Chemosphere 291 (2022) 132795

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Covalent organic framework-based porous materials for harmful

gas purification
Yan Huang a, *, 1, Xiaoqian Hao a, 1, Shuanglong Ma a, **, Rui Wang b, ***, Yazhou Wang a
a
College of Resources and Environmental Sciences, Henan Agricultural University, Zhengzhou, 450002, PR China
b
School of Environmental Science and Engineering, Shandong University, Qingdao, 266237, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Remarkable advantages of COFs as

porous materials are reviewed.
• Various functionalization strategies of
COFs are summarized.
• Recent studies of COFs in harmful gas
purification are discussed.
• For certain gas, adsorption/catalysis/
detection characteristics are studied.
• Faced challenges and future research
directions are proposed.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Grzegorz Lisak Covalent organic frameworks (COFs) with 2D or 3D networks are a class of novel porous crystalline materials,
and have attracted more and more attention in the field of gas purification owing to their attractive physico­
Keywords: chemical properties, such as high surface area, adjustable functionality and structure, low density, and high
Covalent organic frameworks stability. However, few systematic reviews about the application statuses of COFs in gas purification are avail­
Harmful gas
able, especially about non-CO2 harmful gases. In this review, the recent progress of COFs about the capture,
Adsorption
catalysis, and detection of common harmful gases (such as CO2, NOx, SO2, H2S, NH3 and volatile pollutants) were
Catalysis
Functional materials comprehensively discussed. The design strategies of COF functional materials from porosity adjustment to sur­
face functionalization (including bottom-up approach, post-synthetic approach, and blending with other mate­
rials) for certain application were summarized in detail. Furthermore, the faced challenges and future research
directions of COFs in the harmful gas treatment were clearly proposed to inspire the development of COFs.

1. Introduction chemical agent production, waste composting reaction, and breeding

processes, are extensively emitted into the atmospheric environment,
Nowadays, anthropogenic harmful gases from fuel combustion, causing worldwide risks and challenges. Among them, typical harmful

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: sokl_yanhuang@163.com (Y. Huang), shuanglongma168@163.com (S. Ma), wangrui@sdu.edu.cn (R. Wang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.chemosphere.2021.132795
Received 5 September 2021; Received in revised form 23 October 2021; Accepted 2 November 2021
Available online 5 November 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
Y. Huang et al. Chemosphere 291 (2022) 132795

gases (NOx, SO2, H2S, CO2, NH3, and volatile pollutants) are the main objects (Zhi et al., 2020). In design processes of COF materials, the main
contributors of air pollution. Table 1 shows the properties and concen­ concerns usually focus on the porosity structure and surface function­
tration limits of these gases (Barea et al., 2014; Bobbitt et al., 2017). ality (Zhu et al., 2020b). And then, COF materials can be synthesized
Concerning about the environmental impacts caused by harmful gas through appropriate synthetic methods including solvothermal (Ma
emission, such as global warming, acid rain, photochemical smog, and et al., 2019), microwave (Ji et al., 2020), ionothermal (Maschita et al.,
other air quality degradation problems, harmless treatment of these 2020), mechanochemical (Wang et al., 2018b), interfacial (Zhou et al.,
gases is extremely crucial for protecting ecological environment and 2019), and synthesis under ambient conditions (Fang et al., 2019). Ac­
human health. To eliminate these pollutants, various technologies have cording to the above design and synthesis strategies, COF functional
been studied, mainly including adsorption and catalysis. It is noteworthy materials with unique performances can be constructed for certain
that porous materials are the key element during adsorption and catal­ application.
ysis process to weaken or eliminate the adverse effects of these gases.
As a class of novel porous materials, covalent organic frameworks 2.1. Porosity structure
(COFs) with 2D or 3D networks are synthesized by reversible polymeri­
zation reactions of light elements (i.e., C, H, O, N, B and Si) via covalent In the constructing process of functional materials, porosity is the
bonds (Dong et al., 2020). In comparison with conventional porous ma­ first concerning property. To obtain porous COF materials, there are two
terials (carbons, zeolites, silica-supported salts, and so on), COFs have the pore forming methods. One method (templating method) is to introduce
merits of low density, high surface area, regular structure, and diverse structural-directing agents as templates during the building processes of
functions (Wang and Zhuang, 2019; Bagheri et al., 2021). Besides these, COF blocks, and then extract templates from the blocks, which can
COFs also have higher stability than popular metal-organic frameworks provide porous structures for COFs. (Zhao et al., 2019a, 2019b). For
(MOFs) constructed from organic linkers and metal units (Li et al., 2020d; example, Zhao et al. chose polystyrene spheres (PSs) as the hard tem­
Lin et al., 2021). This is because the covalent bonds of COFs are relatively plate for the formation of COFs with interconnected macropores struc­
stronger than the metal-ligand coordination bonds of MOFs, especially tures. The characterization results showed that the specific surface area
under extreme conditions, such as high temperature, strong acidic or (723 m2/g) of COFs after PSs removal through Soxhlet extraction was
alkaline medium (Cote et al., 2005; Shan et al., 2021; Hu et al., 2021). All higher than that of pristine COFs, and the obtained COFs had rich and
these benefits promote COFs gaining more and more attention in the regular pore structure as shown in Fig. 1 (a, b) (Zhao et al., 2019b).
fields of pollutant treatment from heavy metal removal (Li et al., 2019a, Another method is to select the building blocks with rigid π-backbones
2020a, 2021a) to organic pollutant degradation (Fernandes et al., 2021; and lots of reactive sites to create porous COFs via coupling reactions,
Khaing et al., 2020), energy storage (Vitaku et al., 2019; xueshu.baidu. which is more frequently used to prepare porous COFs than the former
com/s?wd=author:(E%20Dmitrieva)%20&tn=SE_baiduxueshu_c1gjeup (Ding and Wang, 2013). As for this method, the key point lies in the
a&ie=utf-8&sc_f_para=sc_hilight=personDmitrieva et al., 2020; Yang choice of building blocks because the shape of the blocks has effects on
et al., 2020b), gas capture (Fan et al., 2018; Cheng et al., 2019; Zhao et al., the pore topology structure of COFs. More importantly, the molecular
2021) and catalysis (Rotter et al., 2019; Lin et al., 2018; Zhi et al., 2020). length of the blocks will affect the pore sizes of COFs, that is, changing
Since the first COF reported in 2005 (Cote et al., 2005), the development the length of the blocks can cause pore sizes vary from micropores to
and applications of COFs are receiving great attention. At the same time, mesopores (Wang et al., 2020c). Generally, the pore size increases with
the reviews of COFs focusing on the capture and reduction of CO2 have the increase of the molecular chain length. For example, Furukawa and
been widely reported (Zeng et al., 2016; Zhi et al., 2020). However, Yaghi (2009) reported that COF-10 constructed from BPDA and HHTP
systematic reviews about application statuses of COFs on non-CO2 blocks had larger pore size (3.2 nm) than COF-5 built by BDDA and
harmful gases are rare. HHTP (2.7 nm) (Fig. 1(c)). According to their spatial structures, building
Hence, the purpose of this review is not to simply repeat those blocks can be divided into two categories of 2D and 3D. In the case of 2D
contents summarized in previous reviews but to introduce and discuss blocks, different geometry marches of these blocks, which can be uni­
the design and synthesis of COFs and COF-based functional materials formly expressed as Cn according to the number of the symmetric
from the angle of harmful gases removal, highlight the recent advances reactive groups, lead to the unique 2D COFs with different pore sizes. As
and application prospects in gas capture and catalysis, and help readers shown in Fig. 1 (d) (Geng et al., 2020), triangular, tetragonal, and
to recognize the limitations of these materials and how to modify COFs. hexagonal COFs can be synthesized by using the combinations of
[C2+C6], [C2+C4], [C2+C3], respectively, and the pore sizes of trian­
2. Design strategies for COF functional materials gular COFs are less than those of tetragonal and hexagonal COFs.
Compared to 2D COFs, the construction of 3D COFs needs at least one
From the viewpoint of synthetic chemistry, COF materials can be building block with orthogonal geometry to promote the extension of
specifically designed and controllably synthesized according to research the polymer skeleton for a 3D network (Guan et al., 2020; Zhu et al.,
2020b). Due to the finite diversity of orthogonal-type blocks and the
Table 1 synthetic and designable difficulty, most of the reported 3D COFs are
Physical parameters and toxicity data for sectional gases (Barea et al., 2014; microporous and low porosity materials (Yahiaoui et al., 2018). In
Bobbitt et al., 2017). addition, the linking forms of building blocks also have major effects on
Typical gas Kinetic diameter (pm) Boiling point (K) IDLHa (ppm) the porosity and crystallinity of COFs. The effects of this level mainly
reflect on the choice of linkages (Liang et al., 2020). For example, Yaghi
NO 349.2 121.4 100
NO2 401–512 302.2 20
and co-workers synthesized COF-1 and COF-5 based on boroxine linkage
SO2 411.2 263.1 100 and boronate-ester linkage, and found that the pore widths of COF-1 and
H2S 362.3 212.8 100 COF-5 were 1.5 and 2.7 nm, respectively (Cote et al., 2005). To date,
CO2 330 216.6 40,000 various COFs have been synthesized with different linkages, which
CO 369 81.7 1200
mainly include boron-based linkages (Evans et al., 2019; Park et al.,
NH3 290 239.8 300
CH3OH 362.6 337.7 6000 2020), triazine-based linkages (Wei et al., 2019; Afshari et al., 2020),
Acetone 460 329.2 2500 imine-based linkages (Nguyen et al., 2020), and other linkages (such as
Benzene 534–585 353.2 500 C–– C linkages, 1,4-dioxin linkages, hydrazone linkages) (Jin et al., 2017;
Toluene 525 383.8 500 Zhang et al., 2018b; Li et al., 2019b). In this regard, various articles and
a
IDLH represents the concentration levels that cause death and adverse reviews have comprehensive illustration and summary, so they are not
effects. be introduced in detail here (Yang et al., 2020a; Ding and Wang, 2013;

2
Y. Huang et al. Chemosphere 291 (2022) 132795

Fig. 1. SEM images of PSs@COFs (a) and COFs after PSs removal (b), reproduced with permission (Zhao et al., 2019b); synthesis of COF-5 and COF-10 (c),
reproduced with permission (Furukawa and Yaghi, 2009); effects of different geometry marches on the pore size of 2D COFs (d), reproduced with permission (Geng
et al., 2020).

Geng et al., 2020; Guan et al., 2020; Yahiaoui et al., 2018; Liang et al.,
2020; Wang et al., 2020b).
2.2. Surface functionalization
Apart from the porosity structure, the performances of COFs such as
adsorption, catalysis, stability, or fluorescence need to be precisely
designed for certain application. In which, the functional groups of pore
surfaces are crucial for the interactions between COFs and target mol­
ecules because the surfaces are related to the physicochemical
characteristics, and the formation of the interface interacting with guest
molecules. The different interactions between functionalized COFs and
target molecules such as π-π interactions, hydrogen-bonding in­
teractions, electrostatic effects, and quadrupole interactions can be
triggered (Li et al., 2017; Huang et al., 2017; EL-Mahdy et al., 2019).
Therefore, how to construct a special surface on the COFs is an impor­
tant topic in developing pore surface chemistry for functionality
exploration. To obtain the functional COFs for certain application, the
surface functionality strategies mainly include the following two
methods: (1) bottom-up approach: the modification of COF building

