
Ankara, Turkey. He then joined quently stored underground13 or can be used in green houses
the laboratory of Prof. J. Fraser to artificially increase the amount of available CO2 for photo-
Stoddart as a postdoctoral synthesis. The cost of this system, however, is still well above
research associate at 500$ per tonne of CO2, which is rather high. Besides environ-
Northwestern University, where mental problems, CO2 also poses dangers to the human health,
he developed dynamic metal– especially in crowded, poorly ventilated rooms, where high
organic frameworks, artificial concentrations of CO2 can result in headaches, fatigue and
molecular machines. He started poor cognition. Accordingly, the capture of CO2 in such spaces
his independent career at Korea is also expected to be an important research direction.14
Ali Coskun Advanced Institute of Science in Porous materials such as activated carbons, silica, zeolites,
Technology in 2012. In 2017, he covalent organic frameworks (COFs), MOFs and POPs have
moved to University of Fribourg, Switzerland as a professor. He is actively been investigated as adsorbents for CO2. Importantly,
currently developing porous organic polymers for CO2 capture, key parameters need to be satisfied including high CO2 uptake
separation and conversion, for environmental remediation as well and working capacity, high CO2 selectivity over other gases
as high energy density for Li-ion batteries. (especially CO2/N2 selectivity) under humid conditions, fast
9832 | Chem. Soc. Rev., 2022, 51, 9831–9852 This journal is © The Royal Society of Chemistry 2022
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adsorption kinetics, low production cost, and low energy con- advantage – especially when compared to their crystalline
sumption during adsorption and regeneration steps.15–17 porous counterparts COFs and MOFs. The fact that POPs are
Besides the molecular properties of the gases or the surface generally obtained as kinetic products allows for easier upscal-
functionalities of the sorbents, textural properties such as the ing as fewer parameters have to be optimized and maintained
surface area, pore volume, and pore size have to be carefully throughout their preparation. It should however be noted that
considered when designing a sorbent for CO2 separation. The even in POPs, the synthetic conditions such as concentration,
adsorption of CO2 can occur via either physisorption or chemi- catalyst amount, and solvent can have a profound impact on
sorption process and the latter one involves the formation of a the porosity of POPs.23 The diversity in structures and suitable
covalent bond between the sorbent and CO2 molecule. The synthetic strategies24 that can be envisioned for POPs are rather
physisorption of CO2 on the surface of porous materials is an rich. Suitably functionalized precursors can be polymerized via
exothermic process that occurs through various non-covalent various strategies and used to tune the desired features of the
interactions. Critically, fine-tuning the pore size/structure can POPs. Recently even the use of shape-persistent molecules or
help to maximize these interactions and to increase the overall building blocks such as molecular cages and macrocycles
CO2 affinity and capacity. Pore sizes o2 nm are referred to have been investigated and have shown promising results in
as micropores, 2–50 nm as mesopores, and 450 nm as complex separation tasks.25
macropores.18 Considering the kinetic diameters of gases, e.g. Although briefly touched upon already, a wide variety of
3.3 Å of CO2, 3.8 Å of CH4 and 3.64 Å of N2, pore sizes closer to sorbents can in theory be used and are being used for the
the kinetic diameters of the gases would offer the highest remediation of CO2. Among the most used sorbents for CO2 are
affinity due to the possibility of multiple gas-surface interac- zeolites, porous carbons, metal oxides, mesoporous silica and
tions, thus microporous and ultra-microporous (pore size their amine functionalized or impregnated analogues. Each of
o0.7 nm) structures are preferred for high CO2 affinity. them with specific tradeoffs in terms of capacity, operating
Considering these aforementioned prerequisites, a key ques- conditions, stability, cost of production, and cost of regenera-
tion of ‘‘How can CO2-philicity over other gases under humid tion resulting in a plethora of factors that need to be consid-
conditions be governed?’’ has to be answered. ered. Taking porous metal oxides as an example one can easily
In organic or metal–organic systems such as POPs, COFs see that their availability, cost, extremely high theoretical
and MOFs, the building blocks determine the pore structure capacities, and good reactivity with CO2 under industrial con-
and the functionalities in the pores. CO2 is a highly stable ditions are considerable advantages. However, such systems –
symmetric molecule with a permanent quadrupole moment. similar to amine scrubbers – bind CO2 chemically (e.g. as
Therefore, dipole–quadrupole interactions can be exploited to MgCO3 in the case of MgO) which in turn requires significantly
attract and bind CO2 molecules, thus surface modification with higher reaction temperatures to regenerate the active material.
electron-rich or deficient atoms such as N, O, P, S or F are One of the main advantages of POPs over these systems is the
commonly employed in porous materials. As a result, the field structural tunability and precise control over the pore environ-
has moved to design cheap, heteroatom-rich POPs, COFs and ment for efficient CO2 capture and conversion.
MOFs with high surface areas, high pore volume and high CO2 Current CCS and DAC technologies are still costly which
affinity as key design factors for CO2 capture and separation. hinders their large-scale deployment. To become industrially
Given suitable functionalization, MOFs, COFs and POPs can relevant, a target cost of 50$ per tonne of CO2 should be
deliver high CO2 affinity, however, whereas MOFs and COFs are reached.26 To reduce the cost and to incentivize CCS, a circular
obtained under thermodynamic conditions, POPs are usually economy should be developed by using CO2 as a sustainable C1
prepared under kinetic conditions and are commonly obtained carbon source in industrial processes. In organic chemistry,
as amorphous materials. Despite crystallinity being a generally high-purity CO2 is used in various chemical transformations
favorable and sought-after property in porous materials, the such as the Grignard reaction, methanol and formic acid
increased cost associated with their preparation is a major synthesis, cyclic carbonate formation or carboxylations. One
factor hindering their wide-range industrial applications. None- of the main advantages of POPs – and porous materials in
theless, since the introduction of MOFs19 and COFs,20 their general – is that they can serve as hosts or directly as hetero-
ordered porosity and wide tunability have attracted consider- geneous catalysts to simultaneously capture and convert CO2.
able interest and the production of some MOFs on an industrial However, due to the high thermodynamic stability of CO2, its
scale has begun. However, in most cases, COFs are still lagging activation is rather difficult, requiring harsh reaction condi-
behind as their synthetic conditions require more precise tions. Therefore, designing POPs for CO2 conversion is signifi-
optimization before industrial applications become feasible. cantly more challenging than designing POPs for CO2 capture
At the same time, POPs have made a significant leap forward in and separation, and to date, there are significantly fewer POP
terms of the variety of available synthetic strategies and have heterogeneous catalysts for CO2 conversion.
shown high potential for CO2 capture, separation, and conver- In addition to the research efforts toward the activation of
sion owing to their high tunability, porosity, and exceptional CO2 in purely organic systems, POPs have also been used as
stability under operating conditions.21,22 Although, the amor- porous supports to incorporate atomically dispersed metal ion
phous nature of POPs is often referred to as a drawback, the catalytic sites, single-atom catalysts (SACs), or nanoparticles
ease of their synthesis has to be considered as a major (Al, Zn, Co, Pd, Ir, Ru and Ni), both of which are herein referred
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to as metal-containing POPs. Commonly employed ligands presented. Later, we discuss how POPs can be used for the
such as salens-, bipyridines-, N-heterocyclic carbenes can be simultaneous capture and conversion of CO2 towards value-
used as POP building blocks. Most synthetic approaches toward added products. We highlight metal-free POPs, namely porous
metal-containing POPs can be classified as follows: (i) polymer- organocatalysts, and evaluate their relative performance and
ization of suitably functionalized molecules featuring com- how they compare with metal-containing POPs. We also show-
plexation sites (e.g. amine-functionalized porphyrins), (ii) case metal-containing POPs in terms of their ability to stabilize
in situ formation of metal complexation sites (e.g. salen-based single metal atoms while maintaining high porosity and their
systems), or (iii) wet-impregnation of metal ions and NPs into applications in CO2 conversion beyond cycloaddition reactions.
POPs. In heterogeneous catalysis, POPs acting as porous sup-
ports have strong advantages. First of all, elaborate control over

the pore structure and heteroatoms contributes to effectively POPs for CO2 capture and separation
forming stable catalytic sites in POPs and enabling higher
catalytic activity. The precise control over the active sites is High surface area, abundant micropores along with the
the most important factor for CO2 conversion. For example, in presence of heteroatoms have been considered as the key
the cycloaddition of CO2 to epoxides, a bifunctional system is parameters for POPs with high CO2 selectivity and uptake
required to activate CO2 while also initiating the ring-opening capacity. Heteroatoms play a central role as high affinity bind-
reaction of the epoxide. In addition, POPs have also been ing sites towards CO2 via dipole–quadrupole interactions, in
studied in electrochemical27 and photochemical CO2 reduction particular, the introduction of nitrogen atoms has been proven
reactions, which are not the subject of this review article.28 to be effective to enhance CO2 affinity over other gases. In this
In this review, we provide (Fig. 1) an overview of the progress direction, amine grafting and amine impregnation have also
of promising POPs classes over the past 5 years with a perspec- been used to boost the CO2 capture performance of POPs.29 In
tive on POPs for CO2 capture, separation, and conversion. First, the latter example, corresponding POPs showed very promising
we discuss heteroatom-rich systems and, in particular, assess CO2 uptake capacities at low partial pressures and warm
different strategies towards their synthesis and the CO2 capture temperatures (up to 50 1C) under humid conditions, which
capabilities of these polymers. We also present an in-depth rendered them suitable for post-combustion CO2 capture and
analysis of various parameters such as surface area, micropor- DAC. It should be also emphasized that these systems showed
osity and heteroatom content on the CO2 uptake capacity and significantly lower regeneration temperatures compared to the
provide key insights into structure–property relationships gov- conventional aqueous amine solutions.29 However, from an
erning CO2 affinity. A perspective on effective control of poros- industrial point of view, a high CO2 sorption capacity alone
ity in POPs by employing specifically designed precursors such does not render a POP interesting. Rather than that, the heat of
as cavitands or cages is also discussed. Subsequently, the use of adsorption (Qst), working capacity, gas selectivity (especially
POPs as heterogeneous catalysts for CO2 conversion is also CO2/N2 selectivity) and operation under humid conditions have
Fig. 1 Schematic representation of various CO2 emission sources and a plot of atmospheric CO2 concentration over the years. An overview of as to how
POPs can contribute to the CO2 circular economy by the capture/separation and the subsequent conversion of CO2 into value-added products.
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to be considered for gas separation tasks. In the following CTF-1 (746 m2 g 1 and 2.47 mmol g 1 of CTF-135), they still
section, heteroatom rich POPs will be discussed and compara- showed significantly higher CO2 Qst of 44.6 kJ mol 1 compared
tively analysed by considering above mentioned parameters. It to that of CTF-1, 27.3 kJ mol 1.36 Moreover, Van der Voort et al.
should however be noted that there are rather limited number also synthesized a series of CTFs bearing aromatic heterocycles
of studies on the CO2 uptake performance of POPs under such as isoxazoles (isox) and pyrazoles (pyz) and investigated
humid conditions. their CO2 affinities. The CTFs showed a marked improvement
in the CO2 uptake capacities. Comparative analysis of pyz-CTF-
Heteroatom containing POPs 5-500 (CO2 uptake capacity of 3.31 mmol g 1, BET surface area
Heteroatoms such as O, S and F and their various combinations of 1405 m2 g 1, N content of 8.9 wt%, C/N ratio: 7.96) with isox-
CTF-5-500 (CO2 uptake capacity of 4.23 mmol g 1, BET surface
with N have been introduced into POPs upon the reaction of

