Synthesis of COF - 3

Advanced Composites and Hybrid Materials (2023) 6:199
https://doi.org/10.1007/s42114-023-00776-4
REVIEW
Recent progress in advanced covalent organic framework composites

for environmental remediation
Kun Hou1 · Haiping Gu1 · Yafeng Yang2 · Su Shiung Lam3,4 · Hanyin Li1 · Christian Sonne5,6 · Hui Ouyang7 ·
Xiangmeng Chen8
Received: 19 August 2023 / Revised: 10 October 2023 / Accepted: 15 October 2023 / Published online: 31 October 2023
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2023
Abstract
With the rapid development of industry, this leads to sewage discharge and air pollution that seriously affect human health
and ecosystem. Therefore, environmental remediation has attracted wide attention in academia in recent years. Covalent
organic frameworks, a new type of porous materials, have been widely developed in this field due to their advantages of
easy modification and high specific surface area. Here, we summarize the research progress of covalent organic framework
materials in the field of environmental remediation in recent years, including sewage treatment, antibacterial application,
atmospheric water extraction, iodine vapor adsorption, and flue gas separation. The synthesis strategies, structures, morpholo-
gies, and modification methods of covalent organic frameworks were discussed as a whole to show how their properties and
long-term use were affected, and the structure-activity relationship between molecular structures and application properties
of covalent organic frameworks was summarized. This review is of great significance for researchers to fully understand the
development status and future trends of covalent organic frameworks in the field of environmental remediation.
Keywords Covalent organic frameworks · Preparation · Molecular structure design · Environmental remediation
1 Introduction pollution, resource shortage, and ecological destruction

[1–3]. For example, environmental problems caused by
Due to the lack of people’s expectation of the negative large amounts of pollutants in wastewater [4], volatile
impact of highly developed industry and the unfavorable iodine in radioactive discharges easily disperses into the
prevention, it has led to three global crises: environmental environment [5], the concentration of C O2 in the atmos-
phere is gradually developing every year, leading to ris-
ing global temperatures and intractable environmental and
Kun Hou, Haiping Gu, and Yafeng Yang contributed equally to this
work.
4
* Hanyin Li Center for Global Health Research (CGHR), Saveetha
lihanyin@henau.edu.cn Institute of Medical and Technical Sciences (SIMATS),
Saveetha University, Chennai, India
* Christian Sonne
5
cs@ecos.au.dk Department of Ecoscience, Aarhus University,
Frederiksborgvej 399, POBox 358, DK‑4000 Roskilde,
* Xiangmeng Chen
Denmark
xmchen0610@163.com
6
Sustainability Cluster, School of Engineering,
1
Henan Province International Collaboration Lab of Forest University of Petroleum & Energy Studies, Dehradun,
Resources Utilization, School of Forestry, Henan Uttarakhand 248007, India
Agricultural University, Zhengzhou 450002, China 7
National & Local United Engineering Laboratory
2
College of Landscape Architecture and Art, Henan of Integrative Utilization Technology of Eucommia
Agricultural University, Zhengzhou 450000, China Ulmoides, College of Chemistry and Chemical Engineering,
3 Jishou University, Jishou 416000, China
Higher Institution Centre of Excellence (HICoE), Institute
8
of Tropical Aquaculture and Fisheries (AKUATROP), School of Science, Henan Agricultural University,
Universiti Malaysia Terengganu, Kuala Nerus 21030, Zhengzhou 450002, China
Terengganu, Malaysia
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199 Page 2 of 39 Advanced Composites and Hybrid Materials (2023) 6:199
health problems, among others [6, 7]. Therefore, there is 3000

an urgent need to develop energy-saving, environmentally COF
friendly, and long-term effective methods to deal with the 2500
current dilemma. Fortunately, with the in-depth study of
Number of articles
environmental protection, adsorption, membrane separa- 2000
tion, and other technologies have gradually matured and
have become a very reliable technology in environmental
1500
remediation to remove various pollutants [8–10].
The materials used for adsorption and membrane sepa-
1000
ration technology are various, porous materials because
of their high specific strength, low relative density, light
weight, high specific surface area, good permeability, heat 500
insulation, sound insulation, and other advantages [11],

such as zeolite [12], diatomite [13], activated carbon [14], 0
2005 2010 2015 2020
metal-organic framework [15], perlite, chitosan [16], gra-
phene oxide [17], and covalent organic framework (COF) year
[18]. Covalent organic frameworks (COFs) are a class of
materials that form two- or three-dimensional structures Fig. 1 Number of publications retrieved annually on the web of sci-
ence from 2005 to 2023
through reactions between organic precursors, thereby
forming strong covalent bonds that provide porous, sta-
ble, and crystalline materials [19]. The construction units Since 2005, extraordinary progress has been made in the
of COF are small organic molecules, which come from a application and development of COFs as adsorbents or sepa-
wide variety of sources and make the construction units ration membrane materials. There have been some investiga-
diversified, and it is convenient to regulate the function tions of COF in areas such as catalysis or electronic sensing
and structure of the target material through the construc- or energy storage, or COF hybrid materials. So far, there
tion units [20, 21]. In addition, the covalent bonds forming has not been a comprehensive review of COF application
a spatial network structure provide thermal and chemical focusing on environmental remediation. Here, we provide
stability [22, 23]. such information focusing on the synthesis, structure, and
Since its discovery in 2005 [24], COFs have been exten- functional advantages of COF nanomaterials and how to
sively used in adsorption, drug slow release, energy storage, apply these as adsorptive separation materials in environ-
catalysis, and other fields because of their advantages of mental remediation including sewage treatment, antibacte-
functionalization, easy modification, and high specific sur- rial application, atmospheric water extraction, iodine vapor
face area. In addition, in the field of electromagnetic meta- adsorption, and flue gas separation. The connection between
material construction [25–28], the designable structure of application performance and molecular structure design of
COF shows strong attraction, so it has potential application COFs was analyzed in detail. Finally, we provide directions
value in electronic devices. The number of articles about for future research of COF nanomaterials and how this may
COF on the Web of Science is also increasing year by year be upscaled.
(Fig. 1). For example, Zhang and co-workers used porphyrin
COF and bacterial cellulose (BC) as materials to prepare
defection-free and continuous BC/covalent organic skel- 2 Preparation method of COFs
eton composite films with their unique structure, and used
them for dye separation [29]. The composite film showed As a new type of porous material, COF has a lot of poten-
attractive antibacterial and antifouling performance. Ma tial applications. Therefore, there are many examples of the
and co-workers report trifluoromethyl functionalized two- preparation and application of COF materials. Among them,
dimension COF (TpTFMB) with 1,3,5-triformylphloroglu- the current synthesis methods of COF materials are similar
cinol (Tp) and 2,2 & PRIME;-bis(trifluoromethyl)benzidine to those of metal-organic framework (MOF) porous materi-
(TFMB) are used to separate isomers [30]. Wang and co- als, including solvothermal synthesis [32, 33], microwave-
workers propose a simple covalent assembly method for the assisted synthesis [34, 35], ionic thermal synthesis [36],
formation of superhydrophobic COF stable MXene separa- mechanochemical synthesis [37–39], and room temperature
tion films [31]. These applications show the controllable chemical synthesis [40, 41]. Solvothermal synthesis is a com-
preparation of COF materials, making it a promising avenue mon method to synthesize COF materials. At present, most
to explore new COFs in environmental remediation, espe- COF materials are synthesized by solvothermal method.
cially in the adsorption removal of toxic pollutants. The solvothermal method is suitable for the preparation of
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Advanced Composites and Hybrid Materials (2023) 6:199 Page 3 of 39 199
a variety of COF materials, which can not only synthesize 2.1 Microwave‑assisted synthesis
powder materials [42–44], but also prepare thin film mate-
rials [45]. A new COF material with onion nanostructure Microwave-assisted synthesis refers to the solvothermal
prepared by hydrothermal synthesis method [46]. The 2D synthesis method using electromagnetic irradiation in the
layer of the onion structure COF has a highly fused aromatic wavelength range of 1 mm ~ 1 m. Compared with the tradi-
skeleton, periodic nanopore (~ 1.2 nm), and π-stacked col- tional methods, microwave heating does not require a heat
umns with a stacking distance of about 0.33 nm between the conduction process and can achieve uniform heating in a
layers. The average size of COF is controlled at 5.7 ± 1.2 nm. short time [50, 51]. Microwave heating method requires
These indicate that it has great application potential. the use of polar solvents to achieve a better heating effect
The simple solvent-thermal synthesis method will cause [52–54]. Compared with the traditional solvothermal syn-
insoluble aggregation in the preparation of COF nano- thesis condition, the microwave-assisted synthesis can
materials, which is not conducive to the later processing. synthesize COF materials with stability and better crys-
Therefore, the method of preparing uniform and stable COF tallization in a shorter time and lower temperature. For
suspensions has received much attention. COF monomers example, Liu and co-workers selected 1,2,4,5-four-carbon
and oligomers can maintain uniform dispersion in dimethy- nitrobenzene (TCNB) as the only organic ligand and used
lacetamide (DMAc) solvent, which can reduce the tendency microwave-assisted synthesis method to synthesis copper
of precipitation and aggregation of nanoparticles in the syn- phthalocyanine-based two-dimensional conjugated organic
thesis of COFs. Fan and co-workers chose DMAc as a sol- framework (CuxPc-COFs). The preparation time was only
vent to slow down the growth rate of COF nanoparticles in 15 min [55]. Ji and co-workers promoted the nucleophilic
the presence of water and an acidic catalyst to prepare a uni- substitution of 2,3,6,7,10,11-hexahydroxytriphenyl with
form and stable suspension of COF nanoparticles, as shown 2,3,5,6-tetrafluoro4-pyridine-carbon nitrile by microwave-
in Fig. 2a [47]. This is because the presence of water can assisted synthesis [56]. The reaction time was only 30 min,
increase the rate of imine hydrolysis. In addition, because and the reaction temperature was only 70 ℃ (Fig. 2b).