3
Y. Huang et al.
blocks (Fig. 2 (a)); (2) post-synthesis approach: the introduction of
functional groups after COF formation (Fig. 2 (b)).
2.2.1. Bottom-up approach
Bottom-up approach has been widely proved to be a simple and
effective strategy for synthesizing functional COFs since Dichtel et al.
reported that COF-102-C12 and COF-102-allyl were successfully pre­
pared by using dodecyl/allyl functionalized monomers in 2012 (Bunck
and Dichtel, 2012). In this synthesis process, the functional groups are
directly linked with the building blocks before the formation of COFs.
The remarkable advantages of this approach lie in that functional groups
can be uniformly dispersed on the skeletons of COFs, and the number of
active sites can be precisely controlled by adjusting the quantity of
building blocks (Ding and Wang, 2013; Guan et al., 2020). To date,
various COFs based on the modification of functional groups have been
widely reported (Qian et al., 2016; Zhang et al., 2015; Xu et al., 2016).
For example, Jiang et al. synthesized two kinds of porphyrin-COFs based
on terephthalaldehyde and squaric acid through the bottom-up func­
tionalization approach, and introduced catalytically active sites on the
porphyrin-COFs via the metal-porphyrin complexation for further
functional modification. The results showed that Mn-porphyrin-COFs
had the highly catalytic efficiency for the selective oxidation of olefins
(Zhang et al., 2015). As a matter of fact, this approach can not only
controllably introduce functional groups, but also tailor pore sizes in the
case of maintaining the skeleton structure of COFs (Wang and Zhuang,
2019). Yuan and co-workers found that the BET surface areas (SBET) of
the [HOOC]-COFs varied from 713 to 652, 458, 279, and 150 m2/g with
the increase of carboxyl group content, and the pore sizes accordingly
changed from 1.50 to 1.48, 1.44, 1.11, and 0.97 nm (Yang et al., 2018).
Therefore, the physicochemical properties (e.g., porosity, stability) of
COFs should be considered owing to effects of modified block content.
However, it is hard to synthesize specific functionalized blocks for
certain application. Moreover, the active parts of functionalized blocks
need to be protected to avoid side reaction with active terminals of COFs
(Yusran et al., 2020). These defects cause adverse effects on synthesizing
COFs with regular skeletons so that limits the applications of bottom-up
approach (Gan et al., 2021). More recently, the non-covalent in­
teractions (such as aromatic, van der Waals and dipolar force in­
teractions) between COF layers have become a new design direction in
the bottom-up synthesis because the ordered stacking of the layers is
important for improving the catalysis, adsorption properties of COFs
(Alahakoon et al., 2020; Zhao et al., 2018; Cai et al., 2019).
2.2.2. Post-synthetic approach
In consideration of the limitations of bottom-up approach, such as
the difficulty of building block functionalization, and adverse effects of
some functional groups on the formation of crystal skeletons, the post-
synthetic approach is widely applied in the synthesis of functional
COFs (Gan et al., 2021; Yusran et al., 2020). In this method, the
Fig. 2. General functionality methods of COFs.
4
Chemosphere 291 (2022) 132795
functional moieties are introduced into the pristine skeleton for
obtaining functional COFs. Whereas, this process may cause the skeleton
damage of pristine COFs under some cases (Guan et al., 2020). Here, the
crucial point of this method is to choose appropriate functional moieties
and modification conditions for ensuring the skeleton structure stability.
As shown in Table 2, the present post-synthetic methods can be divided
into the following categories: (1) encapsulation various active metal
species into the COFs via the coordination between building blocks and
metal ions, including Pt, Ca, Ni, Fe, Pd, Zn, and so on (Fig. 3 (a)) (Lu
et al., 2017; Gao et al., 2020; Yue et al., 2019; López-Magano et al.,
2020; Dai et al., 2018; Xu et al., 2020; Zhuang and Wang, 2021); (2)
covalent bond formation of the pendant groups on the COFs based on
reversible chemical reactions (Lu et al., 2018; Gao et al., 2019); (3)
chemical conversion of linkers (Fig. 3 (b)) (Guan et al., 2019; Grunen­
berg et al., 2021; Yan et al., 2020). Generally, the formation of func­
tional COFs based on these modification methods needs functional
moieties in the initial skeletons as reactive sites to supply a modified
platform (Segura et al., 2019).
2.3. Blending with other materials
Apart from the above modification methods, blending method is to
synthesis the composite materials combining the merits of blending
materials via a simple and feasible modification. In which, choosing the
appropriate blending materials is significant for achieving specific
application of COFs. At present, COFs have been widely blended with
other materials (Fig. 4), such as carbon nanotubes (Chen et al., 2019;
Gomes and Bhattacharyya, 2020), carbon nitride (Luo et al., 2019,
2020), graphene (Li et al., 2020c; Gao et al., 2021), metal (Aiyappa
et al., 2016; Liao et al., 2017; Zhang et al., 2019), and MOFs (Sun et al.,
2018b; Li et al., 2019c; xueshu.baidu.com/s?wd=author:(A%20L%C3%
B3pez-Magano)%
20&tn=SE_baiduxueshu_c1gjeupa&ie=utf-8&sc_f_para=sc_hilight=per­
sonWang et al., 2020a). Generally, different blending strategies are
adopted according to certain application. In the terms of adsorption,
carbon nanotubes, graphene, MOFs, and magnetic materials (like Fe3O4)
have been introduced into the skeletons of COFs to improve the
adsorption, separation, and regeneration ability (Li et al., 2020b). For
example, Ma et al. combined the good stability of graphene with the easy
functionalization of COFs by introducing COFs on graphene sheets to
obtain a G-COF composite with the excellent adsorption performance for
uranium (Wen et al., 2018). The results showed that the adsorption
capacity (144.2 mg/g) of G-COF was obviously higher than those of
pristine GO (92.5 mg/g) and COF (105.0 mg/g). In the catalysis field,
metal and non-metal elemental doping is a useful method to improve the
catalytic performance of COFs (Wang et al., 2020b). Besides this,
blending with supporting materials has also been proved to be a feasible
method to promote catalytic reaction (Luo et al., 2020; Yao et al., 2019).
For example, Li et al. studied the catalytic ability of hollow
Y. Huang et al. Chemosphere 291 (2022) 132795

Table 2
Post-synthetic modification of recent COFs and their applications.
COFs Moieties Strategies SBET (m2/g) Applications Ref.

3D-COOH-COF OH–COF Ring-opening reaction 540 Extraction of lanthanide ions Lu et al. (2018)
MCNC@COF@Zr4þ OH–COF Sequential functionalization 49 Enrichment of phosphopeptides Gao et al. (2019)
amidoxime-COFs CN-COFs Solvothermal reaction 513 Extraction of uranium Sun et al. (2018a)
SO3H–COF OH–COF Postsynthetic modification 1510 5-hydroxymethyl- Sun et al. (2019)
furfural transformation
COF-S-SH vinyl-COF Click reaction 1152 Removal mercury Sun et al. (2017)
COF-316-CONH2 1,4-dioxin–COF–316 Substitution reaction 395 / Zhang et al. (2018a,b)
EDTA@NH2–COF NO2–COF Postsynthetic modification / Removal heavy metal ions Jiang et al. (2019)
Au–S–COF propenyl-COF Click reaction 31 Reduction of 4-nitrophenol Zhang et al. (2020b)
(Cyclen@Ni0⋅5Fe0.5)@COF–SO3 NH4@COF–SO3 One-pot post synthesis 42 Electrocatalysts Feng et al. (2020)
thiazole-COF NH2–COF Postsynthetic modification 1431 / Haase et al. (2018)
COF-616-CON(CH3)R1 COF-616-COOH Postsynthetic modification 12–47 Uptake of heavy metal ions Guo et al. (2020a)
COF-616-COOR2
COF-616-COSR2
NH2@COF vinyl-COF Click reaction 335 Extraction of pesticides Ji et al. (2019)
thiol-COF alkynyl-COF Click reaction / Enrichment of Hg2+ Sun et al. (2021)

Pd-NPs@COF for 4-nitrophenol at room temperature, and found that it
exhibited superior catalytic activity and stability under the synergy
between Pd and COF for the reduction of 4-nitrophenol (Cui et al.,
2019). As for detection, fluorescently-labeled probes (as donors) intro­
duced onto the surface of COFs (as acceptors) through π-π stacking and
hydrogen-bonding interactions as signal sensors have been successfully
applied in the detection of pollutants (Li et al., 2017). Mandal and
co-workers synthesized an azine-triazine based COF (ANCOF) as a
sensor via solvothermal method to detect organic wastes (dichloran and
4-nitroaniline) in aqueous solution, and found that its detection limits
for dichloran and 4-nitroaniline were 142 and 89 ppb, respectively,
which achieved the ultrafast and sensitive detection (Das et al., 2020).
3. Applications in harmful gas removal
After the functional design of porosity structure and surface, COFs
with specific physicochemical properties provide a porous platform for
the capture and catalysis of harmful gases, which promotes the highly
efficient removal of the gases. In recent years, COFs have been devel­
oped for various target gases, from CO2 to NOx, SO2, H2S, CO, NH3 and
volatile pollutants.
3.1. CO2 capture and reduction
Due to the extensive consumption of fossil energy, CO2 has become
the major contributor of greenhouse effect at present (Lin et al., 2021).
According to the research data from ESRL’s Global Monitoring Labora­
tory (GML), the content of atmospheric CO2 has continued to increase to
416.34 ppm as of March 2021, which is 2.89 ppm higher than the same
period last year. How to reduce the CO2 emission and weaken the
greenhouse effect is the key to achieve the carbon neutralization. The
research on improving the capture ability of COFs for CO2 has aroused
great interests since the first report in 2009 (Guo et al., 2021a). Table 3
summarizes the typical COFs for CO2 capture in recent years.
About CO2 adsorption, COFs exhibited different adsorption potenti­
ality under different conditions such as SBET, temperature, and pressure,
as shown in Table 3. Under the same conditions, the research showed
that COFs had higher adsorption ability for CO2 at low temperature
(273 K) than high temperature (298 K). The adsorption capacity of COFs
for CO2 had an obvious decrease as pore size increasing at low pressure
(1 bar), especially when pore size was larger than 1 nm, illustrating that
CO2 capacity had a direct relationship with pore sizes. However, high-
pressure (55 bar) adsorption results showed that the adsorption capac­
ity of COFs (e.g., COF-10) with high SBET for CO2 (1010 mg/g) was better
than those of COFs with low SBET, indicating that SBET and pore volume
had a significant effect on the CO2 capacity at high pressure (Furukawa
and Yaghi, 2009; Zeng et al., 2016). In addition, owing to the chemical
stability, COFs after functionalization still exhibit ideal stability. For
example, Jiang et al. reported that [HO2C]100%-H2P–COF after CO2
adsorption can be effectively regenerated under high vacuum at 353 K,
and its CO2 capacity (180 mg/g) had no significant decline after ten
cycles, demonstrating excellent recycling performance (Huang et al.,
2015). Recently, Smit et al. evaluated the carbon capture performance of
more than 69,000 hypothetical COFs by calculating the CO2 Henry co­
efficient, and found that pore topology had a leading effect on improving
the capture performance of COFs (Deeg et al., 2020). Wang and
co-workers obtained binder-free COF monolith (SNW-1) via 3D printing
process, and found that SNW-1 had higher CO2 adsorption (58.42
cm3/g) compared to the COF made with F127 binder (5.80 cm3/g) at
273 K and 1 bar, and the N2 uptake of SNW-1 was only 6.59 cm3/g under
the same conditions, proving the high adsorption affinity of binder-free
COFs for CO2 (Liu et al., 2021). In addition, COFs in Table 3 are superior
to most zeolite-based materials (e.g., 13X, 4A, 5A, NaX) in CO2
adsorption (Zagho et al., 2021).
In terms of CO2 separation, the research mainly focuses on studying
the CO2/N2, CO2/CH4 separation performance. Due to the adjustable
pore structure, COFs can be designed to possess the pore size nearing the
size of gas molecules for gas separation. However, when the kinetic
diameter of the interfering gas is close to that the target gas, like that the
kinetic diameters of CO2 and N2 are 3.3 Å and 3.64 Å, respectively, it is
difficult to separate CO2 from N2 via molecular sieving (Wang et al.,
2020c). To further improve the selectivity of COFs, the general strategy
is to introduce some functional groups with high CO2 affinity into the
channels of COFs. For example, Darmawana et al. studied the separation
performance diamine-linked COF (IPB–1H and IPB-2H) for CO2/N2 by
exploring the adsorption sites and adsorption energies, and found that
the CO2/N2 selectivity of IPB-1H and IPB-2H were approximately 2 in
mixture gases at 353 K (Apriliyanto et al., 2020). Zhong et al. found that
the COF membranes with high throughput could realize the CO2/CH4
separation by computational screening method, and identified that the
CO2/CH4 separation performance of COFs after –F and -Cl groups
modification can be improved (Yan et al., 2018). In addition, the
research proved that choosing the strategy of preparing COF membrane
also can be used to promote the CO2 separation from interference gases.
For example, Wang et al. prepared mixed matrix membranes (MMMs) by
using poly-vinylamine (PVAm) to modify COF-LZU1 for CO2 separation.
This membrane with 0.932 nm channels exhibited optimal separation
performance of CO2 permeance (957 GPU) and CO2/H2 selectivity
(17.1) at 2.0 MPa, which was better than the CO2/H2 selectivity of
MMMs-MOF (MIL-53(Al)) membrane (13.3) (Cao et al., 2020; Nabais
et al., 2019).
In addition, the conversion of CO2 into high-value chemicals (i.e.,
CO, CH4, C2H4, HCOOH, MeOH) through catalytic reaction is another
extremely significant research subject to eliminate the greenhouse effect