suitably functionalized monomers through cyclization, conden- area of 1537 m2 g 1, N content of 7.9 wt%, C/N ratio: 8.99)
sation, or various C–C, C–N bond formation reactions. In this revealed the critical role of surface area and higher basicity of
direction, trimerization reactions have been actively investi- isoxazole ring.37 It should be, however, noted that while these
gated, in particular, covalent triazine frameworks (CTFs), which functionalization strategies are useful to increase CO2 affinity,
can be synthesized through the trimerization of aromatic they are not expected to perform well under wet conditions
nitriles, gained a lot of traction. First reported in 2008 by owing to the competitive binding of water molecules. In this
Thomas et al., CTFs proved to be an intriguing class of sense, incorporating F atoms is rather interesting as it would
materials due to their conjugated nature, high heteroatom create hydrophobic pockets within the polymer network while
content and surface areas.30 Through systematic studies, which maintaining high heteroatom content. The trimerization of
involved control over the linkers length, salt amount and (per-)fluorinated precursors results in CTFs bearing C–F moi-
reaction temperature, the surface areas and heteroatom con- eties in their skeleton. The defluorination of the backbone is
tents of CTFs can be controlled.31 It should be, however, noted commonly observed during the synthesis of CTFs at elevated
that CTFs showed significantly lower heteroatom contents temperatures. Nevertheless, high heteroatom contents of these
compared to the theoretically attainable amounts owing to polymers located within the ultramicropores (o0.7 nm)
the high reaction temperatures and irreversible side reactions enabled high CO2 uptake capacities (Table 1, entry 3–5, 7, 9,
during their formation. Moreover, partial carbonization is 11, 12).35,38–40 Such a CTF was showcased by Han et al. through
commonly observed for the CTFs synthesized above 350 1C. the polymerization of perfluoroterephthalonitrile. The result-
For example, CTF-0 prepared upon polymerization of 1,3,5- ing F-CTF featured a highly microporous structure with a BET
tricyanobenzene under ionothermal conditions at 600 1C surface area of 1535 m2 g 1 and CO2 uptake capacity of
showed an exceptionally high surface area of 2011 m2 g 1 3.41 mmol g 1 at 298 K, 1 bar. Most notably, F-CTF was able
however at the expense of crystallinity, formation of defects, to maintain a stable adsorption capacity over multiple adsorp-
increased mesoporosity and depletion of nitrogen content. tion–desorption cycles in the PSA process, which was attributed
Nevertheless, the resulting polymer still retained high nitrogen to the hydrophobicity of the fluorine moieties.35 In a similar
content of 19.3 wt% owing to the high nitrogen amount of the fashion, Dai et al. reported a series of tailor-made, extensively
monomer as well as a high micropore content, thus resulting in fluorinated CTFs with various oxygen containing flexible fluori-
CO2 uptake capacity of 4.22 mmol g 1 at 273 K, 1 bar.32 In this nated monomers.41 The polymers showed BET surface areas of
direction, various aromatic nitriles with high heteroatom con- up to 2085 m2 g 1, well defined ultramicropores (0.5–1.6 nm)
tents have been adapted as a general approach to enhance CO2 and high CO2 adsorption capacities up to 6.58 and 4.33 mmol g 1
affinity.33 Besides increasing the nitrogen amount, pairing with at 273 and 298 K, respectively. Interestingly, a deep learning
other heteroatoms such as O have also been investigated. Dai study performed by the authors predicted an optimal F content
and coworkers showed that the introduction of methoxy groups of (B4.8 wt%) and an optimal pore size 0.7 nm to result in the
onto a rigid hexaazatriphenylene precursor enabled CO2 uptake highest CO2 uptake capacity. Utilizing a backpropagation algo-
capacity of 6.3 mmol g 1 at 273 K, 1 bar in the resulting rithm with surface area, micropore volume, mesopore volume,
HAT-CTF synthesized at 600 1C with a BET surface area of adsorption temperature and pressure as the input parameters,
1090 m2 g 1. The high CO2 affinity of the HAT-CTF was they predicted the CO2 uptake considering each condition. The
attributed to the synergistic effect of heteroatoms and their design of new POPs guided by machine learning is expected to
distribution within the polymer network.34 Notably, the HAT- dominate the field in the coming years. The success of this
CTF also showed a rather high CO2 uptake capacity of 3 mmol g 1 approach, however, depends heavily on the availability of
at 0.15 bar, 273 K, which is more relevant to realistic carbon standardized data sets in the POP literature. Recently, Das
capture since flue gas contains approximately 15% CO2 at total et al. reported an intriguing approach combining N-rich aro-
pressures of around 1 bar. Similarly, Guipeng and coworkers matic moieties with perfluorinated subunits to form Tz-PFCN
investigated the effect of carboxylic acid and carboxylate (Fig. 2). Their idea was not only to use the building blocks to
moieties on the CO2 affinity of CTFs. Although CTF-CSUs obtain CTFs with high heteroatom contents, but also to delib-
showed significantly reduced surface areas in the range of erately induce thermal defluorination to obtain large amounts
326–491 m2 g 1 and relatively low CO2 uptake capacities of of ultra-micropores (Tz-df-CTF). As a result, Tz-df-CTF600
1.56–2.33 mmol g 1 at 273 K, 1 bar when compared to parent showed a surface area of 2106 m2 g 1 and a remarkable CO2
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Table 1 Selection of POPs containing heteroatoms
Heteroatom contenta CO2 uptake CO2 Qst (kJ CO2/N2

(wt%) (mmol g 1) mol 1) selectivityd
Stotal Smicro/Stotal Vtotal Vmicro/Vtotal 273 298
Sample (m2 g 1) (%) (cm3 g 1) (%) C N F O S (K) (K) — 273 (K) Ref.
1 CTF-1 746 0.62 — — 87.1 11.4 — — — 3 1.41 27.5 20 35
2 CTF-1-600 1553 0.10 — — 84.6 13.6 — — — 3.82 2.25 30.0 13 35
3 FCTF-1 662 0.94 — — 63.3 12.0 23.8 — — 4.67 3.21 35.0 31 35
4 FCTF-1-600 1535 0.49 — — 82.2 15.4 — — — 5.53 3.41 32.0 19 35
5 F-DCBP-CTF-1 1574 — 0.51 0.34 59.7 11.3 4.2b — — 5.98 3.82 33.1 31e 38
6 CTF-3 1454 — 0.98 0 — — — — — 2.13 1.34 21.0 24.5 41