the protonated amine group must first undergo proton trans- Interestingly, the surface area (1254 m 2 g−1) of TH-COF
fer before reacting with the dialdehyde, acidic catalysts can prepared under microwave conditions greatly surpass that
protonate the amine group, which can slow down the growth of COF-318 (576 m 2 g−1) of the same framework prepared
of imine COFs. Solvothermal synthesis method can not only by conventional techniques. Given the huge application
form a film by preparing COF nanoparticles, but also grow potential of microwave-assisted synthesis of COFs, it is
COF layer directly on the support body for environmental imperative to develop more sustainable processes for the
remediation. Fan and co-workers synthesized a COF-LZU1 synthesis of high-quality COFs with high crystallinity
film (400 nm) on the ceramic tube by in situ solvothermal and porosity. However, the harmful and high boiling point
method [48]. The surface of the alumina tube altered by organic solvents, such as 1, 4-dioxane, mesitylene, N,
3-aminopropyltriethoxysilane (APTES) can be well grafted N-dimethylacetamide (DMA), o-dichlorobenzene (DCB),
with 1,3,5-triformylbenzene (TFB). In addition, TFB con- and N, N-dimethylformamide (DMF), are still one of the
structs a coordination bond between the amino aluminum disadvantages that hinder the development of COF appli-
substrate and the para-phenylenediamine (PDA) ligand, cations, so green synthesis solutions for the production
which greatly promotes the nucleation and growth of COF- of COFs are particularly important. Liu and co-workers
LZU1 on the substrate. However, the preparation time of used water as a solvent to prepare imine-based COFs at a
this synthesis method is longer and the required temperature relatively low temperature [57]. TAPB-BTCA-COF was
is higher. In addition, the yield of the material prepared by obtained within 5 h (TAPB: 1,3,5-tris-(4-aminophenyl)
solvothermal method is milligram-level, and the solvent is benzene; BTCA: 1,3,5-benzenetricarbaldehyde), and its
expensive, which is not applicable for large-scale prepara- yield was comparable to the reaction of conventional heat-
tion of COF materials. Although there has been a report ing for 5 days (85%). The synthesized COFs have good
that the COF crystallinity of the two steps of the solvent is crystallinity and high porosity. Similarly, a plan of mak-
increased, applied to the amplification of the high-quality ing a highly substituted cationic azacalix[4]arene-based
COFs, which is the first step to focus on the condensation COF (ACA-COF) with water and ethanol as solvent under
of the monomer without the optimization of the crystalliza- microwave irradiation was also reported [58]. It uses the
tion condition [49]. In the second step, using the appropriate chemical functionalization of organic macrocycle to limit
solvent thermal conditions, the COF crystallization is pro- their conformational flexibility, resulting in ordered mate-
moted through defect correction and structural restoration. rials. In addition, the synthesis of COF-mixed matrix films
However, in fact, more simple and efficient methods and by microwave-assisted synthesis was reported [59].
synthesis of COF materials need to be explored.
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Fig. 2 a Roadmap for solvothermal preparation of COF [47]. b (Tp: 1,3,5-triformylphloroglucinol; Pa-1: p-phenylenediamine; Pa-2:
Roadmap of TH-COF-SPME fiber synthesized by microwave [56]. 2,5-dimethyl-p-phenylenediamine; BD: benzidine) [61]. e Schematic
c Synthesis diagram of TAPA-PMDA-COF and TT-PMDA-COF diagram of rapid prepare of TAPB-OMePDA COF catalyzed by tran-
in eutectic salt mixtures under ionic thermal conditions (TAPA: sition metal nitrates at room temperature (OMePDA: 2,5-dimethoxy-
2,4,6-tris(4-aminophenyl)-amine; PMDA: pyromellitic dianhydride; terephthalaldehyde) [62]. f Schematic illustration of ultrasonic chemi-
TT: 2,4,6-tris(4-aminophenyl)-triazine) [60]. d Schematic diagram cal synthesis of COF nanomaterials [63]. g Schematic illustration of
of the mechanochemical synthesis of TpPa-1, TpPa-2, and TpBD photochemical synthesis of COF materials [64]
2.2 Ionic thermal synthesis solvents used in the synthesis process are harmful to the
environment. The newly developed ionic thermal synthesis
Although solvothermal synthesis and microwave-assisted process does not require the participation of toxic solvents,
synthesis are widely used, it is undeniable that the toxic which avoids the impact on the environment to a certain
13
extent. For example, in zinc chloride melt at 400 °C, a skeleton carbon nanotube composites (MCNTs@TpPa-1)
microporous polytriazine network with high surface area were prepared by mechanical grinding and used as adsorbent
and porosity is obtained by trimerization of nitrile [65]. [68]. TpAzo COF was favorably prepared by an easy and
The surface area (791 m2 g−1) and total pore volume (0.40 rapid mechanochemical reaction between 4,4′-azodianiline
cm3 g−1) of the covalent triazine-based framework (CTF- (Azo) and 1,3,5-triformyl-phloroglucinol (Tp) [69]. Moreo-
1) were close to those of COF-1 prepared by hydrothermal ver, a mechanochemical synthesis of nanoporous fluorine-
synthesis. However, the ionic thermal synthesis method has functioned COF (TPA-F) with an F-containing forerunner
high reaction temperature and strict reaction conditions, and (2-fluoro-1,4-phenylenediamine) for C 2H2/CO2 separation
the thermal stability of the reaction unit is also increased, has been reported, showing excellent adsorption capacity
so how to reduce the reaction temperature has become a and exceptional thermal stability up to about 673 K. It also
focus of research. Instead of using zinc chloride, Maschita exhibits chemical stability in acidic/alkaline or organic solu-
and co-workers proposed to use Z nCl2-containing three-salt tions [70].
eutectic mixture (KCl/NaCl/ZnCl2) as the reaction system to Interestingly, the addition of different substances during
prepare COF materials, as shown in Fig. 2c [60]. The experi- mechanical grinding also has an effect on the microstruc-
mental results show that the reaction temperature reduced ture of the final COF. Lv and co-workers explored cata-
to 250 ℃, and the synthesis yield of TAPA-PMDA-COF lyst-assisted, liquid-free ball milling, and solvent-assisted
and TT-PMDA-COF can reach 85% and 64%, respectively. routes [71]. In the absence of p-toluenesulfonic acid (PTSA),
Although there is a decrease in COF yield relative to the TpMA (MA: melamine) synthesized without solvent or
use of pure ZnCl2, the decrease in reaction temperature is 1 mL solvent had mediocre morphology and crystallization.
still a very attractive scheme. It is noteworthy that the spe- With the addition of PTSA, T pMAC(1 ml) has great crystal-
cific surface area (1592 m 2 g−1) of the ionic thermal syn- lizability and well defined interweave shape, with an aver-
thesized TAPA-PMDA-COF is significantly higher than age diameter range of 60 ~ 100 nm. These results signify
that of the solvothermal technique (1027 m2 g−1), and the that PTSA plays an important role in the mechanochemical
crystallinity of the four COFs synthesized by the ionic ther- preparation of TpMA. Recently, Zhang and co-workers built
mal method is comparable to or even higher than that of a melt polymerization method for the first time to synthesize
the solvothermal synthesized COFs. In addition, by using a COFs [72, 73], but the extant literature are still limited to
three-salt eutectic mixture instead of pure ZnCl2, it is possi- C=C-linked COFs. To expand the application of this synthe-
ble to apply this ion-thermal synthesis scheme to less stable sis method, they used benzoic anhydride as a functional and
linked molecules such as 2,4,6-tris(4-aminophenyl)-triazine green medium to prepare four C=N-linked 2D COFs [74].
(TT) and 2,4,6-tris(4-aminophenyl)-amine (TAPA), which The porosity of the prepared COFs is comparable to that
greatly widens the range of imine-linked COFs. Therefore, of traditional solvothermal COFs that have been reported.
ionic thermal synthesis method is particularly important for Notably, BTCA-TAPB-COF was synthesized in a one-pot
expanding COF materials in future applications. reaction at gram yield.
2.3 Mechanochemical synthesis 2.4 Room temperature chemical synthesis
Compared with traditional non-expandable and environmen- In the chemical synthesis industry, the development of a
tally unfriendly solvothermal methods, the mechanochemi- mild condition, friendly environment, convenient, and fast
cal synthesis of COF materials by grinding solid reactants synthesis method has been the focus of researchers. Synthe-
with solvent-free or very small number of solvents has the sizing COF at room temperature is a simple and fascinating
characteristics of simple operation, fast speed, environ- strategy that reduces energy loss and fits in with the world’s
mental friendliness, and large production capacity. Due ideas of emission reduction and energy conservation. As a
to its elimination of potentially toxic organic solvents, the new type of green medium, deep eutectic solvent (DESs) is
synthesis process is more environmentally friendly. Since assembled by the strong hydrogen bond interaction between
Biswal and co-workers first identified the preparation of hydrogen bond acceptor (HBA) and hydrogen bond donor
COFs by grinding Tp and benzidine (BD), 2,5-dimethyl- (HBD) and has accepted extensive attention in many areas.
p-phenylenediamine (Pa-2) or p-phenylenediamine (Pa-1) Qiu and co-workers are the first to report the preparation of
with a pestle at room temperature (Fig. 2d) [61], mecha- 2D and 3D COFs under environmental conditions by explor-
nochemical synthesis has been popular and developed to ing DESs as a green medium [75]. Compared with the long-
a certain extent [66]. For example, the triptycene-based time solvothermal synthesis, the reaction time was shortened
imine-linked covalent organic polymer TP-COP was syn- by 70 h. The new method avoids the use of harmful organic
thesized by manual grinding of monomers (terepthaldehyde solvents and high temperatures. Moreover, the total pore vol-
and triaminotriptycene) [67]. Magnetic covalent organic ume (1.2 cm3 g−1) and specific surface area (747 m2 g−1) of
13
the prepared COF are much higher than those of TpPa (535 yellow benzoxazole-linked COF LZU-191 crystal with high
m2 g−1) prepared by solvothermal synthesis reported previ- yield was obtained. Notably, the preparation of LZU-191
ously. In addition, it is noteworthy that the prepared COF by the “windowsill” reaction performed on the gram scale,
has a high chemical stability; its crystal structure remains which is significantly different from solvothermal synthesis,
good in aqueous acid and alkali solutions and boiling water was performed at the milligram level. In conclusion, it is
produced in grams. Zhu and co-workers also catalyzed the very important to understand the different COF synthesis
rapid preparation of imine COFs under environmental con- methods for the future application of COF.