5
Y. Huang et al.
Fig. 3. Synthesis routes of NiFe@COF–SO3 (a), reproduced with permission (Gao et al., 2020); post-synthetic sequence of imine-COF via the strategy of chemical
conversion of linkers (b), reproduced with permission (Grunenberg et al., 2021).
of CO2 and promote the recycling of carbon resources (Yuan et al.,
2020b). A series of COF catalysts have been widely explored for CO2
reduction under the conditions of photocatalysis or electrocatalysis, as
shown in Table 4.
In field of CO2 reduction, porphyrin and its metal derivatives are an
important kind of COF-based catalysts. Yaghi and co-workers developed
COF-367-Co and COF-366-Co for the electroreduction of CO2 to CO by
utilizing the retention role of cobalt in the coordinating porphyrin units
(Lin et al., 2015). Compared to COF-366-Co, COF-367-Co with a larger
pore size was more conducive to the reduction of CO2 to CO. The reason
is that larger pore sizes can promote CO2 adsorption, which can further
enhance the electrocatalytic activity of cobalt porphyrin active sites.
Furthermore, tetrathiafulvalene (TTF) can be used as electron donor or
carrier to construct an oriented electron transmission pathway with
metalloporphyin. Based on this, a 2D Co-TTCOF with high electro­
catalytic performance was developed and applied in the conversion of
CO2 to CO, which had high FE (CO) value (91.3%, − 0.7V) and cycling
6
Chemosphere 291 (2022) 132795
stability (>40 h) (Zhu et al., 2020a). Interestingly, the FE (CO) of
Co-TTCOF nanosheets after exfoliation can increase to almost 100%
(99.7%, − 0.8 V).
On the other hand, different metal ions as active sites are introduced
into the reticular structure of COFs, which have different catalytic ac­
tivity and products proved by Kang’s team (Lu et al., 2019a). They
prepared various COF-M (M = Co, Ni, Zn) as photocatalysts utilizing Co,
Ni and Zn ions as active sites, respectively (Fig. 5 (a)). The results
showed that DQTP COF–Co can achieve the highly efficient conversion
of CO2 to CO with production rate of 1020 μmol h− 1 g− 1 (turnover
number (TON) = 2.18, turnover frequency (TOF) = 0.55 h− 1), and DQTP
COF–Zn exhibited the highest conversion efficiency (152.5 μmol h− 1
g− 1) for HCOOH production (TON = 0.33 and TOF = 0.08 h− 1) under
visible light irradiation (Fig. 5 (b)). Recently, Lu et al. synthesized a
series of dioxin-linked metallophthalocyanine COFs as photo-coupled
electrocatalysts for CO2 reduction (Lu et al., 2021). Under the electro­
chemical condition, the FE (CO) of NiPc-TFPN COF and CoPc-TFPN COF
Y. Huang et al.
Fig. 4. Common composite materials based on COFs.
can reach up to 99.8% and 96.1% at 0.9 V vs. RHE, respectively.
Compared to the electrochemical condition, the FE (CO) and current
density of NiPc-TFPN COF further increased under the conditions of
photo-coupled electrocatalysis and a wide potential range from 0.6 to
1.2 V vs. RHE.
3.2. NOx and SOx removal
The nitrogen and sulfur oxides are common gaseous pollutants that
are produced in the process of fossil fuel combustion. Nitrogen oxides (i.
e., NO and NO2), mainly from automobile exhaust and power stations,
can cause a series of environmental problems, such as haze, ozone
depletion, photochemical smog, and acid rain (Lei et al., 2021). Sulfur
dioxide is mainly found in waste gas from coal-fired stations, which also
can cause acid rain when it meets with O2, water vapor and other
compounds (Yun et al., 2019). In this part, we will summarize and
highlight some recent research related to the applications of COFs on
NOx and SOx removal.
Zhao et al. studied the adsorption performances of COF-105 and
COF-108 for NO and NO2 by grand canonical Monte Carlo (GCMC)
simulations. They found that the NO adsorption capacity of COF-105 can
reach 3.6 mmol/g, and the NO2 adsorption capacity of COF-108 reached
up to 6 mmol/g at 10 bar and room temperature (Wang et al., 2012).
Wang et al. performed density functional theory (DFT) calculations to
study the adsorption properties of metal (Li, Na, K, Sc)-COFs for SO2, and
reported that the calculated interaction energies between the absorbed
SO2 and Li@COF-105, Na@COF-105, K@COF-105, Sc@COF-105 com­
plexes were − 25.46, − 21.87, − 19.14, and − 41.36 kcal/mol, respec­
tively (Wang et al., 2018c). Lee et al. prepared imide-functionalized COF
(PI-COFs) as a SO2 adsorbent, and found that its SO2 adsorption capacity
7
Chemosphere 291 (2022) 132795
could reach up to 6.30 mmol/g. The regeneration experiment showed
that the used PI-COFs can be completely regenerated through N2 purg­
ing, and the SO2 capacity had no obvious decrease during five
adsorption-desorption cycles, suggesting the chemical stability of
PI-COFs (Lee et al., 2017). Recently, Li and co-workers constructed a
series of germanate-based anionic COFs (Ge-COFs) with different pore
properties by incorporating alkali metal cations (Li+, Na+, and K+) into
the 2D framework of Ge-COFs (Fig. 6) (Ashraf et al., 2020). The results
showed that K+-based Ge–COF–K with a surface area of 1252 m2/g and
pore volume of 0.84 cm3/g had higher SO2 breakthrough capacity (154
mg/g) under ambient conditions than the other metal-based Ge-COFs,
and the Ge–COF–K regenerated through N2 flow at 150 ◦ C can basically
maintain stable capacity and initial crystallinity after five cycles. In
comparison with 5A (109 mg/g) and ash-derived zeolites (49 mg/g),
Ge–COF–K exhibited better adsorption performance for SO2 (154 mg/g)
under similar conditions (Pedrolo et al., 2017).
In addition, COF-based materials are also applied in the detection of
NOx and SOx. Mirica et al. designed a novel 2D conductive COF (COF-
DC-8) for the detection of NO and NO2 (Meng et al., 2019). They re­
ported that this material had the intrinsic bulk conductivity of 2.51 ×
10− 3 s/m, which was the highest conductivity achieved within an
intrinsically conductive COF, and it can sensitively response to NO and
NO2 with ultralow limits of detections (LODs) of 5 and 16 ppb. Ayub
et al. explored COF electrochemical sensors (CTF-FUM) for toxic gas (i.
e., NO, NO2, H2S and SO2) detection, and found that CTF-FUM had
higher sensitivity and selectivity towards NO, SO2 and H2S related to
other gases (Yar and Ayub, 2020).
Y. Huang et al. Chemosphere 291 (2022) 132795

Table 3
Typical COFs in CO2 capture.
COFs Linkage SBET (m2/ Pore size Pore volume (cm3/ Conditions Capacity (mg/ Selectivity Ref.
g) (nm) g) g)

COF-1 boroxine 750 0.9 0.30 273 K + 1 bar 102 Furukawa and Yaghi
298 K + 55 bar 230 (2009)
COF-6 boronate ester 750 0.9 0.32 273 K + 1 bar 170 Furukawa and Yaghi
298 K + 55 bar 310 (2009)
COF-8 boronate ester 1350 1.6 0.69 273 K + 1 bar 66 Furukawa and Yaghi
298 K + 55 bar 630 (2009)
COF-5 boronate ester 1670 2.7 1.07 273 K + 1 bar 62 Furukawa and Yaghi
298 K + 55 bar 870 (2009)
COF-10 boronate ester 1760 3.2 1.44 273 K + 1 bar 54 Furukawa and Yaghi
298 K + 55 bar 1010 (2009)
[HO]25%-H2P-COFs imine 1054 2.5 0.89 273 K + 1 bar 54 Huang et al. (2015)
298 K + 1 bar 31
[HO]50%-H2P-COFs imine 1089 2.5 0.91 273 K + 1 bar 46 Huang et al. (2015)
298 K + 1 bar 34
[HO]75%-H2P-COFs imine 1153 2.5 0.96 273 K + 1 bar 52 Huang et al. (2015)
298 K + 1 bar 32
[HO]100%-H2P-COFs imine 1284 2.5 1.02 273 K + 1 bar 63 Huang et al. (2015)
298 K + 1 bar 35
[HO2C]25%-H2P- imine 786 2.2 0.78 273 K + 1 bar 96 Huang et al. (2015)
COFs 298 K + 1 bar 58
[HO2C]50%-H2P- imine 673 1.9 0.66 273 K + 1 bar 134 Huang et al. (2015)
COFs 298 K + 1 bar 67
[HO2C]75%-H2P- imine 482 1.7 0.54 273 K + 1 bar 157 Huang et al. (2015)
COFs 298 K + 1 bar 72
[HO2C]100%-H2P- imine 364 1.4 0.43 273 K + 1 bar 174 Huang et al. (2015)
COFs 298 K + 1 bar 76
RIO-13 hydroxylated 1205 1.3 318 K+1atm 25.0 Louis et al. (2021)
azine
RIO-12 hydroxylated 804 1.3 318 K+1atm 16.2 Louis et al. (2021)
azine
RIO-11m hydroxylated 961 1.3 318 K+1atm 10.1 Louis et al. (2021)
azine
RIO-11 hydroxylated 242 1.3 318 K+1atm 6.0 Louis et al. (2021)
azine
acac-CTF-5-400 azine 1131 0.90 273 K+ 1 bar 126 CO2/N2 Jena et al. (2018)
298 K+ 1 bar 83
acac-CTF-10–400 azine 1150 0.95 273 K+ 1 bar 135 CO2/N2 Jena et al. (2018)
298 K+ 1 bar 86
acac-CTF-5-500 azine 1556 1.20 273 K+ 1 bar 145 CO2/N2 Jena et al. (2018)
298 K+ 1 bar 87
acac-CTF-10–500 azine 1626 1.60 273 K+ 1 bar 139 CO2/N2 Jena et al. (2018)
298 K+ 1 bar 84
ACOF-1 azine 1310 273 K+ 1 bar 172 CO2/CH4 Shan et al. (2016)
TMFPT-COF triazine 1407 1.86 0.97 273 K+ 1 bar 75 CO2/N2 Li et al. (2021b)
Cz-COF carbazo-le 871 0.72 273 K+ 1 bar 2.5 CO2/N2 An et al. (2019)
298 K+ 1 bar 1.5
Tz-COF benzobi-sthiazole 1439 1.18 273 K+ 1 bar 3.5 CO2/N2 An et al. (2019)
298 K+ 1 bar 2.3

3.3. H2S removal
Hydrogen sulfide (H2S) is a colorless and toxic acid gas, mainly
derived from natural gas, syngas, landfill, petroleum cracking. Its strong
toxicity and corrosivity not only can cause the extensive corrosion of the
pipeline and combustion equipment, but also can pose serious threats to
human health. According to the rules of Occupational Safety and Health
Administration (OSHA), the toxicity of H2S can be divided into three
levels: 1) low toxicity: < 10 ppm; 2) medium toxicity: 10–30 ppm; 3)
high toxicity: > 30 ppm (Huang et al., 2019). Therefore, the effective
removal and sensitive detection of H2S are extremely significant for the
utilization of fossil energy and the protection of atmospheric
environment.
On the one hand, partial 2D and 3D COF materials have been suc­
cessfully utilized as adsorbents for H2S removal (Wang et al., 2015).
However, to the best of our knowledge, relevant research has not been
widely performed yet. Cao et al. studied the adsorption and separation
performances of 2D (COF-5, COF-6, COF-8, COF-10) and 3D (COF-102)
materials for H2S (Wang et al., 2015). They found that the maximum
uptakes followed the order of COF-102 (35.57 mmol/g) > COF-10
(29.19 mmol/g) > COF-5 (22.986 mmol/g) > COF-8 (16.16 mmol/g) >
COF-6 (7.927 mmol/g) at high pressure, and COF-6 exhibited the
highest separation ability for H2S/N2, H2S/CO2 and H2S/CH4 three gas
mixtures at 303 K in comparison with the other materials. Notably, the
as-synthesized COF-102, COF-10 and COF-5 materials showed enhanced
H2S adsorption capacities compared with MIL-100 (16.7 mmol/g) and
SWNTs (5.41 mmol/g). In addition, Zheng et al. synthesized a series of
CTF-1-x at different temperatures (x = 400, 500, 600, 400–600 ◦ C) as
catalysts for H2S removal (Peng et al., 2021). Among them,
CTF-1-400-600 with largest BET surface area exhibited the highest H2S
capacity (12.8 mmol/g) at 0 ◦ C and 1.0 bar, and its H2S capacity had no
change after five cycles. Additionally, it is noteworthy that this material
can achieve the H2S dissociation to S in the presence of O2, and its
conversion can reach up to 80.5% at 90 ◦ C.
On the other hand, the research about COF-based materials for H2S
detection has been successively reported in recent years. Zhang et al.
created a COF-based hybrid probe (TpASH-NPHS) by combining the
advantages of COFs and small-molecule probes to detect H2S in bio­
logical systems (Wang et al., 2018e). Mirica et al. studied the response
ability of COF-DC-8 for H2S, and found that the detection limits for H2S

8
Y. Huang et al. Chemosphere 291 (2022) 132795

Table 4
Various COFs for CO2 reduction in recent years.
Catalysts Covalent bond SBET (m2/g) Conditions Chemicals Production Ref.
a
FE Yield (μmol/(g*h))

COF-367-Co imine 1470 electrocatalysis CO 91% Lin et al. (2015)

COF-366-Co amino 1700 electrocatalysis CO 87% Diercks et al. (2018)
COF-366-Co@CNT amino electrocatalysis CO 92% Lu et al. (2020)
COF-366-(OMe)2–Co@CNT amino 196 electrocatalysis CO 94% Lu et al. (2020)
COF-366-(OH)2–Co@CNT amino electrocatalysis CO 90% Lu et al. (2020)
COF-366-(F)4–Co@CNT amino electrocatalysis CO 91% Lu et al. (2020)
Co-TTCOF C=N 481 electrocatalysis CO 91.3% Zhu et al. (2020a)
Co-TTCOF NSs C=N electrocatalysis CO 99.7% Zhu et al. (2020a)
NiPc-COF pyrazine 358 electrocatalysis CO 99.1% Zhang et al. (2020a)
NiPc-TFPN COF dioxin 252 electrocatalysis CO 99.8% Lu et al. (2021)
CoPc-TFPN COF dioxin electrocatalysis CO 96.1% Lu et al. (2021)
TTCOF-Zn C=N 565 photocatalysis CO 12.33 μmol (60 h) Lu et al. (2019b)
CT-COF carbazole-triazine 521 photocatalysis CO 102.7 Lei et al. (2020)
Ni–COF bipyridine 973 photocatalysis CO 966 Zhong et al. (2019)
COF-367-Co NSs imine photocatalysis CO 2587 Liu et al. (2019)
SnS2/S-CTFs 122 photocatalysis CO 123.6 Guo et al. (2020b)
CH4 43.4
Mo–COF bipyridine 323 photocatalysis CO 6.19 Kou et al. (2021)
CH4 1.08
C2H4 3.57
FN-CTF-400 817 electrocatalysis CH4 99.3% Wang et al. (2018a)
COF-367-Co III imine 489 photocatalysis HCOOH 93.0 Gong et al. (2020)
Ru/TpPa-1 ketoamine 385 photocatalysis HCOOH 108.8 Guo et al. (2021b)
DQTP COF–Co 196 photocatalysis CO 1020 Lu et al. (2019a)
DQTP COF–Zn 346 photocatalysis HCOOH 152.5 Lu et al. (2019a)
a
Faradaic efficiency (%).