7 F12CTF-3 1558 — 1.32 0.44 — 5.5b 3.7b — — 6.58 4.33 24.5 32.4 41
8 O-CTF-3 1450 — — — — — — — — 3.17 1.70 — — 41
9 O-F12CTF-3 1822 — — — — — — — — 5.59 3.04 — — 41
10 O-CTF-2 1130 — — — 81.4 2.7 — — — 2.65 2.06 — — 41
11 O-F16CTF-2 948 — — — 53.1 5.4 16.9 — — 5.10 3.30 — — 41
12 Tz-df-CTF600 2106 — 1.43 0.64 48.4 6.2 — — — 7.65 5.08 20.0 16.8 39
13 HAT-CTF-450/ 1090 — — — — 32.8 — 9.4b — 6.3 4.8 27.1 110 34
600
14 Isox-CTF-5-400 1683 — 0.70 — 53.6 7.4 — 6.0 — 4.92 2.86 29 83e 37
15 CTF-CSU38 491 — 0.44 0.24 58.8c 20.6c — 15.7b — 2.2 39.2 72.0 36
16 CICF-KCl/NaCl- 590 0.94 — — 64.1 14.1 — — — 5.9 4.04 35.9 — 47
500
17 CQN-1g 1870 0.68 0.93 — 63.5 24.5 — — — 7.16 4.57 40.6 42.7e 42
18 BTAP-1 750.9 — — 0.86 69.8 4.9 — — 20.9 3.26 1.78 31.7 40 24
19 BTAP-2 445.6 — — 0.77 65.6 5.4 — — 24.9 2.55 2.23 — 52 24
20 BTAP-3 419.9 — — 0.79 65.7 5.1 — — 24.3 1.58 1.41 33.8 62 24
21 BTLP-4 1011 — 0.53 — 64.1 7.3 — — 16.7 4.3 2.7 28.7 41 50
22 BTLP-5 705 — 0.41 — 62.3 6.6 — — 15.0 3.2 1.98 29.1 45 50
23 BOLP-4 698 — 0.54 — 71.7 8.2 — 16.3 — 3.1 2.0 33.6 79 50
24 BOLP-5 759 — 0.52 — 73.8 7.2 — 15.0 — 2.9 1.8 32.9 95 50
25 BILP-4 1135 — 0.65 — 67.1 14.0 — — — 5.3 3.6 28.7 79 48
26 BILP-5 599 — 0.36 — 72.7 12.7 — — — 2.9 2.0 28.8 95 48
27 Th-1 726 — 0.45 0.49 55.2 0.0 — — 23.1 2.88 — 27 39 57
28 Py-1 437 — 0.38 0.37 55.9 10.9 — — 0.8 2.71 — 36 117 57
29 Fu-1 514 — 0.36 0.42 60.6 0.0 — — 0.3 2.21 — 28 50 57
30 HMC-1 855 — 0.30 — 60.7 5.8 — — 27.2 5.8 — 34.0 72 58
31 HMC-2 425 — 0.19 — 59.9 5.1 — — 27.7 6.6 — 60.0 70 58
32 HMC-3 566 — 0.16 — 60.5 5.9 — — 28.0 7.1 — 52.0 23 58
33 Tp-POP — — — — — — — — — 1.32 — — — 59
34 Tt-POP-1 258 — 0.31 — 54.1 16.2 — — 26.1 0.75 0.29 50.12 30 59
35 Tt-POP-2 368 — 0.40 — 66.3 9.8 — — 18.8 0.91 0.49 58.77 26 59
36 Tt-POP-3 974 — 0.62 — 76.2 6.4 — — 12.0 0.78 0.45 54.23 25 59
37 TAP1 474 — 0.74 — 78.1b 11.4b — 10.6b — 2.2 1.4 35.6 94 60
38 TAP2 772 — 1.41 — 73.8b 12.4b — 13.9b — 3.2 2.3 37.2 112 60
39 TAP3 729 — 1.04 — 72.2b 13.7b — 14.2b — 3.4 2.3 36.1 114 60
40 PFPOP-1 570 0.67 0.32 0.6 68.2 0.0 — — — 2.8 1.2 26.9 43.7e 61
41 PFPOP-2 630 0.65 0.35 0.54 72.53 0.0 — — — 3.4 1.5 30.2 52.1e 61
42 PFPOP-3 530 0.66 0.30 0.53 68.09 1.3 — — — 3.9 1.7 32.5 56.5e 61
43 PMOP 1604 — 0.885 0.65 — — — — — 5.00 3.17 32.2 47.1 62
44 TBOSBL1 649 — 0.527 — — — — — — 4.0 2.1 35.1 68 63
45 TBOSBL2 570 — 0.384 — — — — — — 3.4 2.6 32.1 106 63
46 TBOSBL3 493 — 0.467 — — — — — — 2.8 2.2 32.7 108 63
47 COP-190H-en 456 — 0.142 0.96 83.3 3.4 — 8.7 — 3.6 2.19 100 171e 64
48 COP-190H-deta 72 — 0.047 0.24 83.8 3.7 — 9.0 — 2.7 1.79 73 121e 64
49 COP-190H-CN 661 — 0.21 0.95 73.6 5.0 — 13.2 — 3.2 2.11 42 91e 64
50 COP-190H-SH 773 — 0.25 0.92 72.5 — — 10.8 7.7 3.6 2.28 37 76e 64
a
Elemental analysis. b XPS analysis. c EDS analysis. d
IAST (ideal adsorbed solution theory) calculation for the flue gas condition CO2/N2:
15/85 (v/v) at 273 K. e At 298 K.
uptake capacity of 7.65 mmol g 1 at 273 K, 1 bar along with O content, retaining some of the F moieties could also enable
CO2/N2 selectivity of 16.8 under the simulated dry flue gas operation under wet conditions.
condition. Moreover, the authors also performed a break- Besides the trimerization of aromatic nitriles, several other
through test, in which the Tz-df-CTF600 produced 99% pure trimerization reactions have also been used for the preparation
N2 (up to 5.210 mmol g 1) and captured 0.987 mmol g 1 of of POPs. A rather intriguing example of such a trimerization
CO2.39 Whereas this material showed the complete loss of its reaction in POPs was reported by Buyukcakir et al., who
F inventory accompanied by a significant increase in the prepared a porous quinazoline network (CQN) through the
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Fig. 2 Schematic illustration of the formation of Tz-df-CTFs via a Dual Strategic Approach. Reproduced from ref. 39 with permission of the publisher.
trimerization of o-aminonitriles (Fig. 3). CQNs showed excep- reactants or even post-functionalization, they generally show
tional stability, partial crystallinity, and surface areas of decent CO2 uptake capacities and allow post-polymerization
up to 1870 m2 g 1. This, together with their microporous functionalization through their aminal linkages. For example,
nature resulted in an outstanding CO2 uptake capacity of Yavuz and coworkers prepared such an amide-linked polymer
7.16 mmol g 1 at 273 K, 1 bar and a high IAST CO2/N2 through the polymerization of melamine with a triacid chloride
selectivity of 74.7 at 298 K under dry flue gas conditions in different solvents and found that the choice of solvents has a
(CO2/N2: 10/90 v/v).42 Interestingly, unlike CTFs, which suffer profound effect on the morphology of the polymers and thus
from the depletion of nitrogen content, CONs showed near their CO2 uptake capacity (DMAc-NMP: 0.134 mmol g 1 at
ideal C/N ratios in the range of 3.12–3.19 (calculated 3.00) 273 K vs. dioxane: 0.09 mmol g 1 at 273 K).43 Although the
pointing to the efficient stabilization of nitrogen atoms. uptake capacity in itself is far from top-performing systems, it
Besides the in situ formation of triazines through a trimer- clearly shows that textural properties have to be carefully
ization reaction or condensation, another strategy for triazine- monitored and tuned in order to obtain good sorbents. Besides
containing polymers is to use cheap and readily available acid chlorides, especially formaldehyde resins have been
precursors such as melamine or cyanuric acid. Due to the N- explored extensively, many of which can reach high CO2
rich nature of the derived polymers as well as their easy capacities of above 3 mmol g 1 at 273 K.44 Recently, Reimer
functionalization and tunability through the choice of the et al. presented the kilogram-scale preparation two melamine
and cyanuric acid–based polymers and their CO2 uptake capa-
city as pristine materials and after addition of diethylenetri-
amine. Whereas the non-impregnated system showed rather
typical uptake characteristics (0.91 mmol g 1 at 298 K) the
amine-treated system showed a much higher capacity of
1.92 mmol g 1 but more importantly, most of the uptake
occurred at low pressures below 0.15 bar which is highly
relevant for industrial applications. Part of this steep uptake
has to be attributed to the chemisorption of CO2 on the
supported amine while the authors also partially attribute it
to the incorporation of cyanuric acid. The profound effect of the
cyanuric acid was also shown through sorbent recycling experi-
ments, where a very stable capacity was found for the cyanuric
acid systems whereas a continuous drop in capacity was
observed for the systems without the acid.45 One shortcoming
of directly using melamine is the exceptionally small pores that
are formed, which often results in low surface areas due to pore
collapsing. Hence, a variety of research groups explored larger
melamine building blocks such as phenyl-spaced diaminotria-
Fig. 3 The synthetic route for covalent quinazoline networks (CQNs). (a)
Preparation of model compound, tricycloquinazoline (mCQN). (b) The
zines. An example of such an approach was presented by Wang
synthesis of CQN-1. Reproduced from ref. 42 with permission of the et al. who utilized three different diaminotriazine-derived
publisher. building blocks to obtain highly nitrogen-rich polymers with
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Fig. 4 The synthetic route for the preparation of covalent isocyanurate frameworks (CICFs). High heteroatom content improves CO2 uptake capacity
and binding affinity. Reproduced from ref. 47 with permission of the publisher.
surface areas of up to 1228 m2 g 1 and CO2 capacities of cooperative supramolecular interactions to increase CO2 bind-
4.61 mmol g 1.46 ing affinity.49 Furthermore, imidazoles provide ample opportu-
In an effort to maintain high heteroatom content, Song and nities for post-polymerization modification, thus providing the
coworkers investigated the effect of salt-templation in the necessary means to tune the polymer’s properties to desired
formation of covalent isocyanurate frameworks (ClCFs) via tasks such as the conversion of CO2 to carbonates. In a similar
the cyclotrimerization of 1,4-phenylene diisocyanate under fashion, benzoxazoles and benzothiazole-linked POPs were also
ionothermal conditions (Fig. 4). The CICFs synthesized using investigated.24,50,51 El-Kaderi et al. showcased the synthesis of
a salt mixture containing KCl/NaCl/ZnCl2 showed near ideal benzothiazole- and benzoxazole-linked polymers (BTLPs and
heteroatom content at 500 1C, CICF-KCl/NaCl-500, whereas the BOLPs) via condensation reactions, that proceed via Schiff-base
ones synthesized using only ZnCl2 exhibited more than 50% reaction and subsequent cyclodehydrogenation. Although the
depletion of heteroatom content. These results revealed the authors set out to showcase the synergistic effects of the
critical role of the template effect originating from the interac- different heteroatom-containing linkages on CO2 uptake, no
tions between alkali metal ions and oxygen atoms of isocyanu- specific effect/correlation on the uptake, the Qst or the selectiv-
rate moiety. Interestingly, the authors also observed a ity could be elucidated.50 Coskun et al. introduced a solvent and
significant change in the morphology from micron-sized parti- catalyst free approach for the synthesis of an ultra-microporous
cles to a sheet-like morphology in the presence of a template. benzothiazole polymers (BTAPs) using elemental sulfur, which