ditions by transition metal nitrates (Fig. 2e), and all tested
transition metal nitrates prepared crystalline COF products
even in the presence of oxygen [62]. The prepared P-COF 3 Structure and molecular design of COFs
films by in situ growth at room temperature have good pore
size distribution (1.1 nm) and excellent specific surface area The use of COF materials for environmental remediation
(565 m2 g−1), which can be applied in nanofiltration [76]. and a detailed understanding of the determining factors that
In contrast to the previous methods, ultrasonic chemistry play an important role in environmental remediation can pre-
uses ultrasonic waves in the frequency range of 20 kHz to cisely design the molecular structure of COF materials, thus
about 1 MHz, and its chemical effects are caused by sonic promoting their application in environmental remediation.
cavitation. The violent implosion of bubbles creates tem- COFs play the role of adsorption and size screening in envi-
porary extreme conditions such as immersion pressure ronmental remediation. Adsorption is a universal phenom-
(> 1000 atm), high temperatures (> 5000 K), fast heating, enon that can occur through chemical interactions (chem-
and cooling speed. The use of ultrasonic chemistry to pre- isorption) or physical interactions (physical adsorption).
pare COF is reported in the literature [77–79], and some In general, the adsorption properties of COFs are highly
advantages have been shown, such as ultrasonic treatment influenced by the binding affinity or interaction between the
is very effective in promoting the uniform mixing of slightly functional material and the guest molecule, which depends
dissolved 1,4-benzene diboronic acid (BDBA) in solvent on the pore environment, morphology, pore shape and size,
mixtures. What is more, liquid-phase ultrasonic stripping specific surface area, and the properties of the adsorbent.
is a widely used method for layering and layering materi- The size of the physical aperture determines the application
als. However, an inevitable trouble of ultrasonic stripping chance of the separation process. In addition, in the range
is that the yield of ultra-thin 2D COF nanosheets is very of environmental remediation, it is essential to play a role
low, which grow into a barrier for the practical application in the water environment, so the stability of COF materials
of COF nanosheets. Gan and colleagues have studied a new in water is an important factor. A large number of COFs
method of direct ultrasound-mediated monomer polycon- have great thermal stability, but stability in aqueous solu-
densation under mild conditions to produce ultra-thin 2D tions remains a challenge. The microstructure design of COF
COF nanosheets at the gram level in a short time, as shown materials has always been one of the research hotspots. How
in Fig. 2f [63]. This method is simple and efficient, and to accurately design the molecular structure of COF and
2D COF nanosheets with excellent properties are prepared how to find the relationship between its molecular structure
by ultrasound in a beaker. In addition, photochemical syn- and application results is heavy research. Therefore, in this
thesis as one of the most efficient and important chemical chapter, we will evaluate in detail the factors affecting the
synthesis processes has been studied for a long time [80]. structure and molecular design of COF materials.
Photochemical synthesis provides an ideal chance to achieve
faster reactions through inaccessible chemical pathways. For 3.1 Functional group
example, light energy is used to accelerate the imine conden-
sation reaction and form highly conjugated and crystalline The functional groups in COFs play a crucial role in their
COF (HCC-COF) with high yields in a short reaction time selectivity and adsorption capacity. The microenvironment
[81]. Kim and colleagues for the first time used photochemi- of COF pores is customized by combining functional groups,
cal method to synthesize the uniform particle size of “sea achieved through “bottom-up” or post-synthetic modifica-
urchin shape” COF-5 (UV-COF-5) with a yield of 75% and tion strategies [83–85]. Bottom-up synthesis is a simple and
a growth rate of about 48 times higher than that of the solvo- problematic method of COF design and construction [86].
thermal method [82]. Wu and co-workers applied the natural Before the synthesis is completed, the functional part will
sun-mediated photocatalytic polymerization method to COF be directly included in the construction unit of the design.
preparation, as shown in Fig. 2g [64]. The reaction of 1,3,5- For example, 4-(4-(methylthiophenyl) phenyl) pyridine-2,
tris (4-formylphenyl) triazine (TFPT) with 2,5-diamino- 6-diacetaldehyde (MPPD), which contains the functional
1,4-benzenediol dihydrate (DABD) in the presence of TBA- group of thioanisole, is directly involved in the synthesis of
eosin Y was carried out under solar irradiation, and a dark COF (TAB-MPPD; TAB: tris(4-aminophenyl) benzene) as
13
a monomer (Fig. 3a) [87]. TAB-MPPD shows excellent oil is superior to that of synthetic TpPa-H and most reported
absorption properties because of the existence of thioani- porous physical adsorption materials. Zheng and co-workers
sole functional groups in the MPPD para-position. Liu and prepared fluorine-functionalized spherical COFs (SF-COFs)
co-workers used a fluorine-containing precursor (2-fluor- as stationary phases for high-performance liquid chromatog-
1,4-phenylenediamine) as raw material to synthesize a nano- raphy [88]. SF-COFs packed columns have obvious narrow
porous fluoro-functional COF (TpPa-F) for the separation particle size distribution, monodispersity and high fluoride
of C2H2/CO2 by mechanochemical method, as shown in the content, and have high column efficiency and good resolu-
Fig. 3b [70]. At the same time, they also prepared F-free tion for the separation of organic fluorides containing poly-
COF (TpPa-H). Since the diffraction patterns of both TpPa- fluorobenzene, polychlorobenzene, polybromobenzene, per-
F and TpPa-H are consistent with the hexagonal lattice of fluoroalkyl methacrylate, and halogenated trifluorotoluene.
the P′6 space group, the introduction of fluorine atoms has In the field of environmental remediation, superhydro-
no effect on the crystalline structure of the framework. In philic materials have always been a promising material.
addition, TpPa-F obtained a higher specific surface area Ji and co-workers used a bottom-up strategy to introduce
(1048 m2/g) and a pore size distribution centered at 11.9 Å. hydrophilic sulfonic acid groups into 2D COF (represented
In contrast, TpPa-H has a larger one-dimensional channel by NUS-9), which greatly improved the grafting density
(12.4 Å) and specific surface area (1270 m 2/g). This shows of hydrophilic monomers and made NUS-9 have excellent
that the functionalization of fluorine reduces the pore size of hydrophilicity (Fig. 3c) [89]. Moreover, magnetic adsor-
COF, which leads to the reduction of specific surface area. bents also have great potential. Hu and colleagues reported a
It is worth noting that TpPa-F shows excellent selectivity functionalized covalent organic skeleton composite based on
for C2H2/CO2 and high absorption of C2H2. This behavior core-shell magnetic carboxylic acids (Fe3O4@COF-COOH)
Fig. 3 Bottom-up strategy. a Synthesis of TAB-DFP and TAB-MPPD [89]. d Preparation diagram of magnetic COF modified by carboxyl
by introducing hydrophilic functional group (DFP: 2,6-diformylpyr- group [90]. e Schematic diagram of one-pot synthesis of COF-g-X%
idine) [87]. b Scheme for the synthesis of TpPa-F by condensation poly(acrylic acid) (PAAc) under γ-ray irradiation [91]. f Schematic
of Tp with 2-fluoro-1,4-phenylenediamine (Pa-F). Illustration of comparison between the preparation of bottom-up cross-linked car-
TpPa-NO2 stacking structure [70]. c Synthetic procedure of NUS-9 bon fiber and ordinary 2D carbon fiber [95]
13
13
◂Fig. 4 Post-synthetic modification. a Schematic synthesis of [HO2C] (2D) COF has a limited pore volume and surface area due
X%-H2P-COFs with carboxyl functionalization [100]. b Schematic to its dense deposit structure, which greatly limits its poten-
diagram of COF-S-SH synthesis [101]. c Synthesis of functionalized
magnetic COFs [102]. d Post-synthetic modification of COFs by aza-
tial as adsorbents for gases such as methane, carbon dioxide,
DA reaction [103] and hydrogen. Most 2D COFs have very low efficiency in
terms of gas adsorption. Huang and co-workers used phenol
groups to perform quantitative ring-opening reactions with
[90]. Amino-modified Fe3O4 nanoparticles were prepared succinic anhydride, which decorated the channel wall with
by Schiff base condensation reaction using 1,3,5-triformyl- ring-opening carboxylic acid groups (Fig. 4a) to improve
phloroglucinol (TFP), 2,5-diaminobenzoic acid (DAA), the adsorption capacity of COF materials for carbon dioxide
and p-phenylenediamine (PEA) as monomers, as shown [100]. Considering the remarkable capability of sulfur deriva-
in Fig. 3d. The high magnetic saturation strength of this tives to bind to soft heavy metal species, Sun and colleagues
adsorbent ensures rapid separation during adsorption. The designed a vinyl functionalized COF (COF-V) synthesized
aromatic ring can promote π-π interactions and hydropho- from the condensation of 1,3,5-tri(4-aminophenyl) benzene
bic, while the carboxyl group can engage in weak cation (Tab) and 2,5-divinylterephthalaldehyde (Dva), in which vinyl
exchange interactions. Therefore, through the harmonious can remain intact during COF preparation (Fig. 4b) [101]. The
action of many components, the multi-functional COF- sulfur derivative (mercaptan and/or thioether) is anchored to
COOH adsorption material has excellent adsorption capacity the channel wall using a thiol–ene “click” reaction between
for some organic compounds. Zhang and co-workers intro- 1,2-ethyldimercaptan and the vinyl group in COF-V with the
duced functional grafting chains in situ into the skeleton of help of azobis(isobutyronitrile) (AIBN). COF-S-SH materi-
COFs (Fig. 3e) [91]. The functionalization and preparation als showed excellent adsorption properties for mercury ions.
of COFs are performed simultaneously in chemical systems, Khojastehnezhad and co-workers functionalized core-shell
and many different functionalized COFs are produced under magnetic imine-linked COFs with thiosemicarbazone (TSC)
environmental conditions. The obtained carboxyl-function- through three steps of post-synthetic modification (Fig. 4c)
alized COFs have high adsorption capacity, rapid adsorption [102] to produce magnetic thiocarbonyl linked COFs, which
kinetics, exceptional selectivity to other competing metal achieved magnetic recovery of the adsorbent and demon-
ions, and excellent removal ability of radioactive uranium strated excellent efficiency in selective and ultra-fast removal
in water. of mercury (II) from water.