was 204 ppb when the exposure time was 1.5 min (Meng et al., 2019).
Zhang et al. synthesized a heterogeneous nano-scale COF (NCOF) fluo­
rescence probe through metallization of Cu2+ (Cu–COF), which was
applied on the sensitive and selective detection of H2S. The results
showed that the Cu–COF had sensitive response to H2S with a detection
limit of 10 nM, and its selectivity for H2S was higher than for other thiols
and anionic species (Ge et al., 2021). Different from the above, Star et al.
utilizing 2D COF-5 as templates to prepare graphene with pore structure
through plasma etching, which can create approximately 2.7 nm pores
on the surface of graphene, and its LOD (3 ppb) for H2S was comparable
to the best results from similar graphene-based composites (White et al.,
2019).
3.4. NH3 removal
Ammonia (NH3) is a common industrial gas, and its annual pro­
duction exceeding 200 million (Yang et al., 2018). However, its strong
corrosiveness and toxicity increase the cost and risk of industrial pro­
duction. For NH3 adsorption, various adsorbents had been studied to
improve NH3 uptake, such as carbons, zeolites, MOFs, and COFs, as
shown in Fig. 7 (Zhang et al., 2018a; Kang et al., 2020). Among them,
COF-based materials linked by covalent bonds have been widely stud­
ied, and the boronate-ester-linked COFs are proved as a category of
highly active materials for the NH3 capture because of the strong Lewis
acid-base interactions between the boron sites and the nitrogen lone pair
of NH3 (Geng et al., 2020). For instance, Yaghi and co-workers
compared the uptake capacity of COF-10 with those of 13X zeolite,
Amberlyst, mesoporous silica and MCM-41, and found that COF-10
exhibited the highest NH3 capacity (15 mol/kg) at 298 K and 1 bar
(Doonan et al., 2010). The adsorption/desorption results showed that
the NH3 capacity of COF-10 regenerated at 200 ◦ C and 0.1 torr decreased
by only 4.5% during three cycles, illustrating the good stability of
COF-10.
In recent years, great attention was put on the surface pore func­
tionality of COFs. Yuan’s team explored a series of [HOOC]X-COFs (X =
0, 17, 33, 50, and 100) with different rations of triformylphloroglucinol
(TFP), 2,5-diaminobenzoic acid (DAA), and p-phenylenediamine (PA-1)
for NH3 capture (Yang et al., 2018). Among these materials,
[HOOC]17-COFs had the highest NH3 capacity of 9.34 mmol/g at 298 K
and 1 bar, which was mainly caused by the reduction of surface area as
the load ratio increasing. Interestingly, the NH3 capacity of
[HOOC]17-COFs after introducing metal ions (Ca2+, Mn2+, or Sr2+) onto
the pore surface had an outstanding increase. Among them,
[SrOOC]17-COFs can reach up to the highest capacity of 14.30 mmol/g
under the same conditions demonstrating the strong affinity of open
metal sites for NH3, which was higher than the reported carbon mate­
rials (3.08–4.03 mmol/g) (Yu et al., 2019). Notably, its NH3 capacity
(10.92 mmol/g) had a slightly decrease after three consecutive
adsorption/desorption cycles, which was attributed to that strong
acid-base interactions between ammonia and the framework limited
desorption efficiency under vacuum conditions.
In addition, Ding et al. constructed a series of imine-based COF under
Sc(OTf)3 catalysis for NH3 sensors. The results showed that the NH3
sensing performance of the COF with a disordered structure was far
better than that of the COF with a crystalline structure (Niu et al., 2021).
The literature reported that the detection limits of COF-DC-8 for NH3
was down to 70 ppb when the exposure time was 1.5 min, suggesting the
sensitive response towards NH3 (Meng et al., 2019). Recently, Wei et al.
reported that the self-controlled synthesis of COFs can be realized
through a repolymerization strategy, and the COF film can be directly
used as the sensing interface of graphene transistor sensors, whose NH3
detection limit was down to 100 ppt (Yang et al., 2020a).
3.5. Volatile pollutants removal
In the volatile pollutant field, volatile iodine with radioactivity and
volatile organic compounds (VOCs) (like C2H2) with potential environ­
mental risks were paid attention (Xie et al., 2021), especially volatile
iodine removal. Because of their excellent physicochemical properties,
the applications of COF-based materials in highly efficient capture and
sensitive detection have also been explored.
Two imine-based 2D COFs (TPT-Azine-COF and TPT-TAPB-COF)
were synthesized by using a heteroatom-rich flexible linker 2,4,6-tris
(4-formylphenoxy)-1,3,5-triazine (TPT-CHO) as the main building
block for iodine vapor removal (Ling et al., 2018). The equilibrium
iodine capacities of TPT-Azine-COF and TPT-TAPB-COF were

9
Y. Huang et al.
Fig. 5. Synthesis of DATP COF-M and DQTP COF-M (a); conversion mechanisms of DQTP COF-M for CO2 under the photocatalytic condition (b). Reproduced with
permission (Lu et al., 2019a).
determined to be 219 and 225 wt% at 348 K under ambient pressure,
respectively, demonstrating that the presence of heteroatoms and large
π-conjugated scaffolds can promote the iodine adsorption. Jiang et al.
explored the properties of 2D crystalline porous COFs with 1D open
channels (TPB-DMTP COF and TTA-TTB COF) for iodine capture (Wang
et al., 2018d). The experimental results showed that the iodine capture
capacities of TPB-DMTP COF and TTA-TTB COF were 6.26 and 4.95 g/g
at 350 K under ambient pressure, respectively. Importantly, the pore
accessibility of regenerated TPB-DMTP COF after methanol rinse still
can reach up to >97% after five cycles, demonstrating its excellent
stability. Different from the above, Cheng et al. selected S-rich linker
benzo [1,2-b:3,4-b’:5,6-b’’]trithiophene-2,5,8-tricarbaldehyde (BTT)
and N-rich linker 1,3,5-tris-(4-aminophenyl) triazine (TAPT) as building
blocks to prepare a novel COF adsorbent with rich N and S active sites
for the capture of iodine vapor (Pan et al., 2020). The iodine capacity
can reach up to 276 wt% at 351 K under ambient pressure, and it can
retain above 99% after five cycles. Recently, Luo et al. reported the
adsorption capacities of TTA-TMTA-COF and TTA-FMTA-COF for iodine
were 3.21 and 5.07 g/g (Zhai et al., 2021). Wang et al. constructed a
nitrogen-rich COF (SCU–COF-2) by introducing a bipyridine group into
the building block to capture iodine and methyl iodide (He et al., 2021).
The results showed that SCU-COF-2 had the ultrahigh adsorption ability
10
Chemosphere 291 (2022) 132795
for iodine (6.0 g/g) and the record-high value for methyl iodide (1.45
g/g) under static sorption conditions, further demonstrating the positive
role of N active sites for iodine capture. In addition, the COFs with
excellent adsorption ability (up to 6.26 g/g) for iodine are significantly
better than the reported MOFs (up to 1.75 g/g), demonstrating that
COFs have great application superiority in iodine adsorption (Huve
et al., 2018).
Luo et al. performed a series of C2H2/C2H4 separation experiments
based on a SO3H-anchored COF (COF-ECUT-1) as a porous adsorbent
(Tao et al., 2019). The adsorption capacities of COF-ECUT-1 for C2H2
and C2H4 were 55.39 and 28.63 cm3/g, respectively. More importantly,
the adsorption capacities of COF-ECUT-1 after introducing 4.0 wt%
sodium content (Na@COF-ECUT-1) correspondingly increased to 89.70
and 49.26 cm3/g, respectively, and the selectivity of C2H2/C2H4 was
also enhanced from 6.33 to 9.41. It was deduced that the Na-π in­
teractions within the COF channel afforded stronger affinity for C2H2
than for C2H4. Zhu et al. synthesized a crystalline naphthalene diimide
COF (PAF-110) with high thermal and long-term structural stability, and
studied its adsorption performance for C2H2 and C2H4 (Jiang et al.,
2018). The experimental results showed that the capacity of PAF-110 for
C2H2 (3.48 mmol/g) was two times higher than that for C2H4 (1.61
mmol/g), suggesting that PAF-110 had a higher affinity to C2H2.
Y. Huang et al.
Fig. 6. Schematic diagram of Ge-COFs for toxic acid gases removal (a); synthesis route of Ge-COFs (b); SO2 breakthrough curves for Ge-COFs (c); recyclability tests
for Ge–COF–K (d). Reproduced with permission (Ashraf et al., 2020).
Fig. 7. Classification of porous NH3 adsorbents (Kang et al., 2020).
Moreover, azo groups substituted COFs (Tg-AzoCOF) were proved to
have highly separation performance for C2H2/CH4 by an ideal adsorp­
tion solution theory (IAST) method (Huang et al., 2020). The IAST
selectivity of Tg-AzoCOF for C2H2 was up to 2891 over CH4 at 273 K and
1 bar, which was attributed to the role of surface area and polar envi­
ronment inside the pores.
Besides the above volatile vapors, COF-based materials were also
applied in other VOCs treatment. For example, Zhu and coworkers
synthesized a 3D microporous COF (MCOF-1) with uniform pore size of
0.64 nm, and evaluated its separation property for C3H8/CH4, C2H6/CH4
and C2H4/CH4 at 298 K and 100 kPa (Ma et al., 2013). The selectivity of
MCOF-1 for C3H8, C2H6 and C2H4 towards CH4 were 1800, 88 and 20,
respectively, suggesting that preparing COF-based materials with suit­
able pore sizes can promote the small hydrocarbon separation. Xie et al.
reported that the capture capacities of TTPE-COF for benzene and
11
Chemosphere 291 (2022) 132795
toluene at 293 K and P/P0 = 0.9 were 5.8 and 5.20 mmol/g, respec­
tively, proving the π-π interaction between volatile vapor and the
framework (Cui et al., 2021).
In the detection of VOCs, Cai and co-workers constructed a
benzimidazole-containing COF-based (BABE-TFPy COF) QCM sensor for
the detection of 2-chloroethyl ethyl sulfide (CEES) (He et al., 2019). The
prepared BABE-TFPy COF-based sensor showed higher sensitivity to
CEES than those of the other common VOCs, and its detection limit was
down to 0.96 ppm as shown in Fig. 8 (a). Zhao et al. prepared homo­
geneous BTA-TAPT COF films by the method of situ growth to detect
benzene (Yuan et al., 2020a). At room temperature, the film exhibited
selective response toward benzene with a detection limit of 340 ppb in
comparison with CO2, CH4 and C3H8, suggesting the strong
COF-benzene interactions. Based on hexamethylbiphenyl skeleton, a
3D-LCOF material with turn-on luminescence as a molecular decoder for
Y. Huang et al.
Fig. 8. The sensitivity of BABE-TFPy COF-based sensor for various VOCs (a), reproduced with permission (He et al., 2019); schematic diagram of the decoding of
3D-LCOF (b), reproduced with permission (Liu et al., 2020).
VOCs identification was reported by Liu et al. (Fig. 8 (b)) (Liu et al.,
2020). The 3D-LCOF with high SBET (875 m2/g) can accurately distin­
guish multiple VOCs including aromatic, alcohol-based and other com­
mon VOCs.
4. Conclusions and perspectives
In conclusion, COFs are a novel class of developing porous crystalline
materials. Compared to traditional porous materials, COFs linked by
covalent bonds display the admirable advantages of low density, high
specific surface area, stable and regular structure, and so on. Hence,
COFs are being explored for more extensive applications in the fields of
environmental treatment and energy utilization. In this review, we
summarized the design strategies of COF-based functional materials
from porosity structure adjustment to surface functionalization for
certain application. From the viewpoint of harmful gases treatment, the
recent advances of COFs in the capture, catalysis, and detection of these
gases were systematically investigated.
As porous materials, COFs exhibit good removal ability for harmful
gases (CO2, NOx, SO2, H2S and volatile pollutants). Compared with
conventional porous materials like zeolites with low porosity and
unregular structure, and most MOFs with low stability, stable COFs with
abundant pore channels are beneficial for the fast diffusion of harmful
gases and the multiple cycles of adsorption and desorption. The tunable
pore size also allows them with good separation ability for the target gas
whose kinetic diameter is close to the pore size. In addition, the design of
surface functionalization can enhance the adsorption affinity and cata­
lytic activity of COFs for specific gas. COF-based materials as catalysts
exhibit their potentials in catalytic reactions. For example, designing
COFs through coordination chemistry can incorporate active metals into
COFs, which are used as catalysts for CO2 conversion into CO, CH4, etc.
In the terms of detection, COFs with excellent luminescence activity
have been proven to have the potential to be used as chemical sensors
compared with MOFs. However, the application development of COF-
based materials in harmful gas purification needs to be further
strengthened. For different applications, how to design specific COF-
based materials is worth considering. This mainly includes two key as­
pects. The first is to develop new COF-based materials by taking
advantage of regular pore channels since they are the platform for
synthesizing functional materials, which is closely related to the prop­
erties of mass transfer, adsorption, separation, and catalysis. The syn­
thesis of COFs with high SBET, large pore volume, and suitable pore size
needs to be considered in the molecular design stage. On the other hand,
although COFs have higher stability than most MOFs, their stability after
functionalization whether can be maintained in specific gas environ­
ment is extremely crucial for their regeneration ability and service life.
According to specific application, hence, pore structure and stability
should be paid attention in designing COF-based materials.
12
Chemosphere 291 (2022) 132795
In addition, although the physicochemical properties of COFs have
been efficiently improved with the gradual deepening of research, the
current research is still in its infancy for industrial demand. In order to
further improve the related properties and promote the industrial ap­
plications, there are several issues need to be addressed:
1) The fundamental mechanism of some COF-based materials for gas
removal and detection is still unclear, which hinders the possibility
of further improving their properties. How to accurately analyze
their mechanism by means of experiment, characterization, and
theory calculation is crucial for the follow-up development of COFs
in harmful gas removal.
2) In the field of harmful gases treatment, current research mainly fo­
cuses on the capture and reduction of CO2. Nevertheless, studies on
the effective capture and removal of the other common gases like
NOx and H2S are still limited. As a novel porous crystalline material,
the application potential of COF-based materials deserves further
efforts for various gas purification.
3) The physicochemical properties of COF-based materials are directly
related to their application prospects. In order to enhance surface
area, pore volume, and structural stability, exploring new building
blocks for obtaining novel COFs with excellent mass transfer and
regeneration ability is highly desired. For certain application, novel
functionalization strategies and functional groups need to be further
developed.
4) Various chemicals are used in the synthesis process of COFs. It is
unclear whether the wide utilization of COFs will cause toxicity and
negative effects on human health and ecological environment. To
avoid secondary pollution, it is urgent to explore green synthesis
routes of COFs and clarify their ecological effects.
5) The current synthesis of COF materials is limited to the laboratory
level owing to harsh synthesis conditions (i.e., long reaction time,
high temperature) and high preparation cost. The improvement of
synthesis process by simplifying preparation process and reducing
synthesis cost is the key to promote their large-scale production and
practical utilizations.
Therefore, the development of COF-based materials in the field of gas
removal and purification is a hopeful but challenging research area. In
this context, we believed that this review will provide some ideas about
the synthesis and applications of COF-based materials.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Y. Huang et al. Chemosphere 291 (2022) 132795