The CICF-KCl/NaCl-500 showed a BET surface area of is a major by-product of natural gas purification (Fig. 5).24 The
590 m2 g 1 along with a CO2 uptake capacity of 5.9 mmol g 1 BTAPs were based on different 2D/3D building blocks incorpor-
at 273 K and 1.1 bar owing to its high microporosity and ating p-tolyl and 4-aminophenyl units and were heated to
nitrogen content of 14.1 wt%. In stark contrast, CICF-500 with 275 1C in the presence of elemental sulfur. Subsequent heating
a BET surface area of 1674 m2 g 1 and high mesopore content to 400 1C was employed to remove excess sulfur, while also
showed nitrogen content of only 7.8 wt% and a lower CO2 activating the pores without the need of excessive purification
uptake capacity of 3.95 mmol g 1 at 273 K and 1.1 bar.47 These and post-washing steps. The resulting polymers not only con-
results clearly verify the critical role of the combination of high tained the desired benzothiazole linkages but also excess sulfur
micropore content and high heteroatom content to realize high (up to 10 wt%) due to the formation of short sulfur chains and
CO2 uptake capacity and selectivity. These examples also reveal thiols. Despite that, BTAPs showed surface areas of up to
the potential of in situ formation of heterocyclic units as a 750 m2 g 1 and CO2 uptake capacities up to 3.26 mmol g 1.
powerful strategy in the synthesis of POPs. In this direction, Although these metrics pale in comparison to some of the best
one of the seminal contributions was the synthesis of performers (Table 1), BTAPs proved to be exceptional materials
benzimidazole-linked polymers (BILPs) by El-Kaderi and cow- after performing breakthrough experiments showing excellent
orkers. BILPs were readily synthesized by the condensation CO2/N2 selectivity, while also being produced in a green and
reaction of aromatic o-diamines with aromatic aldehydes.48 environmentally friendly way. These results also highlight the
The authors attributed the high CO2 affinity of BILPs to the critical need for the development of sustainable synthetic
strong dipole–quadrupole interactions between basic nitrogen strategies for the development of POPs. In this direction,
sites with the C atom of CO2, which was further reinforced hydrothermal synthesis of POPs, pioneered by Unterlass
by the hydrogen bonding interactions between O atoms and et al., gained significant traction in recent years as it employs
N–H moieties. This approach is an elegant demonstration of only water as a solvent.52 The resulting polyimide POPs showed
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Fig. 5 Synthetic scheme for the preparation of ultramicroporous benzothiazole polymers (BTAPs) through environmentally benign conditions without
using any solvent or catalyst. BTAPs were synthesized by simply reacting aromatic methyl- (M1 or M2) and amine-substituted monomers (A1 or A2) and
elemental sulfur, S8, at 275 1C in quantitative yields, followed by a heating step at 400 1C for pore activation and sulfur impregnation. Reproduced from
ref. 24 with permission of the publisher.
surface areas of up to 207 m2 g 1 and CO2 uptake capacities of interactions with CO2 and thus higher uptake capacities. The
up to 3.57 mmol g 1. Interestingly, post-polymerization proces- correlation between CO2 adsorption enthalpies (Qst) and CO2/
sing in the form of sintering did not affect the overall surface N2 selectivities, surface area and heteroatom/C ratios were
area too much resulting in only a slight drop to 203 m2 g 1, shown in Fig. 6c and d. For the adsorption enthalpies (Qst)
indicating that the ultramicropores could be maintained.53 above 40 kJ mol 1, the binding mechanism of CO2 is classified
Another intriguing method to introduce a large number of as chemisorption, which is observed for amine functionalized
heteroatoms into a porous polymer is the utilization of inorganic and/or amine impregnated POPs. As the lower surfaces areas
clusters such as siloxanes. Sun et al. demonstrated such a work in generally imply higher amine content, they showed the highest
which they utilized octaphenylsilsequioxane in a synthesis with Qst and CO2/N2 selectivity. When we look at the physisorption
bis(chloromethyl)biphenyl to obtain POPs with surface areas of up regime, which is below 40 kJ mol 1, we observed an increase in
to 1170 m2 g 1 and CO2 capacities of up to almost 3 mmol g 1. the Qst and CO2/N2 selectivity with respect to the increasing
Although such a system lies on the cusp of what can be defined as heteroatom/C ratio. These results further suggest that for an
an organic polymer it clearly shows the interplay between high efficient CO2 capture through physisorption, ideal system
heteroatom contents, large surface areas and CO2 uptake.54 should feature both high micropore content and high hetero-
Utilizing photo-switchable functional units to govern a atom/C ratio. Interestingly, we also did not observe a correla-
polymer’s CO2 adsorption capacity is another way to further tion between the CO2 Qst and CO2/N2 selectivity within the
tune porous polymers for specific applications. Especially azo- physisorption regime. The fact that several publications praise
groups as part of a porewall-functionalization have been fluorine as an attractive heteroatom in POPs for CO2 capture,
employed by Sun and coworkers to tune POPs and MOFs our analysis revealed no apparent trend between fluorine
capabilities for CO2 uptake.55,56 Leveraging the cis/trans iso- content and beneficial interactions with CO2. There is an
merization of the azo moiety upon irradiation with UV light, the argument to be made, that fluorinated precursors can help
authors were able to tune the uptake capacitates thus poten- with generating nicely microporous materials through thermal
tially allowing the preparation of switchable membranes. defluorination, however, compared to other heteroatoms such
In an attempt to unveil the parameters to achieve high CO2 as N, O or S the impact of fluorine on a polymer’s CO2 uptake
affinity, we investigated the impact of surface area, micropore and CO2 selectivity is not as significant. On the other hand, the
content, heteroatom/C ratios on the CO2 binding. The corres- combination of N with O and S consistently showed higher Qst
ponding performance and structural characteristics of the values and CO2/N2 selectivity (Fig. 6e and f), pointing to the
various POPs rich in heteroatoms are surmised in Table 1. positive impact of the synergistic effect of different heteroa-
Based on these characteristics, Fig. 6a and b clearly showed the toms and in most cases increased basicity of the network.
trend that high surface areas and pore volumes as well as a high
ratio of micropores results in an overall higher CO2 uptake POPs based on porous molecular precursors
capacities, highlighting critical role of micropores. A plethora Until now we have established key functional units and para-
of POPs performing at the highest levels contain combinations meters governing high CO2 affinity and selectivity. In this
of nitrogen and other heteroatoms due to their beneficial section, we will focus on some intriguing design strategies.
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Fig. 6 CO2 capture performance of POPs containing heteroatoms with various parameters. (a) CO2 adsorption at 273 K versus total pore volume (Vtotal)
and micropore volume ratio (Vmicro/Vtotal). (b) CO2 adsorption at 273 K versus total surface area (Stotal) and micropore surface area ratio (Smicro/Stotal).
(c) Heat of adsorption (CO2 Qst) and total surface area (Stotal) versus total heteroatom ratio (X/C, X = all heteroatom species in the same POPs) (d) CO2/N2
selectivity at 273 K and total surface area (Stotal) versus total heteroatom ratio (X/C, X = all heteroatom species in the same POPs) (e) heat of adsorption
(CO2 Qst) versus heteroatom ratio (X/N, X = F, O, S). (f) CO2/N2 selectivity versus heteroatom ratio (X/N, X = F, O, S). All the data is summarized in the
Table 1.
Specifically, we will discuss the use of (i) shape persistent large surface area polymers with high accessible pore volumes,
monomers such as triptycenes or spirobifluorenes, (ii) pre- given that pore collapsing can be avoided. Secondly, a wide
and post-polymerization amine functionalized POPs and (iii) variety of linking functionalities can be employed, however
cavitands and cages in order to explain why the use of these most commonly either amine, ether or C–C based linkages
specific motifs resulted in highly CO2-philic systems and in are used, each resulting in specific benefits in terms of stability,
some cases even in excellent catalysts for the up-conversion of CO2-philicity and catalytic activity.
CO2 to value-added products.
Although, on a first glance, all the aforementioned systems Shape-persistent molecules
seem diverse and uncorrelated, many of them combine a In the realm of shape persistent organic precursors especially
specific selection of molecular motifs. For one, they rely on adamantanes, tetraphenylmethanes (TPMs), spirofluorenes/
molecular precursors that directly induce a three-dimensional spirobifluorenes and more recently triptycenes have been
network on a molecular level, thus, in many cases, resulting in employed to obtain higher surface area polymers (Table 2).65
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Table 2 Selection of POPs based on pre-porous precursors and POPs used as organocatalysts. Surface area, CO2 uptake, CO2 Heat of adsorption (Qst)
and CO2/N2 selectivity
SABETa CO2 at 273 K CO2 at 298 K CO2 Qst CO2/N2