Moreover, isopropyl and thioether groups were intro- The imine bond in the two-dimensional COFs can be
duced into the COF structure to create 3D thioether COFs, converted into the corresponding quinoline COFs based
which showed good adsorption ability [92]. A series of on the efficient Povarov (aza-Diels-Alder, aza-DA) reac-
amide-functionalized covalent triazine frameworks (CTF- tion between aryl alkynes and aryl imines. Therefore, by
PO71; CTFs: covalent triazine frameworks; PO71: pigment selecting different substrates for the aza-DA reaction, a large
orange-71) with good porosity were prepared by using the number of different functional groups can be introduced to
monomer containing amide PO71 [93]. The attractive porous selectively modify the wettability and pore surface of the
COFs and the inherent advantages of macrocyclic chemistry resulting COFs (Fig. 4d) [103]. Likewise, Wang and co-
combined to remove Hg2+ from aqueous solutions [94]. The workers attempted to modify the COF-LZU1, the aryl imine
use of custom monomers linked to flexible polyethylene gly- backbone, and amide, via an aza-Diels-Alder reaction [104].
col (PEG) or alkyl chains to connect the layered structures in Superhydrophobic COF-Q-CF3 not only retains the porosity
2D COFs provides a new class of 3D COFs, the cross-linked and crystallinity, but also shows very strong oil adsorption
COFs (Fig. 3f) [95]. All these indicate that more functional capacity and excellent water-in-oil emulsion separation effi-
groups are introduced into primitive COF materials through ciency. In summary, grafting functional groups into COF
bottom-up strategies. It is noteworthy that some functional structures bring a flexible and common way to customize
groups are involved in the reaction during the synthesis of their physicochemical properties. The obtained COFs with
COFs, so the bottom-up strategy will be somewhat limited. designed functional groups have good potential in the area
Post-synthetic modification can avoid the effect of intro- of environmental remediation.
duced functional groups on the structure of COF [96]. Post-
synthetic modification is more extensively used to introduce 3.2 Pore size
functional groups into a COF network [97, 98].
Carboxyl functional groups have unique adsorption prop- Pore size is another key feature of COFs and plays a crucial
erties for some metal ions and carbon dioxide. Carboxyl is role in environmental remediation processes, especially in
grafted on the surface of COF materials containing hydroxyl the most popular implementations of adsorption and mem-
groups through the ring-opening reaction between succinic brane separation techniques. For example, common applica-
anhydride (SA) and hydroxyl group [99]. Two-dimensional tions are desalination and separation of organic pollutants
13
by size exclusion. For ion separation, the pore size of COFs different organic linkers with specific lengths and structures
should not be greater than 1 nm. For the removal of dyes, in the process of synthesizing COF materials. Wang and col-
the pore size can reach 2–3 nm, while for the removal of leagues synthesized COFs (30.29 Å for TFPB-BD, 21.95 Å
proteins, the pore size can be larger. Therefore, in order to for TpBD, and 15.56 Å for TpPa-2; TFPB: 1,3,5-Tris(p-
obtain the ideal COFs for different applications, one should formyl phenyl)benzene; BD: 4,4′-Diaminooctafluorobiphe-
design and manufacture structures with different apertures nyl) with different pore sizes by solvothermal reaction by
[105, 106]. Today, there are two methods; one is to select pairing reaction monomers with each other (Fig. 5a) [107].
Fig. 5 a Synthesis roadmap of Fe3O4/COFs [107]. b Schematic diagram for preparation of TFP-DNF and TFP-DPF COF by intermonomer
Schiff-base condensation reaction [108]. c Preparation diagram of Azo-COF and Tp-COF [109]. d Preparation diagram of TpPa@Hz(X) [112]
13
As the pore size of F e3O4/TpPa-2 is closer to the bisphenol narrow pores were formed on the surface of TpPa, and the
A (9.7 Å), it shows a better adsorption effect. The adsorp- pore size distribution of TpPa@Hz(8) and TpPa@Hz(4)
tion of bisphenol A on F e3O4/TpPa-2 mainly rests on the was shown to be 0.5 nm, thus enlarging the small molecule
synergistic effect of pore size effect and π-π interaction. separation capacity of the films. In conclusion, in order to
Shinde and co-workers used Langmuir–Blodgett strategy satisfy the growing demand for accurate molecular sieving,
to prepare two ultra-thin types (TFP-DNF and TFP-DPF; it is essential to properly adjust the pore size.
DNF: 9,9-dinonylfluorene-2,7-diamine; DPF: 9,9-dipro-
pylfluorene-2,7-diamine), and reasonably controlled the 3.3 Chemical stability
pore sizes of COF films by selecting reaction monomers
with different carbon chain lengths (Fig. 5b) [108]. Due In practical applications, especially in wastewater treatment,
to the longer side chains, the pore size and surface area of the structural stability of materials in aqueous solutions
TFP–DNF (1.22 nm, 172 m2 g−1) were smaller than that of (including alkaline or acidic environments) plays a very
TFP–DPF (1.72 nm, 336 m2 g−1). In addition, the film per- important role [113, 114]. In fact, since the Lewis site of B is
meation results in organic dye molecular sieve applications effortlessly attacked by nucleophiles, the first reported B-O-
and organic solvent nanofiltration showed that the systemic linked COF exhibits poor pH stability and water stability.
changes of membrane flux and molecular weight cutoff val- With the accelerated development of chemistry, some COFs
ues were related to pore size changes. Wang and co-workers with high chemical stability have been developed [115]. For
synthesized two stable mesoporous COFs (Tp-COF and instance, Wang and colleagues applied the 2D COF mono-
Azo-COF) with highly crystallized frameworks by selecting mer polycondensation method to synthesize flower-shaped
reactive monomers of different molecular lengths (Fig. 5c) particles composed of highly crystalline “petals” with a size
and slightly tuned their pore sizes with carefully selected of more than 20 µm [116]. This meta-structure has a very
pyrene junctions and amino bonds [109]. Benefiting from stable mechanical strength and maintains structural integ-
the pore size difference of less than 4 Å, tandem utilization rity even after 900 °C processing. Li and co-workers syn-
of these two COFs showed highly efficient size-selective thesized a novel superhydrophobic COF by solvothermal
separation ability for the low molecular weight myoglobin method [117]. The superhydrophobic monomer Da-octyl
and proteins cytochrome C, with molecular weight differ- was formed by first modifying 2,5-dihydroxyterephthalal-
ences as small as 2 kDa. In addition, Xing and co-workers dehyde (Da) with octyl by nucleophilic substitution reaction.
also selected reaction monomers with only one benzene ring Then, it condensed with 1,3,5-(1,3,5-triazine-2,4,6-triyl)
difference and successfully synthesized COF-1.1 (1.1 nm) triphenylamine (Tz) to synthesize COF TzDa-octyl. COF
and COF-1.3 (1.3 nm) through solvothermal reaction [110]. shows high stability in alkaline, acidic, and various organic
The second type was modified by introducing functional solvents, used in complex environments.
groups after synthesizing COF materials, thus changing Wu and colleagues proposed a bottom-up self-assembly
the pore size. To afford enantioselectivity in the separation strategy to construct 2D COFs with different lengths of
of nanochannel films, Zhang and co-workers separated fluorine chain-functionalized and explore their stability
the nanochannels via in situ synthesis of L-tyrosine- in acid solution [118]. After soaking in some strong acid
functionalized COFs (L-Tyr-COF) [111]. That is, post- for a day, the chemical stability of COF-Fx was tested, as
modification of COOH-COF filled nanochannels (COOH- shown in Fig. 6a. The porosity and crystallinity of COF-
COF channels) by using a chiral receptor (L-Tyr) by amide F6 remained essentially unchanged. The C-F bond is the
condensation reaction. Compared with surface-functionalized strongest bond in organic chemistry, making organic fluo-
nanochannels, L-Tyr-COF-filled nanochannels showed rine stable and hydrophobic. They also tested whether flu-
higher flux (1.33 mmol m−2 h−1) and enantioselectivity orine contributed to superior acid resistance by using the
(94.2%), which enabled efficient separation of chiral drug non-fluoroalkyl analogue COF-42 for analogy. The acid
enantiomers. Cao and colleagues developed a post-synthetic stability of non-fluoroalkyl COF-42 is lower than that of
linker exchange (PLE) strategy to prepare COF films for COF-Fx. The sample of COF-42 partially dissolved and
effective alcohol dehydration, as shown in Fig. 5d [112]. became amorphous, while the sample of COF-F6 main-
The developable PLE strategy exploits the reversible break- tained good crystallinity. Similarly, Li and co-workers oxi-
reforming basis between the post-introduction linker and dized imine-linked COF to synthesize amide-linked COF,
the original COF film to narrow the effective pore size and which showed excellent stability under alkaline conditions
thus enhance the molecular sieving performance. The pore and in organic solvents [119]. At the same time, Yang and
distribution of the three membranes at 1.2 nm derived from co-workers converted hydrazone-linked COF (hydrazone-
the original TpPa, which was lower than that of the reported MTH-TFPB COF; MTH: (S)-2,5-Bis(2-methylbutoxy)tere-
TpPa due to bias overlap stacking. Due to the linker exchange phthalohydrazide) to hydrazide-linked COF (hydrazide-
of p-phenylenediamine (Pa) with hydrazine hydrate (Hz), MTH-TFPB COF) by mild oxidation [120]. They examined
13
Fig. 6 a PXRD patterns (Cu Kα) of acid stability tests for COF-42 TFPB COF and the chemical stabilities of oxidized hydrazide-MTH-
and COF-F6 by soaking them in 85 wt% H 3PO4, 38 wt% HCl, and TFPB COF and hydrazone-MTH-TFPB COF in different harsh envi-
65 wt% HNO3, respectively [118]. b Preparation of hydrazide-MTH- ronments [120]
the chemical stability of COFs by soaking them in assorted 4 Application of COF nanomaterials
organic solvents. After treatment with N,N-Dimethylfor-
mamide (DMF), tetrahydrofuran (THF), Dichloromethane COF materials have the advantages of regular pores, great
(DCM), MeOH, and EtOH, both COFs maintained their thermal and chemical stability, large specific surface area,
crystallinity. However, due to the presence of reversible ultra-low density, and easy-to-regulate structure, which
hydrazone bonds in the hydrazone-MTH-TFPB COF, after makes these materials have great development prospects
24-h treatment with boiling water, strong acid, and base, in important fields such as energy storage materials, gas
its crystallinity decreased significantly, while hydrazide- adsorption and separation, biological drug delivery, het-
MTH-TFPB COF showed excellent stability under simi- erophane catalysis, optoelectronics, and sensing. In this
larly harsh conditions (Fig. 6b). section, we focus on the application of COF porous mate-
Using the representative Groebke–Blackburn–Bien- rials for environmental improvement through their own
aymé (GBB) reaction based on isocyanide chemistry, Liu adsorption separation.