Acknowledgements TOF turnover frequency

TpASH-NPHS 1,3,5-triformylphloroglucinol (Tp) 4-aminosalicylhy­
This work was supported by the funding of the Top Talent Project in drazide (ASH) nanoprobe for hydrogen sulfide (H2S)
Henan Agricultural University (No. 30500945). TPB triphenylbenzene
TpPa-1 ketoamine-based COF
Abbreviations TPT tris(4-formylphenoxy)-1,3,5-triazine
TTA 4,4′ ,4′′ -(1,3,5-triazine-2,4,6-triyl)trianiline
1D one-dimensional TTB 4,4′ ,4′′ -(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde)
2D two-dimensional TTCOF tetrathiafulvalene covalent organic frameworks
3D three-dimensional TTF tetrathiafulvalene
3D-LCOF three-dimensional luminescent covalent organic framework TTPE tetraphenylethylene
acac acetylacetonate Tz benzobisthiazole
BABE 1-(4,7-bis(4-aminophenyl)-1H-benzoimidazole-2-yl)ethan-1- VOCs volatile organic compounds
ol ZIF-8 zeolitic imidazolate framework-8
BDBA 1,4-benzenediboronic acid
BET Brunauer Emmett Teller Author contributions statement
BPDA 4,4′ -biphenyldiboronic acid
BTA benzene-1,3,5-tricarboxaldehyde Yan Huang: Conceptualization, Investigation, Writing – original
BTT benzo[1,2-b:3,4-b’:5,6-b’‘] trithiophene-2,5,8- draft, Writing – review & editing, Supervision, Funding acquisition.
tricarbaldehyde Xiaoqian Hao: Conceptualization, Investigation, Writing – original
CEES 2-chloroethyl ethyl sulfide draft, Data curation. Shuanglong Ma: Investigation, Writing – review &
CN carbon nitride editing. Rui Wang: Investigation, Writing – review & editing. Yazhou
CNS carbon nitride nanosheet Wang: Investigation, Data curation.
CNTs carbon nanotubes
COFs covalent organic frameworks References
COF-DC 2D conductive covalent organic frameworks
Afshari, M., Dinari, M., Zargoosh, K., Aliabadi, H., 2020. Novel triazine-based covalent
CoPc Co-phthalocyanine
organic framework as a superadsorbent for the removal of mercury (II) from aqueous
CT-COF 9-ethyl-9H-carbazole-2,7-dicarboxaldehyde (donor) tris-(4- solutions. Ind. Eng. Chem. Res. 59 (19), 9116–9126.
aminophenyl)- triazine (acceptor) covalent organic Aiyappa, H., Thote, J., Shinde, D., Banerjee, R., Kurubgot, S., 2016. Cobalt-modified
frameworks covalent organic framework as a robust water oxidation electrocatalyst. Chem.
Mater. 28 (12), 4375–4379.
CTF covalent triazine framework Alahakoon, S., Diwakara, S., Thompson, C., Smaldone, R., 2020. Supramolecular design
CTF-FUM covalent triazine framework fumaronitrile in 2D covalent organic frameworks. Chem. Soc. Rev. 49 (5), 1344–1356.
Cz carbazole An, S., Xu, T., Peng, C., Hu, J., Liu, H., 2019. Rational design of functionalized covalent
organic frameworks and their performance towards CO2 capture. RSC Adv. 9 (37),
DAA 2,5-diaminobenzoic acid 21438–21443.
DATP 2,6-diaminoanthracene-2,4,6-triformylphloroglucinol Apriliyanto, Y., Darmawan, N., Faginas-Lago, N., Lombardi, A., 2020. Two-dimensional
DMTP dimethoxyterephthaldehyde diamine-linked covalent organic frameworks for CO2/N2 capture and separation:
theoretical modeling and simulations. Phys. Chem. Chem. Phys. 22 (44),
Dq diaminoanthraquinone 25918–25929.
DQTP 2,6-diaminoanthraquinone-2,4,6-triformylphloroglucinol Ashraf, S., Liu, C., Li, S., Haq, I., Mehmood, M., Li, P., Wang, B., 2020. Versatile platform
EDTA ethylenediaminetetraacetic acid of ion conducting 2D anionic germanate covalent organic frameworks with potential
for capturing toxic acidic gases. ACS Appl. Mater. Interfaces 12 (36), 40372–40380.
ESRL Earth System Research Laboratories
Bagheri, A.R., Aramesh, N., Sher, F., Bilal, M., 2021. Covalent organic frameworks as
FMTA 5′ -(4-formyl-3-methoxyphenyl)-3,3′′ -dimethoxy-[1,1′ :3′ ,1′′ robust materials for mitigation of environmental pollutants. Chemosphere 270,
terphenyl]-4,4′′ -dicarbaldehyde 129523.
FN-CTF perfluorinated covalent triazine framework Barea, E., Montoro, C., Navarro, J., 2014. Toxic gas removal metal-organic frameworks
for the capture and degradation of toxic gases and vapours. Chem. Soc. Rev. 43 (16),
GCMC Grand Canonical Monte Carlo 5419–5430.
HHTP 2,3,6,7,10,11-hexahydroxytriphenylene Bobbitt, N., Mendonca, M., Howarth, A., Islamoglu, T., Hupp, J., Farha, O., Sunrr, R.,
IAST ideal adsorption solution theory 2017. Metal-organic frameworks for the removal of toxic industrial chemicals and
chemical warfare agents. Chem. Soc. Rev. 46 (11), 3357–3385.
LODs limits of detection Bunck, D., Dichtel, P., 2012. Internal functionalization of three-dimensional covalent
MCNC magnetic colloid nanocrystal cluster organic frameworks. Angew. Chem. 124 (8), 1921–1925.
MOFs metal-organic frameworks Cai, Z., Zhan, G., Daukiya, L., Eyley, S., Thielemans, W., Severin, K., Feyter, S., 2019.
Electric-field-mediated reversible transformation between supramolecular networks
NiPc Ni-phthalocyanine and covalent organic frameworks. J. Am. Chem. Soc. 141 (29), 11404–11408.
NSs nanosheets Cao, X., Xu, H., Dong, S., Xu, J., Qiao, Z., Zhao, S., Wang, J., Wang, Z., 2020. Preparation
OSHA Occupational Safety and Health Administration of high-performance and pressure-resistant mixed matrix membranes for CO2/H2
separation by modifying COF surfaces with the groups or segments of the polymer
PA-1 p-phenylenediamine matrix. J. Membr. Sci. 601, 117882.
PSs polystyrene spheres Chen, X., Zhang, H., Ci, C., Sun, W., Wang, Y., 2019. Few-layered boronic ester based
PTSA p-toluenesulfonic acid covalent organic frameworks/carbon nanotube composites for high-performance K-
organic batteries. ACS Nano 13 (3), 3600–3607.
rGO reduced graphene oxide
Cheng, Y., Zhai, L., Ying, Y., Wang, Y., Liu, G., Dong, J., Ng, D., Khan, S., Zhao, D., 2019.
SWNTs single-walled carbon nanotubes Highly efficient CO2 capture by mixed matrix membranes containing three-
TAPB 1,3,5-tris(4′ -aminophenyl)benzene dimensional covalent organic framework fillers. J. Mater. Chem. 7 (9), 4549–4560.
TAPT 1,3,5-tris-(4-aminophenyl) triazine Cote, A., Benin, A., Ockwig, N., Keeffe, M., Matzger, A., Yaghi, O., 2005. Porous,
crystalline, covalent organic frameworks. Science 310 (5751), 1166–1170.
TFP triformylphloroglucinol Cui, D., Ding, X., Xie, W., Xu, G., Su, Z., Xu, Y., Xie, Y., 2021. A tetraphenylethylene-
TFPN tetrafluorophthalonitrile based covalent organic framework for waste gas adsorption and highly selective
TFPy 1,3,6,8-tetrakis(4-formylphenyl)pyrene detection of Fe3+. CrystEngComm 23 (33), 5569–5574.
Cui, K., Zhong, W., Li, L., Zhuang, Z., Li, L., Bi, J., Yu, Y., 2019. Well-defined metal
Tg-AzoCOF triethylene glycol azo groups covalent organic frameworks nanoparticles@covalent organic framework yolk-shell nanocages by ZIF-8 template
TMFPT 2,4,6-tris-(3-methoxy-4-formylphenyl)- 1,3,5-triazine as catalytic nanoreactors. Small 15 (3), 1804419.
TMTA 2,4,6-trimethoxybenzene-1,3,5-tricarbaldehyde
TON turnover number