Sample (m2 g 1) (mmol g 1) (mmol g 1) (kJ mol 1) selectivityb Application Ref.
NPOF-4 1249 2.50 1.40 23.2 27 Gas sorption 65

NPOF-4-NO2 337 2.42 1.56 32.5 139 Gas sorption 65
NPOF-4-NH2 554 2.90 1.88 30.1 101 Gas sorption 65
Azo-COP-1 635.8 2.44 1.48 29.3 63.7 Gas sorption 23

PAF-1 4100 2.46 — — — Gas sorption 67
PAF-1-CH3 3007 2.45 — — — Gas sorption 67
PAF-1-CH2OH 1727 2.98 — — — Gas sorption 67
PAF-1-phthalimide 974 2.23 — — — Gas sorption 67
PAF-1-CH2NH2 1263 4.37 — — — Gas sorption 67
PAF-1-CH2N = CMe2 1302 3.12 — — — Gas sorption 67
2D-PTNS 690 3.11 — 30.7 93 Gas sorption 68
PNOP-1 830 4.00 2.42 30.0 52.1 Gas sorption 76
PNOP-2 729 3.04 1.96 31.3 80.1 Gas sorption 76
3D-tPOP 22 2.38 — — — Gas sorption 78
3D-tPOP-NaCl-2.0 1058 4.42 2.62 42.1 — Gas sorption 78
CXF1-OMe 626 1.49 — 26.0 — Gas sorption 89
CFX1-OH 540 2.20 1.5 35.0 98 Gas sorption 89
co-CXF3-OPr 2609 2.40 — 23.2 — Gas sorption 89
co-CXF3-OH 1943 2.91 — 30.0 — Gas sorption 89
TMP1 923 3.50 2.04 22.2 64 Gas sorption 69
TMP2 1094 3.70 2.18 21.1 60 Gas sorption 69
TMP3 1372 5.07 3.27 22.0 70 Gas sorption 69
TNHCP1 848 2.89 2.20 30.8 30 Gas sorption 70
NTP 1067 3.45 1.82 26 18 Gas sorption 71
3D-CON 2247 6.07 3.90 31.87 — Gas sorption 71
PMDI-cage 1a 522 2.91 — 27.0 26.9 Gas sorption 80
Cg-Am 104 0.89 — — — CO2 conversion 82
Cage-1 — 0.10 — — 138 Gas sorption 83
F1 — 0.19 — — 64 Gas sorption 79
F2 — 0,23 — — 42 Gas sorption 79
F3 — 0,16 — — 213 Gas sorption 79
Noria 221 1.77 — 30.4 — CO2 conversion 87
NPOP 773 2.09 1.36 28.9 30 CO2 conversion 87
HRN4 156 1.39 — — — CO2 conversion 88
RN4-Az-OH 340 2.04 — 30.8 19 CO2 conversion 88
RN4-OH 720 2.25 — 29.5 20 CO2 conversion 88
RN4-F 1230 2.59 — 28.5 35 CO2 conversion 88
cCTF-400 744 2.86 1.89 49 — CO2 conversion 98
Py-iPOP-1 65 0.82 0.55 — — CO2 conversion 100
a b
Surface area is calculated based on Brunauer–Emmett–Teller (BET) theory. The CO2/N2 selectivity calculated using IAST (ideal adsorbed
solution theory) for the flue gas mixture, CO2/N2:10/90 (v/v) at 298 K.
Although many systems based on these precursors suffer from among the most widely used 3D structure inducing precursors
pore collapse, resulting in much lower surface areas than in POPs and COFs due to their facile synthesis and ease of
theoretically possible, fine-tuned syntheses and work-up proce- functionalization. The high structural tunability allows gener-
dures avoid/alleviate these problems. Especially triptycene- ating a wide range of linking functionalities/chemistries result-
based POPs have gathered significant interest in recent years, ing in highly tunable polymers. To showcase the influence of
since the derived POPs often contain a significant amount of specifically tuned linking units, Coskun et al. reported a series
(ultra)micropores, which are helpful to capture gases. TPMs are of TPM-based POPs linked via azo functionalities resulting in
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excellent CO2-philicity and selectivity over N2. Most notably, the various functional groups on the surface area and gas uptake
systems showed next to no hysteresis thus showing the poly- properties. The free amine functionalized system showed
mer’s capability for energy-efficient recyclability.23 Besides such superior performance in terms of CO2 uptake although having
conventional linkages, imidazoles, thiazole and thiadiazoles one of the lowest surface areas in the series.67 A similar strategy
have also proven to be quite useful for CO2 uptake providing was used by Hopkinson et al., who prepared PIM-1 and further
both a CO2-philic site that can be further functionalized to functionalized it via the hydrolysis of the nitrile moieties and
facilitate the upconversion of CO2.24,66 On top of the vast subsequent treatment with tris(2-aminoethyl)amine. The
amount of linking units, several research groups used side- resulting amine containing system showed significantly
chain functionalization as a tool to tune the pore structure and enhanced CO2 uptake capacities of up to 1.62 mmol g 1 at
environment pre- or post-polymerization.67 0.15 bar and 298 K while showing a good cyclability.74 Similarly,
Whereas TPM-based POPs often suffer from interpenetra- Yavuz et al. prepared a triphenylbenzene-based POP (COP-130)
tion or pore collapse, triptycenes have been proven to be a and subsequently acylated it with chloroacetyl chloride to
reliable building block to induce molecular dimensionality into obtain a ketone and alkyl halide bearing polymer. The obtained
a system while maintaining high porosity. Among C–C linked COP-130-Ac allowed derivatization with various amines through
triptycene-based POPs, both the use of stiff, inflexible linkers Schiff base and nucleophilic amination reactions, thus allowing
such as alkyne-linked systems68 or more flexible linkers based a wide range of functionalization. Although the functionaliza-
on allylhalides68,69 resulted in high surface areas and excep- tion resulted in a significant loss of porosity, the amine
tional CO2 uptake capacities, which can be attributed to the functionalized systems showed CO2 uptake capacities up to
presence of micropores and ultramicropores. However, a major 4.95 mmol g 1 at 273 K (1.31 mmol g 1 at 273 K and 0.15 bar)
shortcoming of such systems unless provided by a co- while having a low Qst value of 25.6 kJ mol 1 indicating that
monomer70 is the lack of acidic or basic sites within the although free amines are present in the system, next to no
polymers hindering their potential as porous organic catalysts. chemisorption occurred pointing to good cyclability and low
Thus, a variety of triptycene POPs linked via amines71,72 or energy regeneration of the sorbents.75 One major advantage of
phenazines73 have been employed to endow the polymers with these systems is their ability to operate under wet conditions,
suitable functional active sites. Both amines and phenazines which is a serious problem for the POPs owing to the compe-
provide basic sites which help polarizing CO2, thus enabling for titive binding of CO2 and H2O molecules. In an attempt to
example the cycloaddition of epoxides to carbonates. A system combine TPM or adamantane linkers with non-metalated por-
nicely showcasing the interplay of dimensionality and CO2 phyrins, Wang et al. exploited aldehyde terminated building
sorption was reported by Baek et al., who employed triptycene blocks and reacted them with pyrrole to obtain nicely porous
hexamine and polymerized it with hexaketocyclohexane to materials with ample Lewis acidic N–H sites in the porphyrin
obtain a phenazine-linked POPs. The obtained highly rigid moieties. The obtained polymers showed good CO2 uptake
polymer showed a BET surface area of 2247 m2 g 1, while capacities of up to 4.0 mmol g 1 and good CO2/N2 selectivities,
featuring excellent CO2 uptake capacity of 4.98 mmol g 1 at thus showcasing how such a simple design approach can lead
273 K and 1 bar owing to strong interactions with the hetero- to highly functional polymers.76
atoms located within the ultramicropores of polymer network.73 Combining N-rich linkages, metal-containing building
blocks and amine-functionalized linkers, Echegoyen et al. pre-
Pre- and post-functionalized POPs pared a phthalocyanine-based POPs via azide Click chemistry
The wide range of possible pre- and post- functionalization utilizing an amine functionalized alkyne linker. The obtained
strategies allows chemists to fine tune specific properties of the polymer had a relatively low surface area of only 342 m2 g 1 but
target porous organic polymers. Among post-polymerization still showed good CO2 uptake capacity of 3.57 mmol g 1 at
strategies, especially impregnation with amines and the con- 273 K and 1 bar due to the combination of highly CO2-philic
version of suitable functional units on the polymer backbone to building blocks.77 Tetraphenylenes are another class of
free amines or amine-containing groups have been heavily porosity-inducing precursors that have recently received a lot
investigated. Like previously introduced, amine scrubbing with of attention, however, most of the literature focussed on
MEA and others, the amine groups act as chemical sorbents for exploiting the conductive properties of the polymers. Among
CO2 resulting in good uptake performance especially at low the few TP-based polymers, Coskun et al. reported the synthesis
partial pressures and low CO2 loadings. Many of these post of a dioxane-linked three-dimensional POPs. Interestingly,
polymerization functionalization strategies revolve around pre- pure solvothermal methods did not result in the formation
paring suitably functionalized precursors often based on the of a nicely porous polymer, while salt templation yielded
shape persistent molecules as building blocks such as adaman- highly porous polymers with CO2 capacities reaching up to
tanes, TPMs or triptycenes. Such systems often contain halides 4.42 mmol g 1.78
or allyl halides that are subsequently converted to the desired
functional groups. An early example of such functionalization Cavitand- and cage-based POPs
was reported Nguyen et al., who prepared a series of TPM based Both cavitands and cages have been known for their large
systems and even used functionalized allyl-TPM precursors for intrinsic surface areas for a long time. However, molecular
post polymerization modification showcasing the effect of cage/cavitand systems suffered from unpredictable stacking in
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the solid-state, which in some cases resulted in a loss of surface epoxide conversion even though having the lowest BET surface
area due to e.g. phenylene-to-window packing in the case of area in the series exemplifying the role suitable functionaliza-
molecular cages.79 Although directed molecular design allowed tion has on the gas uptake and catalytic performance.88 A
to obtain highly porous, selective,80,81 and in some cases recent example of a calixarene-based porous organic polymer
catalytically active cages,82 their often complicated synthesis was reported by Comotti et al., who prepared a series of
and purification hinders widespread application for CCS and differently functionalized calixarenes and reacted them with a
CCC. An intriguing feature of these systems is the possibility to bromo-TPM derivative. The obtained polymers exhibited mod-
design the pore sizes by choosing the linker length in cages or erate to large surface areas up to 2609 m2 g 1 and CO2
by adding/removing linking units in case of cavitands. This capacities up to 2.91 mmol g 1 at 273 K and 1 bar.89
approach allows fine-tuning of the pores towards specific tasks Molecular cages were the first systems for which the cavi-
such as gas sorption by increasing the interactions with a tand/cage-to-framework strategy was employed on, however,
specific gas over another one.79 To avoid a loss of porosity due to the complicated preparation of suitably functionalized
and pore accessibility in the solid-state, researchers developed cages, significantly fewer systems have been reported to date
the ‘‘cavitand/cage-to-framework’’83 design strategy, wherein compared to other systems. In 2015, Coskun and coworkers
suitably functionalized ‘‘pre-porous’’ building blocks are linked reported a triazine-based cage that showed exceptional CO2
via covalent bonds, often utilizing stiff building blocks to uptake capacity and high selectivity towards CO2 over other
endow the polymers with rigidity and structural integrity.25,84 gases thus being highly suitable for CCS.25 Although the system
First introduced by Zhang et al. to obtain a porous cage-POPs,83 featured basic triazine units and aminal linkages, it was found
the strategy was widely adopted and adapted towards cyclodex- to be unsuitable for the direct conversion of CO2 without the
trins, calixarenes, pillarenes,85,86 resorcin[X]arenes and more use of a co-catalyst. Recently, Patra et al. introduced an intri-
specialized systems (e.g. noria-based POPs).87 Whereas cyclo- guing new cage precursor dubbed ‘‘Noria’’ that features 24
dextrins and pillarenes have mostly been used for CO2 uptake phenolic hydroxyl groups and seven accessible windows.
and sequestration,85 especially pillarenes and resorcin[X]arenes Improving on their previous design, the use of a stiff linker
have been employed both as sorbents and catalysts owing to resulted in a highly porous polymer that showed high affinity of
their abundant phenolic OH functionalities, which can be CO2 over N2 and proved to be a suitable catalyst for the
leveraged to polarize substrates such as epoxides thus facilitat- conversion of CO2 to a series of carbonates in the presence of
ing an easier nucleophilic attack by a suitable co-catalyst tetrabutylammonium bromide (TBAB) as a co-catalyst.87
allowing its conversion to cyclic carbonates. Patra et al.
reported a series phenyl resorcin[4]arene-based POPs featuring POPs for CO2 conversion
abundant phenolic OH moieties while being linked through
various different functionalities, thus tuning the porosity and In organic chemistry, CO2 is a well-known and commonly
gas sorption properties of the systems (Fig. 7). All systems employed substrate and various chemical, electrochemical,
proved to be suitable catalysts for the cycloaddition of CO2 to and photochemical strategies have been investigated to
epoxides, however the azo-linked system showed the highest utilize CO2 as a C1 building block. In photocatalytic and
Fig. 7 Phenylresorcin-based POPs. (a) Synthetic schemes of C-phenylresorcin[4]arene-based porous organic polymers (POPs). RN4-Az-OH: diazo
coupling between p-hydroxyphenylresorcin[4]arene and benzidine, RN4-OH: Sonogashira polycondensation between p-bromophenylresorcin[4]arene
and 1,4-diethynylbenzene, and RN4-F: aromatic nucleophilic substitution reaction between p-hydroxyphenylresorcin[4]arene and tetrafluoroterephtha-
lonitrile (12 phenolic OH groups are likely to be equally reactive) digital photographs of the respective POPs in the form of powder Reproduced from