and co-workers constructed a series of pyrimidine-based
COFs from aminopyridine, isocyanide, and aldehyde
monomers in one step [121]. By simply replacing ready- 4.1 Wastewater treatment
made 2-aminopyridine monomers, multiple functions are
integrated from the bottom up. The fused imidazole rings Due to the increase of industrialization in the world, water
commonly formed within the frames ensure their super- resources have been seriously polluted, which has a serious
stability. A work by Zhai and co-workers also shows that threat to the human health and water ecological environ-
integrating methoxy functional groups into the network ment [123]. At the same time, the pollution of a large num-
can improve chemical stability against harsh environments ber of fresh water resources also makes human beings face
[122]. This is due to the delocalization of the electron the problem of exhaustion of water resources [124, 125].
donor group at the vertices from the electron cloud to the Therefore, how to effectively remove the pollutants in the
imine bond via p-π conjugation, thus improving the stabil- water and maximize the use of water resources on the earth
ity of the COFs. In summary, the performance of COFs has become a research hotspot for scientists. Among them,
in environmental remediation is related to their structure. COF is an effective water treatment material because of its
Because the property of MCOFs affected by multiple large specific surface area and high adsorption capacity.
parameters, quantifying the impact of each parameter Table 1 summarizes the separation performance of COF
remains challenging. Therefore, more precise regulation materials in the field of wastewater treatment. This section
is needed in the molecular design of COFs to meet the is divided into three categories according to the types of
growing demand for COF materials.
13
Table 1 Summary of COF materials for wastewater treatment

COFs Reaction monomer Specific surface area Pore size Application Permeance Ref.
TAPB-BMTTPA-COF 1,3,5-Tris(4-aminophe- 1934 m2 g−1 3.2 nm Hg(II) 734 mg g−1 [126]
nyl)benzene
2,5-Bis(methylthio)
terephthalaldehyde
COF-S-SH 2,5-Divinylterephthala- 546 m2 g−1 2.8 nm Hg2+ and Hg0 1350 and 863 mg g−1 [101]
ldehyde
1,3,5-Tris(4-aminophe-
nyl)benzene
T-COF 2,4,6-Tris(4- 328 m2 g−1 19.4 nm Hg2+ 1826 mg g−1 [127]
formylphenoxy)-1,3,5-
triazine
Benzoguanamine
COF2 1,3,5-Triaminobenzene 26.40 m2 g−1 0.327 nm Cr(VI) 649.35 mg g−1 [128]
2,5-Dihydroxyterephtha-
laldehyde
Ni0.6Fe2.4O4-HT-COF Hexachlorocyclo- - - Pb(II) 411.80 mg g−1 [129]
triphosphazene, trithi-
ocyanuric acid, and
Ni0.6Fe2.4O4
TpODH Oxalyldihydrazide 835 m2 g−1 1.99 nm Cu(II) and Hg(II) 324 and 1692 mg g−1 [130]
1,3,5-Triformylphloro-
glucinol
COF-TpAb-AO 2,5-Diaminobenzonitrile 826 m2 g−1 - Uranium 127 mg g−1 [131]
Triformylphloroglucinol
Hydroxylamine
SCU-COF-1 Aminated viologen 22.98 m2 g−1 1.37 nm ReO4− 702.4 mg g−1 [132]
2,4,6-Triformylphloro-
glucinol
Tp-Bpy 1,3,5-triformylphloro- 1 151 m2 g−1 - Acetonitrile 339 L m−2 h−1 bar−1 [133]
glucinol
2,2′-Bipyridine-5,5′-
diamine
TS-COF-1 1,3,5-Tris-(4-aminophe- 1484 m2 g−1 3.1 nm Methylene blue 1691 mg g−1 [134]
nyl)triazine
Triformylphloroglucinol
TpPa-2 1,3,5‒Triformylphloro- 579 m2 g−1 < 2 nm Methylene blue and Removal efficiency of [135]
glucinol rhodamine B 99%
2,5-Dimethyl-p-phe-
nylenediamine
MOF-5/COF MOF-5-NH2 7.025 m2 g−1 - Auramine O and rhoda- 17.95 and 16.18 mg g −1 [136]
Melamine mine B
Terephthaldehyde
COF-SO3Na 1,3,5-Triformylphloro- 179 m2 g−1 1.36 nm Methylene blue and 334 mg g−1 and [137]
glucinol rhodamine B 368 mg g−1
Sodium 2,5-diamin-
obenzenesulfonate
X%[N3]–COFs 1,3,5-Tris(4-aminophe- ≥ 1000 m2 g−1 2.6 nm GenX Removal efficiency of [138]
nyl)benzene 97%
Terephthalaldehyde
A dialdehyde-bearing
azide-functionalized
ethylene glycol side
chains
13
contaminants removed: ions (adsorption of heavy metal Jiang et al. developed a novel imine link stabilized COF
and radionuclide ions), molecules (adsorption of organic (TAPB-BMTTPA-COF; BMTTPA: 2,5-Bis(methylthio)tere-
dye molecules, perfluoroalkanes, and pharmaceutical mol- phthalaldehyde) based on Hg(II)-thionyl linkage chemistry,
ecules), and treatment of bacteria in water. which achieves more efficient removal of Hg2+ from water
under wide pH conditions [126]. The results confirmed that
4.1.1 Adsorption of ions in wastewater water TAPB-BMTTPA-COF could remove more than 99% of Hg2+
within 5 min (Fig. 7c). At the same time, TAPB-BMTTPA-
Since the discharge of heavy metal ions and radionuclide COF showed great Hg(II) ions removal performance under
ions will seriously affect the health of aquatic organisms different pH conditions (Fig. 7d). In addition, repeated cycle
and human beings, how to effectively adsorb and remove stability measurements showed that TAPB-BMTTPA-COF
the two ions is the focus of research on the performance of maintained a great capture efficiency (92%) after 6 cycles
adsorbed materials [139–141]. As a kind of porous mate- (Fig. 7e).
rial with great performance, COFs has been extensively Similarly, Ma et al. treated vinyl functionalized
used in adsorption and removal of radionuclide and heavy mesoporous COF with 1,2-ethyldimercaptan to obtain
metal ions. Among them, the study on the removal of Hg2+ the COF-S-SH material, which achieved high adsorption
is the most systematic and comprehensive [142]. Wang et al. g2+ (1350 mg g−1) and Hg0 (863 mg g−1),
capacities for H
utilized the sulfur-ether functionalized COF material COF- which was much higher than all the mercaptan and thioether
LZU8 for selective sensing and efficient removal of harmful functionalized materials at that time [101]. Laura et al. fur-
Hg2+ (Fig. 7a) [143]. The strong interaction between the ther combined the mercaptan bond with the imine-linked
sulfide group in the COF-LZU8 and Hg2+ makes the fluo- COF to form TPB-DMTP-COF-SH, which showed a great
rescence intensity remain unchanged in three cycles, and the adsorption performance of H g2+ (4395 mg g−1) and a selec-
removal efficiency of Hg2+ is 98% (Fig. 7b). Subsequently, tive removal efficiency of 98% (Fig. 7f and g) [144]. The
Fig. 7 a Schematic illustration of a thioether-based fluorescence g2+ [144]. g Adsorption selectivity of TPB-DMTP-
tion capacity of H
COF (COF-LZU8) for rapid removal and selective detection of Hg2+ COF-SH for Hg2+ in the presence of other ions [144]. h and i The
[143]. b Cyclic stability of COF-LZU8 selectively detects and rapidly influence on the efficiency of Hg2+ by the pH and ambient tempera-
removes toxic Hg2+ [143]. cThe removal process of Hg2+ by TAPB- ture of aqueous solution [127]. j The change of adsorption capacity of
BMTTPA-COF at pH = 7 [126]. d Efficiency of capturing H g2+ under Hg2+ under different pH environments [147]. k The high removal effi-
different pH environments [126]. e Cyclic stability of Hg2+ removal ciency of Hg2+ for M-DAPS50-COF-SH in multiple metal ions [147]
from aqueous solutions [126]. f Comparison of the maximum adsorp-
13
combination of Fe3O4 with porous melamine COF can also has excellent stability under extreme conditions and can
facilitate the removal process of Hg2+ [145]. Moradi et al. effectively remove cadmium cation ( Cd 2+) from aque-
constructed a novel triazine cyclo- COF, showing that a high ous solutions, which is related to the continuous negative
adsorption performance of Hg2+ (1826 mg g−1), which is charge distribution on the surface of CTF-1 and the highly
expected to achieve effective Hg2+ removal in industrial ordered nanopore structure (Fig. 8g and h). Similarly,
wastewater on an industrial scale [127]. In addition, changes nitrogen-rich imine-linked porous COFs are also suitable
in system temperature and solution pH have little effect on as Cd2+ removers, which has been verified in Hatami et al.
the removal efficiency of Hg2+, which is conducive to larger- [154]. Huang et al. prepared functionalized COF of ethyl-
scale application (Fig. 7h and i). Magnetic COF, as a special enediaminetetraacetic acid (COF TpPa-NH 2@EDTA) as
member of COF materials, can also achieve efficient H g2+ an adsorbent for Cu2+ removal (Fig. 8i) [153]. Because
removal after being functionalized by mercaptan [146]. Qin COF TpPa-NH 2@EDTA has a large coordination num-
et al. used a simple salt-mediated crystallization method ber and a large affinity with metal ions, it shows a strong
and cutting strategy to construct mercaptan functionalized adsorption and removal ability (Fig. 8j). In addition, Ye
M-DAPS50-COF-SH (DAPS: 4,4′-diaminodiphenyldisulfide) et al. compared the alkylamine functionalization of COF
that could not be directly synthesized [147]. The composite with different substances and confirmed that the coordi-
structure showed excellent H g2+ adsorption capacity (> 4 nated effect of crystallinity and specific surface area is
times) and excellent selectivity compared with the original conducive to the removal of Cu2+ [130].