13
Y. Huang et al.
Dai, Z., Wang, J., Xue, Y., Wei, T., Bao, J., Zhu, Q., 2018. Fe-porphyrin-based covalent
organic framework as a novel peroxidase mimic for a one-pot glucose colorimetric
assay. ACS Appl. Bio Mater. 1 (2), 382–388.
Das, P., Chakraborty, G., Mandal, S., 2020. Comprehensive structural and microscopic
characterization of an azine-triazine-functionalized highly crystalline covalent
organic framework and its selective detection of dichloran and 4-nitroaniline. ACS
Appl. Mater. Interfaces 12 (9), 10224–10232.
Deeg, K., Borges, D., Ongari, D., Rampal, N., Talirz, L., Yakutovich, A., Huck, J., Smit, B.,
2020. In silico discovery of covalent organic frameworks for carbon capture. ACS
Appl. Mater. Interfaces 12 (19), 21559–21568.
Diercks, C., Lin, S., Kornienko, N., Kapustin, E., Nichols, E., Zhu, C., Zhao, Y., Chang, C.,
Yaghi, O., 2018. Reticular electronic tuning of porphyrin active sites in covalent
organic frameworks for electrocatalytic carbon dioxide reduction. J. Am. Chem. Soc.
140 (3), 1116–1122.
Ding, S., Wang, W., 2013. Covalent organic frameworks (COFs): from design to
applications. Chem. Soc. Rev. 42 (2), 548–568.
Dmitrieva, E., Weidinger, I., Yu, M., Chandrasekhar, N., Raghupathy, R., Ly, H.,
Mirhosseini, H., Liang, C., Lu, X., Kuhne, T., Feng, X., 2020. A high-rate two-
dimensional polyarylimide covalent organic framework anode for aqueous Zn-ion
energy storage devices. J. Am. Chem. Soc. 142 (46), 19570–19578.
Dong, J., Han, X., Liu, Y., Li, H., Cui, Y., 2020. Metal-covalent organic frameworks
(MCOFs): a bridge between metal-organic frameworks and covalent organic
frameworks. Angew. Chem. Int. Edit. 132 (33), 13826–13837.
Doonan, C., Tranchemontagne, D., Glover, T., Hunt, J., Yaghhi, O., 2010. Exceptional
ammonia uptake by a covalent organic framework. Nat. Chem. 2 (3), 235–238.
EL-Mahdy, A.F., Hung, Y.H., Mansoure, T.H., Yu, H.H., Hsu, Y.S., Wu, K.C., Kuo, S.W.,
2019. Synthesis of [3+3] β-ketoenamine-tethered covalent organic frameworks
(COFs) for high-performance supercapacitance and CO2 storage. J. Taiwan Inst.
Chem. E. 103, 199–208.
Evans, A., Castano, I., Brumberg, A., Parent, L., Corcos, A., Li, R., Flanders, N.,
Gosztola, D., Gianneschi, N., Schaller, R., Dichtel, W., 2019. Emissive single-
crystalline boroxine-linked colloidal covalent organic frameworks. J. Am. Chem.
Soc. 141 (50), 19728–19735.
Fan, H., Mundstock, A., Feldhoff, A., Knebel, A., Gu, J., Meng, H., Caro, J., 2018.
Covalent organic framework-covalent organic framework bilayer membranes for
highly selective gas separation. J. Am. Chem. Soc. 140 (32), 10094–10098.
Fang, Q., Liu, Y., Wang, Y., Li, H., Guan, X., Zhu, L., Xue, M., Yan, Y., Valtchev, V.,
Qiu, S., 2019. Ambient aqueous-phase synthesis of covalent organic frameworks for
degradation of organic pollutants. Chem. Sci. 10 (46), 10815–10820.
Feng, X., Gao, Z., Xiao, L., Lai, Z., Luo, F., 2020. A Ni/Fe complex incorporated into a
covalent organic framework as a single-site heterogeneous catalyst for efficient
oxygen evolution reaction. Inorg. Chem. Front. 7 (20), 3925–3931.
Fernandes, S.P., Fonseca, V.F., Romero, V., Duarte, I.A., Freitas, A., Barbosa, J., Reis-
Santos, P., Salonen, L.M., Espiña, B., 2021. Study on the efficiency of a covalent
organic framework as adsorbent for the screening of pharmaceuticals in estuary
waters. Chemosphere 278, 130364.
Furukawa, H., Yaghi, O., 2009. Storage of hydrogen, methane, and carbon dioxide in
highly porous covalent organic frameworks for clean energy applications. J. Am.
Chem. Soc. 131 (25), 8875–8883.
Gan, J., Li, X., Rizwan, K., Adeel, M., Bilal, M., Rasheed, T., Iqbal, H.M., 2021. Covalent
organic frameworks-based smart materials for mitigation of pharmaceutical
pollutants from aqueous solution. Chemosphere 286, 131710.
Gao, C., Bai, J., He, Y., Zheng, Q., Ma, W., Lei, Z., Zhang, M., Wu, J., Fu, F., Lin, Z., 2019.
Postsynthetic functionalization of Zr4+-immobilized core-shell structured magnetic
covalent organic frameworks for selective enrichment of phosphopeptides. ACS
Appl. Mater. Interfaces 11 (14), 13735–13741.
Gao, W., Cheng, J., Yuan, X., Tian, Y., 2021. Covalent organic framework-graphene oxide
composite: a superior adsorption material for solid phase microextraction of
bisphenol A. Talanta 222, 121501.
Gao, Z., Gong, L., He, X., Su, X., Xiao, L., Luo, F., 2020. General strategy to fabricate
metal-incorporated pyrolysis-free covalent organic framework for efficient oxygen
evolution reaction. Inorg. Chem. 59 (7), 4995–5003.
Ge, X., Zhang, H., Zhang, C., Du, M., 2021. A heterogeneous nanoscale covalent organic
framework fluorescence probe for sensitive detection of hydrogen sulfide. Chem.
Nano Mat. 7 (5), 530–533.
Geng, K., He, T., Liu, R., Dalapati, S., Tan, K., Li, Z., Tao, S., Gong, Y., Jiang, Q., Jiang, D.,
2020. Covalent organic frameworks: design, synthesis, and functions. Chem. Rev.
120 (16), 8814–8933.
Gomes, R., Bhattacharyya, A., 2020. Carbon nanotube-templated covalent organic
framework nanosheets as an efficient sulfur host for room-temperature metal-sulfur
batteries. ACS Sustain. Chem. Eng. 8 (15), 5946–5953.
Gong, Y., Zhong, W., Li, Y., Qiu, Y., Zheng, L., Jiang, J., Jiang, H., 2020. Regulating
photocatalysis by spin-state manipulation of cobalt in covalent organic frameworks.
J. Am. Chem. Soc. 142 (39), 16723–16731.
Grunenberg, L., Savasci, G., Terban, M., Duppel, V., Moudrakovski, I., Etter, M.,
Dinnebier, R., Ochsenfeld, C., Lotsch, B., 2021. Amine-linked covalent organic
frameworks as a platform for postsynthetic structure interconversion and pore-wall
modification. J. Am. Chem. Soc. 143 (9), 3430–3438.
Guan, X., Chen, F., Fang, Q., Qiu, S., 2020. Design and applications of three dimensional
covalent organic frameworks. Chem. Soc. Rev. 49 (5), 1357–1384.
Guan, X., Li, H., Ma, Y., Xue, M., Fang, Q., Yan, Y., Valtchev, V., Qiu, S., 2019.
Chemically stable polyarylether-based covalent organic frameworks. Nat. Chem. 11
(6), 587–594.
Guo, L., Jia, S., Diercks, C., Yang, X., Alshmimri, S., Yaghi, O., 2020a. Amidation,
esterification, and thioesterification of a carboxyl-functionalized covalent organic
framework. Angew. Chem. Int. Edit. 59 (5), 2023–2027.
14
Chemosphere 291 (2022) 132795
Guo, Y., Yang, S., Qing, X., Wu, P., Zeng, G., Zeng, G., 2021a. Hierarchical confine of
PtZn alloy nanoparticles and single-dispersed Zn atoms on COF@MOF-derived
carbon towards efficient oxygen reduction reaction. J. Mater. Chem. 9,
13625–13630.
Guo, S., Yang, P., Zhao, Y., Yu, X., Wu, Y., Zhang, H., Yu, B., Han, B., George, M., Liu, Z.,
2020b. Direct Z-scheme heterojunction of SnS2/sulfur-bridged covalent triazine
frameworks for visible-light-driven CO2 photoreduction. ChemSusChem 13 (23),
6278–6283.
Guo, K., Zhu, X., Peng, L., Fu, Y., Ma, R., Lu, X., Zhang, F., Zhu, W., Fan, M., 2021b.
Boosting photocatalytic CO2 reduction over a covalent organic framework decorated
with ruthenium nanoparticles. Chem. Eng. J. 405, 127011.
Haase, F., Troschke, E., Savasci, G., Banerjee, T., Duppel, V., Dorfler, S., Grundei, M.,
Burow, A., Ochsenfeld, C., Kaskel, S., Lotsch, B., 2018. Topochemical conversion of
an imine-into a thiazole-linked covalent organic framework enabling real structure
analysis. Nat. Commun. 9 (1), 1–10.
He, L., Chen, L., Dong, X., Zhang, S., Zhang, M., Dai, X., Liu, X., Lin, P., Li, K., Chen, C.,
Pan, T., Ma, F., Chen, J., Yuan, M., Zhang, Y., Chen, L., Zhou, R., Han, Y., Chai, Z.,
Wang, S., 2021. A nitrogen-rich covalent organic framework for simultaneous
dynamic capture of iodine and methyl iodide. Inside Chem. 7 (3), 699–714.
He, Z., Gong, S., Cai, S., Yan, Y., Chen, G., Li, X., Zheng, S., Fan, J., Zhang, W., 2019.
A benzimidazole-containing covalent organic framework-based QCM sensor for
exceptional detection of CEES. Cryst. Growth Des. 19 (6), 3543–3550.
Hu, S.Y., Sun, Y.N., Feng, Z.W., Wang, F.O., Lv, Y., 2021. Design and construction
strategies to improve covalent organic frameworks photocatalyst’s performance for
degradation of organic pollutants. Chemosphere 286, 131646.
Huang, N., Chen, X., Krishna, R., Jiang, D., 2015. Two-dimensional covalent organic
frameworks for carbon dioxide capture through channel-wall functionalization.
Angew. Chem. 127 (10), 3029–3033.
Huang, S., Hu, Y., Tan, L., Wan, S., Yazdi, S., Jin, Y., Zhang, W., 2020. Highly C2/C1-
selective covalent organic frameworks substituted with azo groups. ACS Appl. Mater.
Interfaces 12 (46), 51517–51522.
Huang, Y., Su, W., Wang, R., Zhao, T., 2019. Removal of typical industrial gaseous
pollutants: from carbon, zeolite, and metal-organic frameworks to molecularly
imprinted adsorbents. Aerosol. Air Qual. Res. 19 (9), 2130–2150.
Huang, N., Wang, P., Addicoat, M.A., Heine, T., Jiang, D., 2017. Ionic covalent organic
frameworks: design of a charged interface aligned on 1D channel walls and its
unusual electrostatic functions. Angew. Chem. Int. Edit. 56 (18), 4982–4986.
Huve, J., Ryzhikov, A., Nouali, H., Lalia, V., Augé, G., Daou, T.J., 2018. Porous sorbents
for the capture of radioactive iodine compounds: a review. RSC Adv. 8 (51),
29248–29273.
Jena, H., Krishnaraj, C., Wang, G., Leus, K., Schmidt, J., Chaoui, N., Voort, P., 2018.
Acetylacetone covalent triazine framework: an efficient carbon capture and storage
material and a highly stable heterogeneous catalyst. Chem. Mater. 30 (12),
4102–4111.
Ji, W., Guo, Y., Wang, X., Lu, X., Guo, D., 2019. Amino-modified covalent organic
framework as solid phase extraction absorbent for determination of carboxylic acid
pesticides in environmental water samples. J. Chromatogr. A 1595, 11–18.
Ji, W., Guo, Y., Xie, H., Wang, X., Guo, D., 2020. Rapid microwave synthesis of dioxin-
linked covalent organic framework for efficient micro-extraction of perfluorinated
alkyl substances from water. J. Hazard Mater. 397, 122793.
Jiang, Y., Liu, C., Huang, A., 2019. EDTA-functionalized covalent organic framework for
the removal of heavy-metal ions. ACS Appl. Mater. Interfaces 11 (35), 32186–32191.
Jiang, L., Tian, Y., Sun, T., Zhu, Y., Ren, H., Zou, X., Ma, Y., Meihaus, K., Long, J.,
Zhu, G., 2018. A crystalline polyimide porous organic framework for selective
adsorption of acetylene over ethylene. J. Am. Chem. Soc. 140 (46), 15724–15730.
Jin, E., Asada, M., Xu, Q., Dalapati, S., Addicoat, M., Brady, M., Xu, H., Nakamura, T.,
Heine, T., Chen, Q., Jiang, D., 2017. Two-dimensional sp2 carbon-conjugated
covalent organic frameworks. Science 357 (6352), 673–676.
Kang, D., Ju, S., Kim, D., Kang, M., Kim, H., Hong, C., 2020. Emerging porous materials
and their composites for NH3 gas removal. Adv. Sci. 7 (24), 2002142.
Khaing, K., Yin, D., Ouyang, Y., Xiao, S., Liu, B., Deng, L., Li, L., Guo, X., Wang, J., Liu, J.,
Zhang, Y., 2020. Fabrication of 2D-2D heterojunction catalyst with covalent organic
framework (COF) and MoS2 for highly efficient photocatalytic degradation of
organic pollutants. Inorg. Chem. 59 (10), 6942–6952.
Kou, M., Liu, W., Wang, Y., Huang, J., Chen, Y., Zhou, Y., Chen, Y., Ma, M., Lei, K.,
Xie, H., Wong, P., Ye, L., 2021. Photocatalytic CO2 conversion over single-atom
Mon2 sites of covalent organic framework. Appl. Catal. B Environ. 291, 120146.
Lee, G., Lee, J., Vo, H., Kim, S., Lee, H., Park, T., 2017. Amine-functionalized covalent
organic framework for efficient SO2 capture with high reversibility. Sci. Rep. 7 (1),
1–10.