ref. 88 with permission of the publisher.
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electrocatalytic applications, semiconducting POPs are of however, only few of these materials were suitable for the direct
immense interest due to their intrinsic conductivity, broad conversion of CO2 to value-added products without the need of
absorption range, high surface area and structural tunability. a specific co-catalysts (Table 2). The problem lies in the
Wherein for photocatalysts, the efficacy of CO2 adsorption, the necessity of providing a range of suitable functionalities near
polymers’ light absorption range, and charge separation deter- one another to ideally enable the activation of both CO2 and the
mine the overall efficiency of the POP catalysts, in electrocatalytic substrate of choice. Besides incorporating metal ions into the
applications the efficiency of POPs is mostly determined by the polymers, two strategies allowing fully organic polymers for the
electronic properties, contact to the electrode and the catalysts conversion of CO2 have been reported: (i) implementing func-
CO2 affinity. In both cases, the incorporation of precious metal tional units for the activation of both CO2 and the substrate and
ions and nanoparticles is often employed to increase the overall (ii) utilizing charged moieties such as pyridyls or imidazoles to
performance. Due to that, a plethora of high-value products such provide an anion for the nucleophilic attack to the substrate.
as CO, methanol, ethanol, methane, and many others are avail- Yavuz et al. demonstrated the first approach based on a
able that can directly be used as substrates or reagents. Although, simple polymer featuring pyridyl salicylimines.97 The polymer
in recent years the interest in electrochemical and photochemical embodied both an acidic site in the form of phenolic OH and a
POPs catalysts has increased, these systems often rely on strict basic site in the form of pyridine. The intriguing feature of this
conditions and the use of precious metals. When it comes to the molecular design lies in the capability of the pyridine moiety to
chemical conversion of CO2, especially the cycloaddition of CO2 to become charged, during the nucleophilic attack on the epoxide
epoxides has been explored intensively due to the high atom removing the necessity of a co-catalyst for the conversion of CO2
economy and readily available substrates. Besides that, cyclic to epoxides (Fig. 8). The wide scope of tested substrates and the
carbonates can be directly used as aprotic polar solvents90 in cyclability of the system nicely demonstrates the interplay
battery electrolytes,91 as precursors for polymers such as between the functional units and showcases how readily avail-
polycarbonates92,93 or phenol resins,94 or as precursors in organic able chemicals and thus polymers can be utilized as highly
synthesis or pharmaceuticals.95,96 Despite research mostly focus- active porous organocatalysts.
ing on the conversion of CO2 to cyclic carbonates, various other Although often resulting in less chemically and thermally
strategies such as the conversion of CO2 to linear carbonates, stable polymers, the utilization of charged linkers is signifi-
cyclic carbamates, to products such as urea or the direct use in cantly more common compared to the strategy introduced
carboxylation reactions can be envisioned given a suitable mole- before. Especially (bi-)pyridyl-linked systems or polymers incor-
cular design. porating or linked by imidazoles have been heavily investigated
for that purpose. Besides having a high nitrogen content and
Co-catalyst free porous organocatalysts thus featuring high CO2-philicity, the charged moiety and the
In the previous section we have presented a variety of design associated counter ion facilitate the nucleophilic attack on the
strategies that enabled CO2-philic, highly porous materials, substrates such as epoxides allowing the cycloaddition of CO2.
Fig. 8 Probable mechanism and recyclability studies. (a) A proposed mechanism for the coupling reaction of an epoxide with CO2 by catalyst 1.
(b) Recycling of the catalyst in the coupling reaction of styrene oxide and CO2 under optimized reaction conditions. Reproduced from ref. 97 with
permission of the publisher.
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To this end, Coskun and coworkers have reported a CO2-philic Most metal-containing POP-based catalysts for CO2 conver-
CTF-based system containing viologen linkers. The electrostatic sion feature cheap and abundant metal ions/NPs such as Fe,
interactions of the charged linkers with CO2 molecules facili- Co, Zn, Mn, Cr, or Al in the oxidation states of either +2 or +3.
tated high gas uptake and enabled the cycloaddition of CO2 to a These metal sites offer a high affinity towards CO2 and help
wide range of substrates.98 It should also be noted that when polarize the substrate, a critical step in activating CO2, thus
using charged units, the counterion does not only affect the enabling the conversion of an otherwise inert molecule. There
available surface area based on the bulkiness of the ion but also have also been various reports on homogeneous catalysts based
affects the catalytic activity of the system. In their series on rare-earth and early transition metals due to the high
consisting of Cl , PF6 and BF4 , the authors demonstrated Lewis acidity of derived coordination compounds,107 however,
that the system with chlorine showed the highest CO2 uptake given the scarce nature and high cost of these metals, readily
and catalytic activity, which was attributed to the higher available transition metals present a more environmentally
nucleophilicity of the anion.99 Along this line, Chen et al. conscious and sustainable choice when designing POP-based
explored the effect and interactions of the anion in their catalysts.
charged cyanovinylene POPs prepared through a Knoevenagel Metalloporphyrin-based conjugated microporous polymers
condensation. Despite the mesoporous nature of the polymer, (M-CMPs)108 and hyper crosslinked polymers (M-HCPs)109 as
it showed good catalytic activity at low CO2 pressure and well as the metal-salene conjugated microporous polymers (M-
moderate reaction temperatures (1 bar and 40–120 1C depend- CMPs, M = Co-, Zn-)110 have been actively investigated for the
ing on the substrate). Interestingly, the authors found that the conversion CO2 into cyclic carbonates. Among these POPs,
catalytic activity of their polymers was dependent on the in situ those containing Co2+, Zn2+, and Fe2+ were reported to be active
formation of HCO3 anions as well as the formation of stable in the cycloaddition of CO2 to epoxides. A member of this
pyridyl radicals.100 Featuring abundant and readily accessible family is the Friedel Crafts derived FePC-POP. The iron-
precursors, Yavuz et al. reported an imidazolium-based POPs containing phthalocyanine was obtained through a Friedel
with exceptional catalytic performance. The charged polymer Crafts reaction with biphenylene.111 The obtained polymers
obtained from the condensation of terephthalaldehyde with showed moderate surface areas of up to 427 m2 g 1 and high
ammonium acetate showed high activity for the fixation of CO2 iron content of 5.42 wt%. FePC-POP proved to be suitable for
even for challenging substrates, thus showcasing the applic- the cycloaddition of CO2 to epoxides showing yields up to 94%
ability of their catalyst.101 at 90 1C and 3 bars. To obtain such high conversions, the
authors used DMAP as a coordinating base. Although the
catalyst showed good conversion for simple epoxide substrates
Metal-containing POPs for CO2 conversion such as epichlorohydrin, more challenging ones such as styr-
POPs are ideal hosts for various metal ions to form hetero- ene oxide or cyclohexane oxide showed significantly lower
geneous catalysts for CO2 conversion. First examples of conversions. This was attributed to electronic reasons in the
metal-containing POPs were based on metal-complexing case of styrene oxide and steric hindrance in the case of
building blocks such as metalloporphyrins,102 metallophthalo- cyclohexane oxide. Besides Friedel Crafts reactions, polycon-
cyanines,103 and salenes.104,105 Whereas POPs incorporating densation reactions are among the most used methods to
these motifs were most often prepared via Friedel Crafts reac- prepare porous single-atom catalysts. Utilizing an amine-
tions or Schiff base chemistry, an alternative strategy is to functionalized Co-PC and a benzoquinone linker, Tang and
prepare the desired coordination site in situ during the coworkers prepared conjugated microporous polymers
polymerization.106 A third way to introduce large amount of (DTTBQ-CMP) with good catalytic activity towards CO2 conver-
metal ions into POPs is wet impregnation with the desired sion under mild conditions (1 bar, 25–60 1C) reaching near
metal ion, thus introducing the metal ions themselves or quantitative yields at low temperature and low CO2 pressure in
inducing the in situ formation of metal nanoparticles. Given presence of a TBAB as a co-catalyst. Interestingly, in the case of
suitable functionalization, the high surface areas and the large a simple substrate such as propylene oxide, catalyst-free con-
heteroatom content of POPs make them ideal candidates for version could be obtained (1 bar, 25 1C), albeit at significantly
the stabilization and distribution of metal ions within the lower yields. Recently, Jiang and coworkers utilized an amine-
polymer matrix, resulting in a high number of available cata- based triptycene linker and an aldehyde functionalized phenol
lytic active sites. Moreover, POPs can be endowed with single- to obtain bimetallic salen-based POPs (Fig. 9).112 Metal ions
atom active sites, that can be leveraged for high conversion and were introduced during the synthesis in the form of different
selectivity. metal salts (M = Al, Co or Ni) and the obtained heterogeneous
In this regard, especially phthalocyanines and porphyrins catalysts showed good activity in the presence of a co-catalyst
have gained tremendous attention as their easy synthesis (TBAB, 25 1C, 1 bar). Triptycenes are often employed to increase
allows the introduction of task-specific metal ions. In the the porosity as well as the accessibility of the catalytic sites.
following section, we will summarize classical and modern Despite showing high metal contents of 8.8, 15.0, and 16.9 wt%
synthetic approaches toward metal-containing POPs and dis- for Fe2+, Co2+, and Ni2+ respectively, the polymers showed poor
cuss their capabilities as heterogeneous catalysts for the up- CO2 conversion efficiency, which could be attributed to their
conversion of CO2. relatively low surface areas (142–280 m2 g 1) and the low CO2
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Fig. 9 Precise positioning of metal ions in bimetallic POPs. Synthetic scheme of BSPOP-M. Reproduced from ref. 112 with permission of the publisher.
uptake capacities (0.74–1.70 mmol g 1). Among these systems, 120 1C in moderate to good yields. This result was attributed to
BSPOP-Co showed the highest heat of adsorption for CO2, the ample amount of functional units endowing the system
indicating a good binding affinity of CO2, which together with with Lewis acidic metal sites along with the presence of Br
having a higher surface area and increased accessibility of the anions, which act as nucleophiles in the ring-opening
catalytic sites compared to the other systems contributed to the of the epoxide.109 Ji et al. reported metallosalen-based ionic
overall better catalytic performance. Overall, such bi-metallic POPs via a radical polymerization of functionalized salphen-
systems such as BSPOPs are of immense interest to the field as imidazolium precursors.114 Similar to the system reported by
the two neighboring metal centers are expected to result in a Wang et al.,113 a cooperative effect between the different metal
synergistic effect, thus improving the catalytic performance. ions (Al3+ and Zn2+) in combination with the Br anion of the
When designing catalysts for the conversion of CO2 to cyclic imidazolium moiety could be observed, resulting in a good
carbonates not only a Lewis acidic site for the fixation/activa- catalytic activity for the cycloaddition of CO2 to epoxides and
tion of CO2 is required but also a nucleophilic moiety is needed also for the N-formylation of amines under mild conditions.
to facilitate the ring-opening of the epoxide. Accordingly, the Importantly, the integration of charged units bearing nucleo-
design of such bifunctional active sites in POPs is a promising philic counter anions such as Cl and Br naturally eliminates
strategy to achieve high catalytic activity. In this direction, both the need for a co-catalyst.
the combination of two different metal ions within a single
system or the generation of charged organic moieties (e.g.
phosphonium or pyridyl moieties) are promising strategies. CO2 conversion beyond cycloaddition
As such, a vinyl-functionalized Mg-porphyrin was co- Besides the conversion of CO2 into cyclic carbonates, other
polymerized with a vinyl-functionalized phosphonium salt uti- chemical conversion pathways are also possible using metal-
lizing free radical polymerization.113 Despite its relatively low containing POPs (Table 3). Formic acid (HCOOH) as a product
surface area (558 m2 g 1), the polymer (Mg-por/pho@POP) of CO2 fixation is considered a key chemical intermediate as it
showed good catalytic activity in the absence of a co-catalyst. can be further converted into other chemicals (e.g. MeOH).
Simple to moderately hindered epoxides ranging from propy- From a molecular design point of view, electron-donating
lene oxide to styrene oxide could be converted at 10–30 bar at ligands (such as pyridyls or phosphines) are indispensable to
Table 3 Selected examples of metal-containing POPs for the CO2 conversion beyond cycloaddition
Metal Coordination BET Yield Conversion TOF