M-COF, showing great application potential in the eradica- Compared with the influence of heavy metal ions on
tion of heavy metal ions in polluted water (Fig. 7j and k). human health and environmental protection, the harm
In addition to the adsorption and removal of H g 2+ caused by radionuclides is more serious. Therefore, COF
by COF, removing the heavy metallic ions for instance materials used for adsorption removal of nuclide ions should
Cr6+, Pd2+, Cd2+, and Cu2+ has also received extensive not only have excellent binding affinity and selectivity, but
attention and research. Zhao and colleagues developed a also have fast kinetics and large capacity. Uranium ions
two-pore COF with hydroxyl (COF-BTA-DHBZ; BTA: are often present in soil in the form of hexavalent U O22+
[1,1′-Biphenyl]-3,3′,5,5′-tetracarbaldehyde; DHBZ: easily transferred to water resources. Ma et al. used a two-
3,3′-dihydroxybenzidine) for the removal of C r6+ from step synthesis method (first nitrile functionalization, then
wastewater (Fig. 8a) [148]. The composite structure exhib- amination) to obtain an amidoxime-functionalized COF
its a rapid removal process (adsorption capacity up to material (COF-TpDb-AO; Db: 2,5-diaminobenzonitrile)
272 mg g−1 in 10 min), which is dependent on the hydroxyl (Fig. 9a) [131]. The equilibrium capacity of COF-TpDb-
group attached (Fig. 8b and c). The adsorption capacity of AO for U O22+ reached within 30 min, and more than 99.7%
Cr6+ was greatly affected by changing the distribution of of uranium species were removed within 5 min. At the
hydroxyl group in COF [128]. In addition, the functionaliza- same time, the material exhibited a great adsorption capac-
tion of imine group, carbonyl group, and nanomaterial can ity (127 mg g−1) in seawater samples (Fig. 9b and c). This
effectively regulate the adsorption capacity of COF [107, research can reflect the great potential of COF materials for
149]. Wang et al. designed a salicylaldehyde diamine COF the elimination of nuclide ions. Luo and co-workers used
material (COF-TzDa; Tz: 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) the SO3H− group and the [ NH4]+ group to combine with the
trianiline) to achieve high performance and selectivity for original COF and obtained the [NH4]+[COF-SO3−] complex
Pd2+ removal [150]. The composite structure exhibits excel- structure, which showed strong adsorption removal ability
lent adsorption properties, including great adsorption capac- [155]. Due to the strong coordination capacity of S O32− in
ity (265.4 mg g−1), rapid adsorption kinetics (99.8% removal [NH4] [COF-SO3 ] and the low activation energy of [NH4]+,
+ −
efficiency within 120 min), and good cycle stability (good the material not only exhibits high stability under strongly
performance in 4 cycles) (Fig. 8e and f). In addition, the acidic and alkaline conditions, but also exhibits an extremely
good Pd2+ removal efficiency is mainly related to the syner- high UO22+ absorption rate of 851 mg g−1 (Fig. 9d and e).
gistic chelation reaction between adjacent oxygen atoms and Qiu et al. then designed an ultra-stable SP2-carbon covalent
two free nitrate ions in the structure (Fig. 8d). Similarly, the organic skeleton (COF-PDAN-AO; PDAN: 1,4-phenylen-
interaction force between sulfhydryl and amide groups and ediacetonitrile), which showed excellent uranium adsorp-
Pd2+, electrostatic attraction, and chelation all make COF tion capacity (5 mg g−1) and good structural stability (410
more effective in removing P d2+, confirmed in the study cycles) (Fig. 9f) [156]. The excellent properties are related to
[105, 129, 151]. the abundant uranium chelating groups of COF-PDAN-AO
In addition, the research on the removal of C u2+ and and the excellent regular pore structure. Similarly, the com-
2+
Cd is also worth summarizing and exploring. Ahmad bination of M nFe2O4@TpPa-1 significantly increased the
et al. used a CTF-1 as a co-adsorbent to eliminate Cd2+ adsorption capacity of U O22+ (from 212.1 to 1235 mg g−1),
from aqueous solutions [152]. It was found that CTF-1 which was confirmed by Hu et al. [157].
13
Fig. 8 a Structure diagram of COF-BTA-DHBZ [148]. bTime curve TzDa [150]. f Cyclic stability of P d2+ removal from aqueous solu-
of COF-BTA-DHBZ removal of C r6+ [148]. c Comparison of maxi- tions [150]. g Schematic diagram of CTF-1 adsorption of Cd2+ [152].
6+
mum adsorption capacity of Cr between COF-BTA-DHBZ and dif- h Time kinetics of CTF-1 removal of Cd2+ [152]. i COF TpPa-NH2@
ferent porous materials [148]. d Diagram of the adsorption of P d2+ EDTA schematic diagram of removing metal ions [153]. j Compari-
2+
by COF-TzDa [150]. e Time change curve of Pd removal on COF- son of time kinetics of elimination of different metal ions [153]
In addition to U, rhodium (Tc) is also a highly hazardous effective adsorption removal of 99TcO4− using COF materi-
radioactive toxin, and T cO4− exists as a large stockpile of als. Due to the similarity of electron distribution, spatial
nuclear waste [160]. Therefore, it is important to study the configuration, and thermodynamic parameters between
13
Fig. 9 a A roadmap of functionalized COF-TpAab-AO for prepa- Adsorption kinetics curve of SCU-COF-1 for T cO4− [132]. h Influ-
ration of amidoxime by two-step method [131]. b Kinetics of ence of pH value on the adsorption capacity of SCU-COF-1 [132].
UO22+ removal efficiency of COF-TpDb-AO in different water i Diagram of the interaction between DhaTGCl (Dha: 2,5-dihy-
samples [131]. c Adsorption kinetics of COF-TpDb-AO to UO22+ droxyterephthalaldehyde; TGCl: triaminoguanidinium chloride) and
in seawater [131]. d Diagram of the coordination between ura- adsorbed ReO4− [158]. j Removal performance of cationic pyridin-
nyl ions and [NH4]+[COF-SO3−] [155]. e Adsorption isotherm of ium salt-based COF for radioactive-contaminated drinking water con-
[NH4]+[COF-SO3−] for uranyl ion [155]. f Adsorption properties of taining different concentrations of ReO4− (10 min) [159]
COF-PDAN-AO on UO22+ under different environments [156]. g
eO4− and TcO4−, ReO4− is used as a non-radioactive sub-

R covalent organic nanosheets (iCON DhaTG) prepared by
stitute to simulate the anion exchange behavior of radio- Yan et al. showed strong adsorption capacity (437 mg g−1)
active TcO4−. Albrecht-Schmitt et al. reported a pure inor- and extremely fast reaction kinetics for ReO4− due to electro-
ganic super tetrahedral cation skeleton material (NDTB-1) static attraction and hydrogen bonding (Fig. 9i) [158]. The
that acts as an anion exchanger for adsorption removal of cationic pyridinium salt-based COF (PS-COF-1) adopted by
TcO4− with an exchange capacity of 162.2 mg g−1 [161]. Wang et al. achieved rapid removal of ReO4− from radioac-
This study confirmed the potential application of COF tive-contaminated drinking water (Fig. 9j) [159]. The above
materials in the removal of TcO4−. Wang et al. then inves- research also provides many examples for COF to further
tigated for the first time the removal of 99TcO4− by a 2D control environmental pollution remediation.
conjugated cationic covalent organic skeleton material
(SCU-COF-1) under extreme environments. SCU-COF-1 4.1.2 Adsorption of molecules in wastewater water
not only showed excellent adsorption properties for TcO4−,
including very fast adsorption kinetics (adsorption equilib- As an adsorbent, COF can not only adsorb and remove
rium can be reached within 1 min), ultra-high adsorption metal ions contained in wastewater, but also adsorb vari-
capacity (702.4 mg g−1), and great anion exchange capacity ous organic molecules produced in industrial production.
[132], it also exhibits superior acid stability and radiation Common adsorbable molecules include dye molecules, bis-
resistance (Fig. 9g and h). Similarly, the layered cationic phenol substances, pharmaceutical pesticides, perfluorinated
13
compounds, and other organic molecules. This section will different charges and sizes [164]. The results show that the
summarize in detail the adsorption removal of dye molecules COF membrane has a high removal rate for potassium per-
by COF materials. manganate (98.1%), fluorescein sodium salt (99.2%) and
Dye discharge not only affects the safety of the environ- anionic dye MO (99.6%), and also has a high removal rate
ment, but also seriously affects the health of organisms and for cationic dyes RB (91.2%), MB (87.2%), and n, n, n-dime-
human beings. However, due to the complex aromatic struc- thyl-p-phenylenediamine hydrochloride (84.9%). However,
ture of dye molecules, most synthetic dyes cannot be biode- the retention rates of neutral dyes (CA: 74.4%, Nile red:
graded. It is therefore important to study efficient adsorp- 22.3%, p-nitroaniline: 15.7%) were low (Fig. 10g). Mean-
tion materials. Among them, COF adsorption is one of the while, the removal efficiency of MO by EB-COF:Br film
methods to be considered. Earlier, Shen et al. synthesized remained > 99% in all 5 cycles (Fig. 10h). The above experi-
magnetic porous covalent triazine matrix composites (CTF/ mental results also indicate that the opposite charge of dye
Fe2O3) by microwave enhancement, which showed good molecules and COF is conducive to the removal of dye mol-
adsorption capacity for methyl orange (MO) [162]. CTF/ ecules, which corresponds to the study of Li et al., in which
Fe2O3 showed high MO adsorption capacity (291 mg g−1) 2D polycationic COF (PC-COF) shows high absorption
and fast adsorption kinetics (kads = 4.31m2 mg−1 min−1), capacity of anionic organic dye pollutants in water [165].