Lei, Z., Hao, S., Yang, J., Zhang, L., Fang, B., Wei, K., Qi, L., Jin, S., Wei, C., 2021. Study
on denitration and sulfur removal performance of Mn-Ce supported fly ash catalyst.
Chemosphere 270, 128646.
Lei, K., Wang, D., Kou, M., Ma, Z., Wang, L., Ma, Z., Wang, L., Ye, L., Kong, Y., 2020.
A metal-free donor-acceptor covalent organic framework photocatalyst for visible-
light-driven reduction of CO2 with H2O. Chem Sus Chem 13 (7), 1725–1729.
Li, Y., Chen, M., Han, Y., Feng, Y., Zhang, Z., Zhang, B., 2020a. Fabrication of a new
corrole-based covalent organic framework as a highly efficient and selective
chemosensor for heavy metal ions. Chem. Mater. 32 (6), 2532–2540.
Li, T., Hu, Z., Meng, J., Zhang, X., Gao, W., Chen, M., Wang, J., 2021a. Zn-based metal
organic framework-covalent organic framework composites for trace lead extraction
and fluorescence detection of TNP. J. Hazard Mater. 411, 125021.
Li, X., Qi, Y., Yue, G., Wu, Q., Li, Y., Zhang, M., Guo, X., Li, X., Ma, L., Li, S., 2019a.
Solvent-and catalyst-free synthesis of an azine-linked covalent organic framework
and the induced tautomerization in the adsorption of U (VI) and Hg (II). Green
Chem. 21 (3), 649–657.
Y. Huang et al.
Li, W., Shi, W., Hu, Z., Yang, T., Chen, M., Zhao, B., Wang, J., 2020b. Fabrication of
magnetic Fe3O4@metal organic framework@covalent organic framework composite
and its selective separation of trace copper. Appl. Surf. Sci. 530, 147254.
Li, X., Su, Q., Luo, K., Li, H., Li, G., Wu, Q., 2021b. Construction of a highly heteroatom-
functionalized covalent organic framework and its CO2 capture capacity and CO2/N2
selectivity. Mater. Lett. 282, 128704.
Li, Y., Wang, C., Ma, S., Zhang, H., Ou, J., Wei, Y., Ye, M., 2019b. Fabrication of
hydrazone-linked covalent organic frameworks using alkyl amine as building block
for high adsorption capacity of metal ions. ACS Appl. Mater. Interfaces 11 (12),
11706–11714.
Li, F., Wang, D., Xing, Q., Zhou, G., Liu, S., Zheng, L., Ye, P., Zou, J., 2019c. Design and
syntheses of MOF/COF hybrid materials via postsynthetic covalent modification: an
efficient strategy to boost the visible-light-driven photocatalytic performance. Appl.
Catal. B Environ. 243, 621–628.
Li, C., Yang, J., Pachfule, P., Li, S., Ye, M., Schmidt, J., Thomas, A., 2020c. Ultralight
covalent organic framework/graphene aerogels with hierarchical porosity. Nat.
Commun. 11 (1), 1–8.
Li, X., Yang, X., Xue, H., Pang, H., Xu, Q., 2020d. Metal-organic frameworks as a platform
for clean energy applications. Energy Chem. 2 (2), 100027.
Li, W., Yang, C., Yan, X., 2017. A versatile covalent organic framework-based platform
for sensing biomolecules. Chem. Commun. 53 (83), 11469–11471.
Liang, R., Jiang, S., Ru, H., Zhao, X., 2020. Two-dimensional covalent organic
frameworks with hierarchical porosity. Chem. Soc. Rev. 49 (12), 3920–3951.
Liao, Y., Li, J., Thomas, A., 2017. General route to high surface area covalent organic
frameworks and their metal oxide composites as magnetically recoverable
adsorbents and for energy storage. ACS Macro Lett. 6 (12), 1444–1450.
Lin, S., Diercks, C., Zhang, Y., Kornienko, N., Nichols, E., Zhao, Y., Paris, A., Kim, D.,
Yang, P., Yaghi, O., Chang, C., 2015. Covalent organic frameworks comprising cobalt
porphyrins for catalytic CO2 reduction in water. Science 349 (6253), 1208–1213.
Lin, R.B., Zhang, Z., Chen, B., 2021. Achieving high performance metal-organic
framework materials through pore engineering. Accounts Chem. Res. 54 (17),
3362–3376.
Lin, C., Zhang, D., Zhao, Z., Xia, Z., 2018. Covalent organic framework electrocatalysts
for clean energy conversion. Adv. Mater. 30 (5), 1703646.
Ling, Y., Chen, W., Hao, W., Li, Y., Chen, L., 2018. Covalent organic frameworks
constructed from flexible building blocks with high adsorption capacity for
pollutants. ACS Appl. Nano Mater. 1 (9), 4756–4761.
Liu, W., Li, X., Wang, C., Pan, H., Liu, W., Wang, K., Zeng, Q., Wang, R., Jiang, J., 2019.
A scalable general synthetic approach toward ultrathin imine-linked two-
dimensional covalent organic framework nanosheets for photocatalytic CO2
reduction. J. Am. Chem. Soc. 141 (43), 17431–17440.
Liu, X., Lim, G., Wang, Y., Zhang, L., Mullangi, D., Wu, Y., Zhao, D., Ding, J.,
Cheetham, A., Wang, J., 2021. Binder-free 3D printing of covalent organic
framework (COF) monoliths for CO2 adsorption. Chem. Eng. J. 403, 126333.
Liu, Y., Yan, X., Lu, H., Zhang, W., Shi, Y., Gu, Z., 2020. A three-dimensional covalent
organic framework with turn-on luminescence for molecular decoding of volatile
organic compounds. Sens. Actuators B Chem. 323, 128708.
Lin, X., Zhu, X., Feng, M., Han, Y., Geng, Z., 2021. Economy and carbon emissions
optimization of different countries or areas in the world using an improved Attention
mechanism based long-short term memory neural network. Sci. Total Environ. 792,
148444.
Louis, B., Maia, R., Oliveira, F., Ritleng, V., Wang, Q., Esteves, P., 2021. CO2 capture by
hydroxylated azine-based covalent organic frameworks. Chem. Eur J. 27 (30),
8048–8055.
López-Magano, A., Platero-Prats, A., Cabrera, S., Mas-Ballesté, R., Alemán, J., 2020.
Incorporation of photocatalytic Pt (II) complexes into imine-based layered covalent
organic frameworks (COFs) through monomer truncation strategy. Appl. Catal. B
Environ. 272, 119027.
Lu, S., Hu, Y., Wan, S., Mccaffrey, R., Jin, Y., Gu, H., Zhang, W., 2017. Synthesis of
ultrafine and highly dispersed metal nanoparticles confined in a thioether-containing
covalent organic framework and their catalytic applications. J. Am. Chem. Soc. 139
(47), 17082–17088.
Lu, M., Li, Q., Liu, J., Zhang, F., Zhang, L., Wang, J., Kang, Z., Lan, Y., 2019a. Installing
earth-abundant metal active centers to covalent organic frameworks for efficient
heterogeneous photocatalytic CO2 reduction. Appl. Catal. B Environ. 254, 624–633.
Lu, M., Liu, J., Li, Q., Zhang, M., Liu, M., Wang, J., Yuan, D., Lan, Y., 2019b. Rational
design of crystalline covalent organic frameworks for efficient CO2 photoreduction
with H2O. Angew. Chem. Int. Edit. 58 (36), 12392–12397.
Lu, Q., Ma, Y., Li, H., Guan, X., Yusran, Y., Xue, M., Fang, Q., Yan, Y., Qiu, S.,
Valtchev, V., 2018. Postsynthetic functionalization of three-dimensional covalent
organic frameworks for selective extraction of lanthanide ions. Angew. Chem. 130
(21), 6150–6156.
Lu, M., Zhang, M., Liu, C., Liu, J., Shang, L., Wang, M., Chang, J., Li, S., Lan, Y., 2021.
Stable dioxin-linked metallophthalocyanine covalent organic frameworks (COFs) as
photo-coupled electrocatalysts for CO2 reduction. Angew. Chem. 133 (9),
4914–4921.
Lu, Y., Zhang, J., Wei, W., Ma, D., Wu, X., Zhu, Q., 2020. Efficient carbon dioxide
electroreduction over ultrathin covalent organic framework nanolayers with isolated
cobalt porphyrin units. ACS Appl. Mater. Interfaces 12 (34), 37986–37992.
Luo, M., Yang, Q., Liu, K., Cao, H., Yan, H., 2019. Boosting photocatalytic H2 evolution
on gC3N4 by modifying covalent organic frameworks (COFs). Chem. Commun. 55
(41), 5829–5832.
Luo, M., Yang, Q., Yang, W., Wang, J., He, F., Liu, K., Cao, H., Yan, H., 2020. Defects
engineering leads to enhanced photocatalytic H2 evolution on graphitic carbon
nitride-covalent organic framework nanosheet composite. Small 16 (20), 2001100.
15
Chemosphere 291 (2022) 132795
Ma, J., Li, J., Chen, Y., Ning, R., Ao, Y., Liu, J., Sun, J., Wang, D., Wang, Q., 2019. Cage
based crystalline covalent organic frameworks. J. Am. Chem. Soc. 141 (9),
3843–3848.
Ma, H., Ren, H., Meng, S., Yan, Z., Zhao, H., Sun, F., Zhu, G., 2013. A 3D microporous
covalent organic framework with exceedingly high C3H8/CH4 and C2 hydrocarbon/
CH4 selectivity. Chem. Commun. 49 (84), 9773–9775.
Maschita, J., Banerjee, T., Savasci, G., Haase, F., Ochsenfeld, C., Lotsch, B., 2020.
Ionothermal synthesis of imide-linked covalent organic frameworks. Angew. Chem.
Int. Edit. 59 (36), 15750–15758.
Meng, Z., Stolz, R., Mirica, K., 2019. Two-dimensional chemiresistive covalent organic
framework with high intrinsic conductivity. J. Am. Chem. Soc. 141 (30),
11929–11937.
Nabais, A.R., Martins, A.P., Alves, V.D., Crespo, J.G., Marrucho, I.M., Tomé, L.C.,
Neves, L.A., 2019. Poly (ionic liquid)-based engineered mixed matrix membranes for
CO2/H2 separation. Sep. Purif. Technol. 222, 168–176.
Niu, F., Shao, Z., Zhu, J., Tao, L., Ding, Y., 2021. Structural evolution of imine-linked
covalent organic frameworks and the NH3 sensing performance. J. Mater. Chem. C 9,
8562–8569.
Nguyen, H., Gropp, C., Yaghi, O., 2020. Reticulating 1D ribbons into 2D covalent organic
frameworks by imine and imide linkages. J. Am. Chem. Soc. 142 (6), 2771–2776.
Pan, X., Qin, X., Zhang, Q., Ge, Y., Ke, H., Cheng, G., 2020. N-and S-rich covalent organic
framework for highly efficient removal of indigo carmine and reversible iodine
capture. Micropor. Mesopor. Mater. 296, 109990.
Park, S., Liao, Z., Ibarlucea, B., Qi, H., Lin, H., Becker, D., Melidonie, J., Zhang, T.,
Sahabudeen, H., Baraban, L., Baek, C., Zheng, Z., Zschech, E., Fery, A., Heine, T.,
Kaiser, U., Cuniberti, G., Dong, R., Feng, X., 2020. Two-dimensional boronate ester
covalent organic framework thin films with large single crystalline domains for a
neuromorphic memory device. Angew. Chem. 132 (21), 8295–8301.
Pedrolo, D.R.S., de Menezes Quines, L.K., de Souza, G., Marcilio, N.R., 2017. Synthesis of
zeolites from Brazilian coal ash and its application in SO2 adsorption. J. Environ.
Chem. Eng. 5 (5), 4788–4794.
Peng, W.L., Kan, X., Chen, W., Mi, J., Zhang, G., Xiao, Y., Liu, W., Liu, F., Zheng, A.,
2021. Efficiently selective oxidation of H2S to elemental sulfur over covalent triazine
framework catalysts. ACS Appl. Mater. Inter. 13 (29), 34124–34133.
Qian, H., Yang, C., Yan, X., 2016. Bottom-up synthesis of chiral covalent organic
frameworks and their bound capillaries for chiral separation. Nat. Commun. 7 (1),
1–7.
Rotter, J., Weinberger, S., Kampmann, J., Sick, T., Shalom, M., Bein, T., Medina, D.,
2019. Covalent organic framework films through electrophoretic deposition-creating
efficient morphologies for catalysis. Chem. Mater. 31 (24), 10008–10016.
Segura, J., Royuela, S., Ramos, M., 2019. Post-synthetic modification of covalent organic
frameworks. Chem. Soc. Rev. 48 (14), 3903–3945.
Shan, Y., Chen, L., Pang, H., Xu, Q., 2021. Metal-organic framework-based hybrid
frameworks. Small Structures 2 (2), 2000078.
Shan, M., Seoane, B., Rozhko, E., Dikhtiarenko, A., Clet, G., Kapteijin, F., Gascon, J.,
2016. Azine-linked covalent organic framework (COF)-based mixed-matrix
membranes for CO2/CH4 Separation. Chem. Eur J. 22 (41), 14467–14470.
Sun, Q., Aguila, B., Earl, L., Abney, C., Wojtas, W., Thallapally, P., Ma, S., 2018a.
Covalent organic frameworks as a decorating platform for utilization and affinity
enhancement of chelating sites for radionuclide sequestration. Adv. Mater. 30 (20),
1705479.
Sun, Q., Aguila, B., Perman, J., Earl, L., Abney, C., Cheng, Y., Wei, H., Nguyen, N.,
Wojtas, L., Ma, S., 2017. Postsynthetically modified covalent organic frameworks for
efficient and effective mercury removal. J. Am. Chem. Soc. 139 (7), 2786–2793.
Sun, D., Jang, S., Yim, S., Ye, L., Kim, D., 2018b. Metal doped core-shell metal-organic
frameworks@covalent organic frameworks (MOFs@COFs) hybrids as a novel
photocatalytic platform. Adv. Funct. Mater. 28 (13), 1707110.
Sun, Q., Ma, W., Dan, O., Li, G., Yang, Y., Yan, X., Su, H., Lin, Z., Cai, Z., 2021. Thiol