Name Catalytic site (wt%) ligand site Preparation method (m2 g 1) Product (%) condition TON (h 1) Ref.
Ir/AP-POPa Ir cluster 1.25 Amide & pyr- Amide formation/wet 43 HCOOH — 3 MPa CO2 25 135 — 115
idine moiety impregnation, NaBH4 3 MPa H2
reduction 80–140 1C
Ru@PP-POPa RuCl3 0.81 Phosphine Telomerisation of 469 DMF 98 80 MPa CO2 16 104 29 000 121
moiety phosphine/wet 140 1C
impregnation
POMP-NHC-Ira Ir+(CO)2BF4 2.89– N-Heterocyclic Fridel-craft reaction 19–704 DMF 90 40 atm 120 1C 1.58 106 — 118
16.12 carbene moiety using bis-NHC-Ir MeOH
complexes
Imine-POP@Pda Pd NPs 8.3 Imine moiety Hydrothermal imine 180 DMF 97 3 MPa CO2 — — 122
formation/wet 3 MPa H2
impregnation 100 1C, K3PO4
a
POPs are employed using high-pressure solvothermal reaction for CO2 conversion.
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provide stability and to modulate the electronic properties of Another industrially important product is N,N-dimethyl-
the active site. Iridium and Ruthenium complexes are excellent formamide (DMF), which can be prepared in a base-catalyzed
examples for this type of chemistry and a variety of different process via an N-formylation of CO with dimethylamine. A
supports based on various functional groups have been devel- more environmentally friendly method of preparing DMF
oped to stabilize such metal species. An example of such a would be to replace CO with CO2. The first catalytic systems
system was recently reported by Zhang et al. who prepared an capable of this were reported in the 1970s, when Kohnle et al.
Ir-based single atom catalyst (Ir-POPs) via a post metalation prepared various metal complexes based on Co, Rh, Ir, Pd, and
process. The polymer showed capabilities to produce formic Ru.116 Following this, various homogeneous catalysts were
acid in a high-pressure solvothermal procedure.115 AP-POP was developed and employed in the synthesis of DMF using CO2
easily prepared by reacting diaminopyridine with 1,3,5- however, in many cases, supercritical media at high pressure
benzenetricarbonyl trichloride. The resulting alternating amide (e.g. 130 atm CO2) were required. To circumvent the necessity of
and pyridine moieties together with the mesoporous structure such high pressures, heterogeneous catalysts based on POPs
proved to be an ideal substrate for wet-impregnation with Ir were investigated.
salts, wherein the Ir3+ ions were coordinated to the carbonyls of Yoon et al. reported a Ru-grafted bisphosphine-based POPs
the amides and the pyridine N moieties forming Ir/AP-POP (PP-POPs) via a post metalation procedure utilizing methanolic
(Fig. 10). Interestingly, spectroscopic analysis of Ir/AP-POP RuCl3, wherein the Ru-ions are stabilized by the phosphine-
supported the formation of single metal ions with a homo- backbone. This approach allowed the authors to perform the
geneous distribution of Ir3+ over the entire structure. Compar- hydrogenation of CO2 at 80 atm and 140 1C with a TON of up to
ing their results to activated carbon (AC) or graphitic 160 000. Additionally, they showed that the catalyst can be
carbonitride (C3N4) treated in the same way revealed stark employed industrially in a continuous flow reactor thus show-
differences between the three systems. Whereas Ir/AP-POP casing the high potential of Ru-containing POPs.117
showed Ir3+, Ir/AC and IR/C3N4 showed Ir(0) species and the N-Heterocyclic carbenes (NHCs) are commonly used as
formation of Ir nanoparticles of up to 2 nm in size. As a result, ligands for homogeneous catalysts, where the derived catalysts
Ir/AP-POP exhibited higher CO2 conversion efficiency to formic show some of the highest activities. Bringing NHCs to hetero-
acid compared to Ir/AC and Ir/C3N4 while also showing good geneous POPs, Tu et al. prepared an Ir-containing NHC
recyclability. This result showcases that single-atom catalysts polymer (POMP-NHC-IR) via direct knitting of a robust bis-
based on POPs can show high catalytic activity for CO2 conver- NHC-Ir complex via a Friedel-Crafts reaction and showcased its
sion and the design of an appropriate chemical environment utilization towards the N-formylation of amines with CO2
with multiple electron-donating groups can efficiently stabilize and H2.118 In a previous work, the authors demonstrated that
certain metal species while suppressing the formation of NPs. a NHC-Ir catalyst showed excellent catalytic activity. However,
Fig. 10 Structure analysis of Ir/AP-POPs. Atomically dispersed and stable Ir metal atoms are analyzed. (A) The solid-state 13C/CP-MAS NMR spectrum of
the AP-POP suggests the presence of CQO, C–N, and C–Ar groups. (B) The N 1s core level XPS spectrum of the AP-POP distinguishes N in the pyridinic
and amide groups in the framework. (C) The UV-vis absorbance spectra of samples with and without Ir indicate the p–p* electron transition of the
conjugated polymer and show the supported Ir single atoms result in a red-shift of absorption. (D) An SEM image shows the spherical particles
morphology of the AP-POP. (E and F) HAADF-STEM images of fresh (E and F) used 1.25% Ir/AP-POP indicate only the atomically dispersed Ir species on
the support, even after the CO2 hydrogenation reaction. Reproduced from ref. 115 with permission of the publisher.
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Fig. 11 Synthesis example of incorporating two different single metal atom species in porous organic polymers. Stepwise synthesis of Ni-Pc-MPOP by
condensing of (NH2)8NiPc and DFP. Reproduced from ref. 120 with permission of the publisher.
the non-porous nature of the linear polymer resulted in a porosity. Although a plethora of porous systems offer some sort
rather low TON of only 730.119 Therefore, they speculated, that of capability to store gases such as CO2 due to their heteroatom
a porous matrix could accelerate the N-formylation process due content or their intrinsic microporosity, proper design allows to
to the well-defined pore-structure and better interactions directly use POPs as sorbents and organocatalysts for the
between the gases. Indeed, their POMP-NHC-Ir catalyst featur- capture and conversion of the CO2 toward value-added pro-
ing Ir3+ sites resulted in high yield and high selectivity (499%). ducts. Among such products, especially cyclic carbonates have
Interestingly, the highest yield and selectivity were obtained for emerged as a common target of chemical conversions due to
the systems with the highest surface areas but with the lowest Ir their relative ease of synthesis, abundant precursors and ample
content and not the systems with the lowest surface area but opportunities to use the obtained products as organic solvents,
the highest Ir content, implying that pore and active site precursors in the synthesis of small molecules and polymers, or
accessibility is of tremendous importance when designing as electrolytes in batteries. We believe that it is imperative to
highly active catalysts. Moreover, heterogenous POMP-NHC-Ir focus the design of new POPs to directly capture and convert
showed much higher catalytic activity than its corresponding CO2 in order to have an impact on climate change. Taking
homogenous counterpart (bis-NHC-Ir complex). Remarkably, inspiration from the best performing systems in literature it is
POMP-NHC-IR showed a record TON (1.58 106) in the DMF clear that molecular design is key. In fully organic systems a
synthesis, and the solid POMP-NHC-Ir catalysts could be reused suitably designed catalyst can facilitate the uptake and direct
for up to 12 runs without obvious losses of its catalytic activity conversion of CO2. Namely, a combination of Lewis acidic or
or selectivity even at extremely low catalyst loadings of 20 ppm, basic sites that polarize CO2 in combination with functional
highlighting their potential in industrial applications. When it units that enable a nucleophilic attack on e.g. an epoxide
comes to catalytically active single metal site catalysts based substrate should be aimed for. This can be achieved by prepar-
on multiple abundant transition metal ions (Cu, Ni or Mn) ing differently functionalized building blocks and polymerizing
their interplay is highly important. Zang et al. reported POPs them. Although it has been shown that such motifs can work,
bearing two different catalytic sites by preparing an amine- the spatial separation of the two active sites onto different
functionalized Ni–PC that was subsequently reacted with an building blocks can be a problem in rigid, more stable systems.
aldehyde functionalized phenol to obtain the corresponding Hence, designing systems to have both functional units in
Ni–PC-salphen hybrid (NiPc-MPOP, M = Ni or Co). The mixed proximity should be prioritized. Additionally, creative molecu-
metal system NiPc-CoPOP proved to be an ideal catalyst for the lar design can also allow the generation of charged moieties on
photocatalytic reduction of CO2 to CO (Fig. 11).120 This can be the polymer backbone during the catalytic reaction, leading to
attributed to the well-defined coordination environment of the additional stability since no more labile ionic moieties have to
different metal ions and the availability of multiple active sites. be incorporated directly. Compared to their fully organic coun-
Interestingly the authors were also able to show that the Ni- terparts, metal-containing POPs have the advantage, that the
salphen active site in the NiPc-NiPOP had a higher catalytic metal-complexing moiety directly acts as a Lewis acidic, CO2-
activity than the NiPC system for the reduction of CO2 (CO2RR). philic site and hence only a suitable nucleophile-bearing or
stabilizing functional unit is required. Despite that, many
metal-containing systems rely on co-catalyst such as TBAB to
Outlook and perspective supply a nucleophile or utilize bases such as DMAP to facilitate
substrate activation. In any case, judicious control over poros-
Porous organic polymers offer a versatile platform to specifi- ity, pore size, and textural properties, in general, are of utmost
cally design and tune polymers towards their desired applica- importance to facilitate good mass transfer properties as these
tions while offering key features such as high stability and will directly influence how CO2 and substrates can interact.
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This is especially true for systems that require bulky co-catalysts being said, systems such as cage-based polymers or metalated
such as TBAB to facilitate the nucleophilic attack on epoxide POPs provide invaluable information by studying their inter-
substrates. action with both CO2 and potential substrates due to their
Operating conditions reported in literature vary drastically defined cavities and distinct metal sites. Taking the recent work
in terms of catalyst amount (wt% vs. mol% or active site vs. total by Reimer et al. as an example45 it is clear that POPs can be
amount), use and amount of co-catalysts, temperature, reaction produced on a kilogram scale – even under lab conditions –
times, and CO2 pressure. Although this is understandable as while obtaining highly functional polymers with exceptional
different systems offer varying performances under different CO2 uptake at low relative pressures. Especially under these
conditions, as a community we should strive to always test a set conditions only few systems can outperform their melamine-
of benchmark conditions (e.g. 5 mmol substrate, 5% catalyst, based POPs; among them are amine scrubbers such as MEA.
none/5% co-catalyst, 80 1C, 24 h, 1 bar CO2) to enable our peers These amine scrubbers however come at the cost of signifi-
to more easily compare the performance of POPs and to draw cantly more energy-intensive purification/regeneration,
conclusions about the molecular design based on these perfor- whereas the shown POPs were easily regenerated and used for
mance parameters. These issues are often amplified because several cycles. One should also avoid precious metal catalysts
standard characteristics like TON or TOF are only occasionally and complex syntheses without sacrificing the performance in
discussed in systems where active sites can be easily deter- order to reach the cost target of 50$ per tonne of CO2.
mined (e.g. active metal sites based on the metal content of a
polymer). Besides the operating conditions, recyclability tests
are also subject of much ambiguity. The catalysts are often not Conclusions
thoroughly investigated in terms of their recyclability and in
Within this review article, we have highlighted the key para-
many cases, conditions are only described sparingly. This is
meters governing CO2 uptake, separation, selectivity and con-
especially important for metal-containing systems, where dif-
version in POPs. The wide range of available building blocks
ferent binding motifs result in varying amounts of metal loss.
and the vast amount of feasible, industrially relevant syntheses
Although some reports in the literature address these points by
endows POPs with a degree of tunability unlike any other class
evaluating the total metal content of the catalysts after each
of materials. The fact that both the pore structure and the
cycle presenting such data might lead to scrutiny during the
chemical environment within the pores can be tuned towards
publication process. Nonetheless, in order to make an impact
specific applications allows the preparation of highly task-
in the field and on our society, such data is required. Another
specific polymers. Although most POPs show some capabilities
critical point lies in how such potentially useful polymers are
towards CO2 uptake, the importance of specific moieties in
produced. Although the community has shown a continued
POPs for high CO2 uptake and direct conversion must be
drive toward more sustainable protocols and even environmen-
highlighted. We have presented a plethora of suitable design
tally friendly methods, a plethora of materials are produced
strategies based on (i) high heteroatom content, (ii) intrinsically
with sustainability as an afterthought. Considering that the
porous molecular precursors and (iii) metal-containing sys-
entire field of carbon capture and conversion is dedicated
tems. Whereas heteroatom-rich systems and systems based
toward reducing humankinds’ impact on the environment this
on porosity-inducing precursors still often rely on co-catalysts
is a surprising and worrying trend.
for the conversion of CO2 to value-added products, special
To that end, computational materials design can be an
design strategies based on charged building blocks or precisely
exceptional tool in the repertoire of chemists. Not only to
tuned active moieties allow the conversion of CO2 without the
reduce the endless amount of potential candidate polymers
need of co-catalysts. POPs incorporating homogenously dis-
but also to help optimize reaction conditions through statistical
persed metal ions are of special importance as they enable a
analysis. However, one major culprit of such computational inves-
variety of industrially relevant applications and provide a
tigations lies in the availability and inhomogeneity of data – the lack
suitable coordination environment within the system. For these
of clearly defined benchmark conditions being just one of them –
systems, an in-depth understanding of the nature of catalytic
thus making such approaches even more work-intensive, while
sites would be highly beneficial in order to establish a correla-
reducing the potential impact of such investigations.
tion between the structure and the catalytic activity.
Especially for industrial purposes the cost of production is a
Overall, POPs are an intriguing platform for CO2 capture, separa-
key that is especially hard to assess from an academic point of
tion, and conversion. However, even though a plethora of POPs have
view. On the one hand a clear differentiation between systems
been reported for CO2 uptake, only few have been explored for the
of purely academic interest and systems that are more suitable
conversion of CO2 towards value-added products. With this contribu-
for industry has to be made. Let’s take cage-based polymers as
tion, we want to stimulate the community towards the design of new
an example. Although such systems can provide good CO2
POPs aimed at CO2 capture and conversion.
uptake and, in some cases, even conversion capabilities, their
often complex synthetic requirements would make industrial
implementation more unfeasible compared to polymers of Conflicts of interest
lower performance but significantly easier synthesis such as
functionalized porous melamine formaldehyde resins. That There are no conflicts to declare.
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Acknowledgements 25 O. Buyukcakir, Y. Seo and A. Coskun, Chem. Mater., 2015,