which is related to the wide pore size distribution of the Fan et al. prepared 2D imine-linked COF films (COF-LZU1)
composite. Kharul et al. constructed four COF films with on tubular alumina carriers, which showed high selectivity
different pore sizes (Tp-Azo, Tp-Bpy, Tp-Tta, and Tp-Ttba; in the dye separation in brine [48]. Similarly, the removal
Bpy: 2,2′-bipyridine-5,5′-diamine; Tta: 4,4′,4″-(1,3,5-tri- effect of different dye molecules related to the pore size and
azine-2,4,6-triyl) trianiline; Ttba: 4,4′,4″-(1,3,5-tria- the charge carried by the dye (Fig. 10i). Besides, the permea-
zine-2,4,6-triyl) tris(1,1′-biphenyl) trianiline) to further tion flux of COF-LZU1 in aqueous solution can reach 760
explore the adsorption effect of COF films on dye molecules L m−2 h−1 MPa−1, and the waste rate of chromium black T
(Fig. 10a) [133]. For Congo red (CR), bright blue-G (BB), remains unchanged (~ 99%) in 80 h (Fig. 10j). Later, Rahul
Rhodamine B (RH), and acid fuchsia (AF), the removal et al. synthesized four kinds of COF foams using in situ
efficiency of Tp-Bpy was up to 80% (CR), 94% (BB), 98% vapor phase foaming scheme to achieve efficient and rapid
(RH), and 97% (AF). The efficiency of TP-azo was 79% adsorption removal of dye molecules [135]. These COF
(CR), 90% (BB), 99% (RH), and 99% (AF) (Fig. 10b). In foams can separate various dyes (such as, RB, MB, AF, and
addition, the Tp-Bpy film remained stable over 5 cycles Bengal rose) from water within 10 s, with a > 95% removal
when AF was removed (Fig. 10c). efficiency (Fig. 10k). At the same time, the change of pH
In the same year, Dai et al. used mesoporous triazine did not affect the adsorption and removal efficiency of COF
functionalized polyimide COFs to obtain excellent adsorp- foam on dyes (Fig. 10l). Later, Xiao et al. prepared the COF
tion properties of methylene blue molecules (maximum of three fluorene by changing the drug in COF synthesis,
adsorption capacity:1691 mg g−1) [134]. This study con- showing a high RB adsorption capacity (2127 mg g−1) and
firmed that the adsorption properties of COF materials to a high removal efficiency (99.5% in 5 min) [166].
dye molecules are related to the internal pore size. Similarly, Compared with a single COF material, the composite
Lu et al. investigated the adsorption behavior of salicylani- material composed of COF has a large specific surface
line-based COFs (SA-COF) on dye molecules of differ- area, which shows a higher removal efficiency [167]. Wang
ent sizes [163]. Three dye molecules, Rhodamine B (RB), et al. combined COF microcrystals with polysulfone (PSF)
Chrome-blue copper S (CA), and methylene blue (MB), ultrafiltration substrates to form a TpPa/PSF membrane,
were selected as the study objects (the pore sizes of the three which demonstrated a stable 99.5% removal rate of Congo
molecules were MB < RB < CA). The results showed that red and a water permeability of up to 50 L m−2 h−1 MPa−1,
the affinity of SA-COF to binding dye molecules decreases which is 2–10 times higher compared with many filtration
with the increase of molecular size (Fig. 10d). MB was films [168]. Similarly, Jiang et al. constructed a high-water-
completely removed in 98 min, while the concentration of flux TpPa-1/HPAN membrane with excellent separation
CA remained largely unchanged (Fig. 10e). In addition, the performance by growing a TpPa-1 layer on a polyacryloni-
obvious contrast of MB removal efficiency under acidic and trile (PAN) porous substrate [169]. The TpPa-1/HPAN film
alkaline conditions also confirms that electrostatic attraction exhibits a highwater flux (418.5 L m−2 h−1 MPa−1) and good
plays an important role in dye adsorption (Fig. 10f). dye separation properties (93.91% for Orange GII; > 99%
As for the effect of electrostatic attraction and pore size for Congo red, Alsin Blue, and MB), as well as excellent
on the adsorption of dye molecules, the same proof was acid–alkali resistance and stability over 200 h. In the above
obtained from Ma et al. They constructed a 2D cationic COF research, the price of the substrate material is low, which is
composed of EB-COF:Br (EB: ethidium bromide) film to beneficial to the application and large-scale production of
investigate the adsorption properties of dye molecules of composite film.
13
Fig. 10 a Schematic diagram of selective molecular separation of Removal rate of different dyes by EB-COF:Br film [164]. h Cyclic
covalent organic skeleton films constructed by interfacial crystalliza- stability of EB-COF:Br membrane for MO removal [164]. i Water
tion [133]. b Removal efficiency of Tp-Azo and Tp-Bpy films for dif- permeability and removal rate of COF-LZU1 membrane for differ-
ferent dye molecules [133]. c Cyclic stability of Tp-Bpy films [133]. ent dye solutions [48]. j Cyclic stability test of COF-LZU2 membrane
d Change of dye concentration with time after SA-COF adsorption for removal of chromium black dye [48]. k Kinetics of TpPa-2 foam
[163]. e Size-selective separation of different dye molecules [163]. adsorption of different pollutants [135]. l Adsorption kinetics of COF
f Charge selective separation of different dye molecules [163]. g foam at different pH [135]
The pore size structure of graphene, graphene oxide, and COF-1 to construct a high-throughput hybrid 2D GO/COF-1
MOF material itself combined with COF composite material nanocomposite (Fig. 11a) [171]. The GO/COF-1 nanocom-
can effectively improve the removal efficiency of dyes [170]. posites exhibited good water permeability (water permeance:
Firstly, Zhang et al. combined graphene oxide (rGO) and 310 L m−2 h−1 MPa−1) and stability (3 days) and showed a
13
Fig. 11 a Schematic diagram of the GO/COF-1 nanocomposite selec- e Cyclic stability of M5C composites for removal of dye molecules
tively separating dye molecules [171]. b Determination of rejection [136]. f Adsorption and removal of MG from wastewater by Cage-
rate and water permeance of GO/COF-1 adsorbing different dye mol- COF-TP [173]. g Comparison of adsorption equilibrium time of Rho-
ecules [171]. c Stability test of GO/COF-1 [171]. d Interaction mech- damine B (RhB) by COF powder and CGA [137]. h Mechanism dia-
anism diagram between dye molecules and M5C composites [136]. gram of adsorbing dyes on ultra-thin COF [137]
retention rate of > 99% for water-soluble dyes (Fig. 11b and of AO and RB molecules in all 6 cycles (Fig. 11e). Besides,
c). The good properties of the composite are directly related the construction of certain-shape COFs structure can help to
to the introduction of GO pores and the electrostatic attrac- increase the adsorption site, affinity of dye molecules, and
tion of GO to dye molecules, which has the potential to treat improve the removal efficiency of dye molecules. Wang et al.
dye wastewater. Similarly, Sun et al. constructed a HP-COF- constructed a Cage-COF-TP (T: bis(tetraoxacalix[2]arene[2]
TpPa/GO (HP: hot-pressing) composite membrane using hot triazine); P: piperazine) material for the removal of mala-
pressing method, showing high water permeability (166.8 chite green (MG) molecules [173]. Due to the high matching
L m−2 h−1 bar−1) and significantly improved removal rates, of MG size and shape to the constricted channels in Cage-
which are related to the aperture channel and enhanced affin- COF-TP and the enhanced affinity of the nitrogen-rich tria-
ity of the introduction of GO [172]. Kheibar et al. constructed zine unit, Cage-COF-TP can remove 200 mg g−1 MG from
a new hybrid material MOF-5/COF (M5C) by hybridization wastewater at ambient temperatures (Fig. 11f). Later, Freddy
of zinc-based metal MOF-5 and COF materials [136], and et al. constructed a three-dimensional ultra-light COFs/gra-
the M5C composite realizes the efficient and rapid removal phene aerogel (CGA) based on anthraquinone [137]. In the
of auramine O (AO) and RB dyes from aqueous solutions composite material, COFs and rGO work together to provide
by means of hydrogen bonding, electrostatic, π-π stacking, conjugated structure and negative charge on the surface of
and Lewis acid–base interaction (Fig. 11d). Moreover, M5C the material, which is beneficial for the dye molecules to
maintained a removal efficiency of > 90% for the removal bind to the composite through intermolecular H bond, π-π
13
interaction, and electrostatic attraction, thus greatly short- pH range, and excellent renewability when removing BPA
ening the adsorption time of dye molecules by the aerogel molecules (Fig. 12c and d). Simultaneously, further theo-
(Fig. 11g and h). retical calculations confirmed that bisphenol was mainly
Bisphenol A (BPA) is a common endocrine disruptor, removed by complexation with the phenolic (C=O) groups
which is widely found in water environments. It will be of TpND. In the same year, Hu et al. prepared magnetic
transferred to the food, further accumulation into the bio- COFs with β-ketoimine bonds (Fe3O4@TpPa-1), which
logical body, and the human health has a great harm [107]. significantly improved the BPA adsorption capacity [149].
Therefore, a suitable adsorbent (e.g., COF) is selected to Fe3O4@TpPa-1 showed excellent adsorption capacity for
remove BPA by adsorption. Among them, the magnetic COF BPA (maximum adsorption capacity: 1220.97 mg g−1),
composites have been used in the removal of BPA [174]. which is related to the uniform distribution of imine and
Yan et al. prepared F
e3O4@TpBD magnetic core-shell car- carbonyl functional groups of TpPa-1, the presence of
bon nanospheres, which can rapidly remove BPA, from hydrogen bonds in the frameworks, and π-π interaction
the aqueous solutions (the equilibrium maximum adsorp- (Fig. 12e). Compared with 2D COF material, 3D structure
tion capacity reached 160.6 mg g−1 within 5 min) [175]. has higher specific surface area and more abundant reaction
Ye et al. combined 2D COF powder into layered porous sites. Xie et al. firstly combined 3D COFs with magnetic
whole M16, showing strong retention and rapid adsorp- nanoparticles to construct F e3O4@3D-COF-TpTAM (TAM:
tion of BPA in water media (Fig. 12a) [176]. Due to π-π tetra(p-aminophenyl)-methane) composite material [178].