functionalized covalent organic framework for highly selective enrichment and
detection of mercury by matrix-assisted laser desorption/ionization time-of-flight
mass spectrometry. Analyst 146 (9), 2991–2997.
Sun, Q., Tang, Y., Aguila, B., Wang, S., Xiao, F., Thallapally, P., AI-Enizi, A., Nafady, A.,
Ma, S., 2019. Reaction environment modification in covalent organic frameworks for
catalytic performance enhancement. Angew. Chem. 131 (26), 8762–8767.
Tao, Y., Krishna, R., Yang, L., Fan, Y., Wang, L., Gao, Z., Xiong, J., Sun, L., Luo, F., 2019.
Enhancing C2H2/C2H4 separation by incorporating low-content sodium in covalent
organic frameworks. Inorg. Chem. Front. 6 (10), 2921–2926.
Vitaku, E., Gannett, C.N., Carpenter, K.L., Shen, L.X., Abruna, H.D., Dichtel, W.R., 2019.
Phenazine-based covalent organic framework cathode materials with high energy
and power densities. J. Am. Chem. Soc. 142 (1), 16–20.
Wang, Y., Chen, J., Wang, G., Li, Y., Wen, Z., 2018a. Perfluorinated covalent triazine
framework derived hybrids for the highly selective electroconversion of carbon
dioxide into methane. Angew. Chem. Int. Edit. 57 (40), 13120–13124.
Wang, J., Li, N., Xu, Y., Pang, H., 2020a. Two-dimensional MOF and COF nanosheets:
synthesis and applications in electrochemistry. Chem. Eur J. 26 (29), 6402–6422.
Wang, X., Ma, R., Hao, L., Wu, Q., Wang, C., Wang, Z., 2018b. Mechanochemical
synthesis of covalent organic framework for the efficient extraction of benzoylurea
insecticides. J. Chromatogr. A 1551, 1–9.
Wang, H., Wang, H., Wang, Z., Tang, L., Zeng, G., Xu, P., Chen, M., Xiong, T., Zhou, C.,
Li, X., Huang, D., Zhu, Y., Wang, Z., Tang, J., 2020b. Covalent organic framework
photocatalysts: structures and applications. Chem. Soc. Rev. 49 (12), 4135–4165.
Wang, L., Wang, L., Zhao, J., Yan, T., 2012. Adsorption of selected gases on metal-
organic frameworks and covalent organic frameworks: a comparative grand
canonical Monte Carlo simulation. J. Appl. Phys. 111 (11), 112628.
Y. Huang et al.
Wang, J., Wang, J., Zhuang, W., Shi, X., Du, X., 2018c. Properties of metal-doped
covalent organic frameworks and their interactions with sulfur dioxide. J. Chem.
2018.
Wang, P., Xu, Q., Li, Z., Jiang, W., Jiang, Q., Jiang, D., 2018d. Exceptional iodine capture
in 2D covalent organic frameworks. Adv. Mater. 30 (29), 1801991.
Wang, H., Zeng, X., Wang, W., Cao, D., 2015. Selective capture of trace sulfur gas by
porous covalent-organic materials. Chem. Eng. Sci. 135, 373–380.
Wang, Z., Zhang, S., Chen, Y., Zhang, Z., Ma, S., 2020c. Covalent organic frameworks for
separation applications. Chem. Soc. Rev. 49 (3), 708–735.
Wang, P., Zhou, F., Zhang, C., Yin, S., Teng, L., Chen, L., Hu, X., Liu, H., Yin, X.,
Zhang, X., 2018e. Ultrathin two-dimensional covalent organic framework nanoprobe
for interference-resistant two-photon fluorescence bioimaging. Chem. Sci. 9 (44),
8402–8408.
Wang, J., Zhuang, S., 2019. Covalent organic frameworks (COFs) for environmental
applications. Coord. Chem. Rev. 400, 213046.
Wei, S., Zhang, F., Zhang, W., Qiang, P., Yu, K., Fu, X., Wu, D., Bi, S., Zhang, F., 2019.
Semiconducting 2D triazine-cored covalent organic frameworks with unsubstituted
olefin linkages. J. Am. Chem. Soc. 141 (36), 14272–14279.
Wen, R., Li, Y., Zhang, M., Guo, X., Li, X., Li, X., Han, J., Sheng, H., Tan, W., Ma, L., Li, S.,
2018. Graphene-synergized 2D covalent organic framework for adsorption: a mutual
promotion strategy to achieve stabilization and functionalization simultaneously.
J. Hazard Mater. 358, 273–285.
White, D., Burkert, S., Hwang, S., Star, A., 2019. Holey graphene metal nanoparticle
composites via crystalline polymer templated etching. Nano Lett. 19 (5), 2824–2831.
Xie, G., Chen, H., Zhang, F., Shang, X., Zhan, B., Zeng, L., Mu, Y., Mellouki, A., Tang, X.,
Chen, J., 2021. Compositions, sources, and potential health risks of volatile organic
compounds in the heavily polluted rural North China Plain during the heating
season. Sci. Total Environ. 789, 147956.
Xu, H., Ding, S., An, W., Wu, H., Wang, W., 2016. Constructing crystalline covalent
organic frameworks from chiral building blocks. J. Am. Chem. Soc. 138 (36),
11489–11492.
Xu, C., Lin, J., Yan, D., Gou, Z., Austin, D., Zhan, H., Kent, A., Yue, Y., 2020. Pd
nanoclusters supported by amine-functionalized covalent organic frameworks for
benzyl alcohol oxidation. ACS Appl. Nano Mater. 3 (7), 6416–6422.
Yahiaoui, O., Fitch, A., Hoffmann, F., Froba, M., Thomas, A., Roeser, J., 2018. 3D anionic
silicate covalent organic framework with srs topology. J. Am. Chem. Soc. 140 (16),
5330–5333.
Yan, T., Lan, Y., Tong, M., Zhong, C., 2018. Screening and design of covalent organic
framework membranes for CO2/CH4 separation. ACS Sustain. Chem. Eng. 7 (1),
1220–1227.
Yan, Q., Xu, H., Jing, X., Hu, H., Wang, S., Zeng, C., Gao, Y., 2020. Post-synthetic
modification of imine linkages of a covalent organic framework for its catalysis
application. RSC Adv. 10 (30), 17396–17403.
Yang, Y., Faheem, M., Wang, L., Meng, Q., Sha, H., Yang, N., Yuan, Y., Zhu, G., 2018.
Surface pore engineering of covalent organic frameworks for ammonia capture
through synergistic multivariate and open metal site approaches. ACS Cent. Sci. 4
(6), 748–754.
Yang, L., Guo, Q., Kang, H., Chen, R., Liu, Y., Wei, D., 2020a. Self-controlled growth of
covalent organic frameworks by repolymerization. Chem. Mater. 32 (13),
5634–5640.
Yang, X., Hu, Y., Dunlap, N., Wang, X., Huang, S., Su, Z., Shaima, S., Jin, Y., Huang, F.,
Wang, X., Lee, S., Zhang, W., 2020b. A truxenone-based covalent organic framework
as an all-solid-state lithium-ion battery cathode with high capacity. Angew. Chem.
Int. Edit. 59 (46), 20385–20389.
Yao, Y., Hu, Y., Hu, H., Chen, L., Yu, M., Gao, M., Wang, S., 2019. Metal-free catalysts of
graphitic carbon nitride-covalent organic frameworks for efficient pollutant
destruction in water. J. Colloid Interface Sci. 554, 376–387.
Yar, M., Ayub, K., 2020. Expanding the horizons of covalent organic frameworks to
electrochemical sensors; A case study of CTF-FUM. Microporous Mesoporous Mater.
300, 110146.
Yu, M., Zeng, S., Wang, Z., Hu, Z., Dong, H., Nie, Y., Ren, B., Zhang, X., 2019. Protic
ionic-liquid-supported activated carbon with hierarchical pores for efficient NH3
adsorption. ACS Sustain. Chem. Eng. 7 (13), 11769–11777.
Yuan, H., Li, N., Linghu, J., Dong, J., Wang, Y., Karmakar, A., Yuan, J., Li, M.,
Buenconsejo, P., Liu, G., Cai, H., Pennycook, S., Singh, N., Zhao, D., 2020a. Chip-
level integration of covalent organic frameworks for trace benzene sensing. ACS
Sens. 5 (5), 1474–1481.
16
Chemosphere 291 (2022) 132795
Yuan, H., Qian, X., Luo, B., Wang, L., Deng, L., Chen, Y., 2020b. Carbon dioxide
reduction to multicarbon hydrocarbons and oxygenates on plant moss-derived,
metal-free, in situ nitrogen-doped biochar. Sci. Total Environ. 739, 140340.
Yue, J., Wang, L., Ma, Y., Yang, P., Zhang, Y., Jiang, Y., Tang, B., 2019. Metal ion-assisted
carboxyl-containing covalent organic frameworks for the efficient removal of Congo
red. Dalton Trans. 48 (48), 17763–17769.
Yun, J., Zhu, C., Wang, Q., Hu, Q., Yang, G., 2019. Catalytic conversions of atmospheric
sulfur dioxide and formation of acid rain over mineral dusts: molecular oxygen as the
oxygen source. Chemosphere 217, 18–25.
Yusran, Y., Guan, X., Li, H., Fang, Q., Qiu, S., 2020. Postsynthetic functionalization of
covalent organic frameworks. Natl. Sci. Rev. 7 (1), 170–190.
Zagho, M.M., Hassan, M.K., Khraisheh, M., Al-Maadeed, M.A.A., Nazarenko, S., 2021.
A review on recent advances in CO2 separation using zeolite and zeolite-like
materials as adsorbents and fillers in mixed matrix membranes (MMMs). CEJ Adv. 6,
100091.
Zeng, Y., Zou, R., Zhao, Y., 2016. Covalent organic frameworks for CO2 capture. Adv.
Mater. 28 (15), 2855–2873.
Zhai, L., Han, D., Dong, J., Jiang, W., 2021. Constructing stable and porous covalent
organic frameworks for efficient iodine vapor capture. Macromol. Rapid Commun.
42 (13), 2100032.
Zhang, Y., Hu, Y., Zhao, J., Park, E., Jin, Y., Liu, Q., Zhang, W., 2019. Covalent organic
framework-supported Fe-TiO2 nanoparticles as ambient-light-active photocatalysts.
J. Mater. Chem. 7 (27), 16364–16371.
Zhang, W., Jiang, P., Wang, Y., Zhang, J., Zhang, P., 2015. Bottom-up approach to
engineer two covalent porphyrinic frameworks as effective catalysts for selective
oxidation. Catal. Sci. Technol. 5 (1), 101–104.
Zhang, J., Ouyang, J., Ye, Y., Li, Z., Lin, Q., Chen, T., Zhang, Z., Xiang, S., 2018a. Mixed-
valence cobalt (II/III) metal-organic framework for ammonia sensing with naked-eye
color switching. ACS Appl. Mater. Inter. 10 (32), 27465–27471.
Zhang, M., Si, D., Yi, J., Zhao, S., Huang, Y., Cao, R., 2020a. Conductive phthalocyanine-
based covalent organic framework for highly efficient electroreduction of carbon
dioxide. Small 16 (52), 2005254.
Zhang, Q., Sun, Y., Cheng, G., Wang, Z., Ma, H., Ding, S., Tan, B., Bu, J., Zhang, C.,
2020b. Highly dispersed gold nanoparticles anchoring on post-modified covalent
organic framework for catalytic application. Chem. Eng. J. 391, 123471.
Zhang, B., Wei, M., Mao, H., Pei, X., Alshmimri, S., Reimer, J., Yaghi, O., 2018b.
Crystalline dioxin-linked covalent organic frameworks from irreversible reactions.
J. Am. Chem. Soc. 140 (40), 12715–12719.
Zhao, C., Diercks, C., Zhu, C., Hanikel, N., Pei, X., Yaghi, O., 2018. Urea-linked covalent
organic frameworks. J. Am. Chem. Soc. 140 (48), 16438–16441.
Zhao, Y., Liu, P., Ying, Y., Wei, K., Zhao, D., Liu, D., 2021. Heating-driven assembly of
covalent organic framework nanosheets for gas separation. J. Membr. Sci. 632,
119326.
Zhao, X., Pachefule, P., Li, S., Langenhahn, T., Ye, M., Tian, G., Schmidt, J., Thomas, A.,
2019a. Silica-templated covalent organic framework-derived Fe-N-doped
mesoporous carbon as oxygen reduction electrocatalyst. Chem. Mater. 31 (9),
3274–3280.
Zhao, X., Pachfule, P., Li, S., Langenhahn, T., Ye, M., Schlesiger, C., Praetz, S.,
Schmidt, J., Thomas, A., 2019b. Macro/microporous covalent organic frameworks
for efficient electrocatalysis. J. Am. Chem. Soc. 141 (16), 6623–6630.
Zhi, Y., Wang, Z., Zhang, H., Zhang, Q., 2020. Recent progress in metal-free covalent
organic frameworks as heterogeneous catalysts. Small 16 (24), 2001070.
Zhong, W., Sa, R., Li, L., He, Y., Li, L., Bi, J., Zhuang, Z., Yu, Y., Zou, Z., 2019. A covalent
organic framework bearing single Ni sites as a synergistic photocatalyst for selective
photoreduction of CO2 to CO. J. Am. Chem. Soc. 141 (18), 7615–7621.
Zhou, D., Tan, X., Wu, P., Tian, L., Li, P., 2019. Synthesis of C-C bonded two-dimensional
conjugated covalent organic framework films by suzuki polymerization on a liquid-
liquid interface. Angew. Chem. Int. Edit. 58 (5), 1376–1381.
Zhu, H., Lu, M., Wang, Y., Yao, S., Zhang, M., Kan, Y., Liu, J., Chen, Y., Li, S., Lan, Y.,
2020a. Efficient electron transmission in covalent organic framework nanosheets for
highly active electrocatalytic carbon dioxide reduction. Nat. Commun. 11 (1), 1–10.
Zhu, Q., Wang, X., Clowes, R., Cui, P., Chen, L., Little, M., Cooper, A., 2020b. 3D cage
COFs: a dynamic three-dimensional covalent organic framework with high-
connectivity organic cage nodes. J. Am. Chem. Soc. 142 (39), 16842–16848.
Zhuang, S., Wang, J., 2021. Magnetic COFs as catalyst for Fenton-like degradation of
sulfamethazine. Chemosphere 264, 128561.