27, 4149–4155.
This publication was created as part of NCCR Catalysis (grant 26 N. Buli, K. Abnett and S. Twidale, 2021, https://www.
number 180544), a National Centre of Competence in Research reuters.com/business/energy/eu-carbon-price-tops-50-
funded by the Swiss National Science Foundation. euros-first-time-2021-05-04/.

27 F. Franco, C. Rettenmaier, H. S. Jeon and B. R. Cuenya,
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Porous organic polymers for CO2 capture,

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ports have strong advantages. First of all, elaborate control over

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with N have been introduced into POPs upon the reaction of

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Table 1 Selection of POPs containing heteroatoms

Heteroatom contenta CO2 uptake CO2 Qst (kJ CO2/N2

6 CTF-3 1454 — 0.98 0 — — — — — 2.13 1.34 21.0 24.5 41

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SABETa CO2 at 273 K CO2 at 298 K CO2 Qst CO2/N2

NPOF-4 1249 2.50 1.40 23.2 27 Gas sorption 65

Azo-COP-5 127.6 2.04 1.24 27.3 73.8 Gas sorption 23

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Metal Coordination BET Yield Conversion TOF

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Acknowledgements 25 O. Buyukcakir, Y. Seo and A. Coskun, Chem. Mater., 2015,

funded by the Swiss National Science Foundation. euros-first-time-2021-05-04/.

Carbon Dioxide, https://gml.noaa.gov/ccgg/trends/mlo. 29 A. K. Sekizkardes, P. Wang, J. Hoﬀman, S. Budhathoki and

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Review Article Chem Soc Rev

2018, 8, 419–450. S. Yoon, ChemSusChem, 2020, 13, 1735–1739.

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