interaction and hydrogen bond interaction, M16 contain- Fe3O4@3D-COF-TPTAM showed higher BPA adsorption
ing 28% COF has a 61.3 mg g−1adsorption capacity after capacity (maximum adsorption capacity of 209.9 mg g−1)
removing 29 mL of 22.8 mg L −1 BPA solution (Fig. 12b). than 2D-COF. In addition, the recoveries of BPA from
Later, Wang et al. successfully synthesized Fe3O4@TpND Fe3O4@3D-COF-TpTAM in milk and river samples ranged
(ND: 1,5-naphalenediamine) composite structure by sol- from 93.8 ± 1.4% to 101.4 ± 5.1% and 100.4 ± 1.9% to
vothermal method, which was also used for BPA removal 107.3 ± 1.2%, respectively (Fig. 12f). On the one hand, the
[177]. Fe3O4@TpND has good adsorption capacity (up to excellent adsorption properties of BPA related to the pore
114.97 mg L−1, 298 K, pH 6.0), fast absorption rate, wide size matched by the complex material. On the other hand,
Fig. 12 a Process diagram and characterization of multistage porous BPA removal [177]. e Adsorption mechanism diagram of BPA at
monolithic M16 constructed with COF powder [176]. b Removal effi- Fe3O4@TpPa-1 [149]. f Adsorption kinetics of BPA on Fe3O4@COF-
ciency of BPA by M16 adsorption [176]. c Adsorption kinetics curve TpTAM [178]
of BPA at F e3O4@TpND [177]. d Fe3O4@TpND cyclic stability of
13
the presence of hydroxyl and amino groups enhances the can completely separate TC and CTX within 2 s, and kinetic
adsorption capacity by forming hydrogen bonds with BPA. data show that the maximum adsorption capacity of CTX
The widespread use and discharge of pharmaceutical and TC is 309.26 and 388.52 mg g−1, respectively (Fig. 13a
and pesticide products have also caused great harm to bio- and b). The adsorption mechanism of TC is characterized
logical health and the environment. Rahul et al. prepared by complexation, cation exchange, electrostatic attraction,
flexible continuous COF films (COMs) for the extraction hydrogen bond, and π-π interaction. For CTX, the adsorp-
of active pharmaceutical ingredients (APIs) in organic sol- tion theory includes electrostatic attraction, condensation
vents, showing high throughput in different solvents [179]. reaction, π-π interaction, and hydrogen bond (Fig. 13c).
Later, Duan et al. constructed NiFe2O4/COF/CS/TPA nano- Xia et al. used 2D nanosheet structure Fe(III) functional-
composite films (NCCT) for the adsorption of cefotaxime ized magnetic COF (MCOF(Fe)) to remove the nonsteroi-
(CTX) and tetracycline (TC), which showed a super-fast dal anti-inflammatory drug phenylbutanone from aqueous
adsorption process [180]. As a thin film adsorbent, NCCT solution through π-π interaction, hydrogen bonding, and
Fig. 13 a and b Adsorption properties of TC (a) and CTX (b) on of pH value on adsorption capacities [83]. f Regeneration efficiency
NCCT [180]. c Adsorption mechanism of CTX and TC on the surface of Fe3O4@COF-TpDBd [83]. g Interaction between QN and Fe3O4@
of NCCT [180]. d Adsorption of MCOF (Fe) in different samples, COF-TpDBd at different pH values [83]
including deionized water, tap water, and lake water [181]. e Effect
13
electrostatic interaction [181]. By comparing the adsorp- skeleton M-TpPa-SO3Na, which utilized its high affinity
tion properties of MCOF(Fe) for phenylbutanone in deion- with p-benzoylurea (BU) insecticides to achieve a more
ized water, tap water, and lake water, it was found that the efficient recovery of BU in different samples [183].
adsorption capacity of MCOF(Fe) for phenylbutanone was Perfluorinated compounds are synthetic compounds
very similar, which also provided theoretical evidence for whose carbon backbone is surrounded by fluorine atoms,
the removal of phenylbutanone in actual samples (Fig. 13d). used in textiles, dyes, and other applications. However, resi-
Recently, Feng et al. designed magnetic carboxyl-function- due in the environment will cause a great harm [184]. There-
alized COFs (Fe3O4@COF-TpDBd; DBd: 4,4′-diamino- fore, developing effective adsorbents to remove perfluori-
[1,1′-biphenyl]-2,2′-dicarboxylic acid) as new adsorbents nated compounds is essential. William et al. constructed a
for quinolones (QNs) [83]. Fe3O4@COF-TpDBd exhibited hexagonal-imide-linked 2D COF material (X%[N3]-COFs,
fast adsorption kinetics (10 min) and significantly great where X stands for amine loading) that rapidly adsorbed
adsorption capacity (removal efficiency > 92.5%) in the perfluoro-2-propoxy-propionate (GenX) in water (Fig. 14a)
neutral conditions, while the adsorption capacity remained [138]. As 20%[NH2]-COF exhibits a 240 mg g−1 maximum
above 80% after 80 cycles (Fig. 13e and f). In addition, the adsorption capacity, which is the result of synergistic inter-
adsorption capacity of Fe3O4@COF-TpDBd varies under action between polar groups and hydrophobic surfaces
different pH conditions, related to the electrostatic force of (Fig. 14b). Later, Deng et al. synthesized hexagonal COF
the surface (Fig. 13g). In addition to drug molecules, the with double-pore structure and investigated the mechanism
adsorption removal of pesticides is also extremely important and adsorption behavior of GenX and hexafluoropropyl-
[182]. Wang et al. constructed a magnetic covalent organic ene oxide trimer acid (HFPO-TA) [185]. The capacity of
Fig. 14 a Schematic diagram of

the amine-functionalized COFs
to remove GenX from water
[138]. b Relationship between
amine load and GenX removal
efficiency [138]. c Comparison
of GenX adsorption by different
adsorbents [185]. d Adsorp-
tion kinetics of GenX [185]. e
COF-mixed matrix membrane
used for adsorption and removal
of bovine serum protein [193].
f The adsorption capacity curve
varies with the concentration of
TCS and TCC [192]
13
COF supported by quaternary ammonium groups for GenX by itself, contain some groups (guanidine and pyridinyl) or
is 2.06 mmol g−1, and the adsorption equilibrium reached grafted antibacterial substances (drug molecules or biologi-
within 5 h, exceeding that of many porous adsorbents cal enzymes) to destroy the cell wall of bacteria, to achieve
(Fig. 14c and d). The interaction between anion exchange on the purpose of killing bacteria [194].
quaternary ammonium group and hydrophobic correlation First of all, COF materials could control the growth of
of COF hydrophobic group has a great impact on the high- bacteria and achieve the purpose of antibacterial by grafting
performance removal of GenX from water. Similarly, Shu some groups with antibacterial properties (such as antibod-
et al. also constructed CTF/Fe3O4 containing amine groups, ies and biological enzymes) or changing their own structure
and the maximum adsorption capacity for sodium per- [195]. Ayyappanpillai et al. reported a method using cucur-
fluoronoxybenzenesulfonate (OBS) and hexafluoropropyl- bit[7]uril (CB[7]) to induce reversible spalling, repacking,
ene oxide triacid (HFPO-TA) was 1.18 and 1.02 mmol g−1, and surface charge control of the propidium iodide-based
respectively, due to the increased affinity of the ammonium ionic COF (PI-TFP) for bacterial growth control [196]. After
group [186]. In addition, the introduction of amino group is adding CB, the number of E. coli was 90% and Staphylo-
beneficial to the removal of perfluorinated compounds in coccus aureus was 95% (Fig. 15a). Later, the addition of
water, which has also been verified in the report of Fe3O4@ 1-amantadine hydrochloride (AD) reduced the number of E.
[NH2]-COF synthesized by Zhao et al. [187]. coli to 51% and Staphylococcus aureus to 57% (Fig. 15b). In
In addition to the above molecules, a number of other addition, the absence of any antibacterial activity on the sur-
compounds, such as bovine serum albumin, triclosan, face of neutral COF DPP-TFP (DPP: 3,8-diamino-6-phenyl
monoaminoneurin, nitro-aromatic compounds, Benzo[a] phenanthridine) proves that the destruction of the cell wall
pyrene, and flavonoids, were removed by adsorption with by ionic charges is the cause of bacterial death (Fig. 15c).
COF materials [188–193]. Katie et al. used carboxyl- Similarly, Zhou et al. constructed a novel antimicrobial agent
functionalized covalent organic skeleton and polyacrylonitrile (DC-COF-SNP; DC: dual-cationic) based on the active bi-
(PAN) to form a mixed matrix membrane (MMM) for cationic COF encapsulation of sodium nitroprusside (SNP)
adsorption and separation of bovine serum protein (Fig. 14e) compounds, which also inhibits gram-positive and gram-
[193]. Compared with the original PAN membrane, the PAN negative bacteria by destroying the negatively charged cell
MMM with a COF of 0.8 wt% showed a high-water flux membrane of bacteria [197]. Tian et al. formed Ag/COFTET2
of 940 L m −2 h−1 MPa−1, better protein adsorption, and by combining guanidine-containing cation COFTET2 with Ag
thermal stability. In the same year, Cai et al. constructed particles, which also used cell wall destruction to inhibit
core-shell magnetic COF nanocomposites (Fe3O4@COFs), bacteria [198]. The damage of Ag/COFTET2 to bacterial cell
which showed high adsorption capacity and rapid adsorption wall was demonstrated by comparing the morphological
behavior for triclosan (TCS) and Triclocarban (TCC) [192]. changes of E. coli (Fig. 15d and e). Similarly, Shen et al.’s
By comparing the adsorption properties of Langmuir and PCOF@E-Exo composite also kills gram-negative, gram-
Freundlich isotherms, F e3O4@COFs exhibits multi-layer positive, and drug-resistant bacteria by destroying bacterial
adsorption through the interaction of van der Waals force, cell membranes and biopermeable membranes [199]. In
π-π packing of benzene ring and spatial embedding effect, in addition to guanidine group, the grafting of pyridine group
the low concentration range, and then Fe3O4@COFs through on COF material can also effectively prevent the growth
the single-layer adsorption of strong π-π packing in the high of bacteria [200]. In addition, in bacteriostatic studies, the
concentration range (Fig. 14f). Among them, the removal minimum concentration of Ag/COFTET2 to inhibit Escheri-
efficiency of TCC and TCS in fetal bovine serum (FBS) was chia coli and Staphylococcus aureus can reach 100 and
at least 10 times higher (82.3 to 95.4%), recovery rate (92.9 50 µg mL−1, respectively.
to 109.5%) and reuse rate. In addition, COF materials can also inhibit bacterial
growth by promoting the release of bactericidal drugs [201].
4.2 Antibacterial application For example, Dai et al. used the construction of ENR-FM-
COF-TPU composite material ((a β-cyclodextrin covalent
Bacterial resistance has become one of the serious threats to organic framework loaded with enrofloxacin and flun-
human health worldwide. In addition to the rapid replication ixin meglumine)-incorporated enrofloxacin thermoplastic
and high mutation rate of bacteria, the overuse of existing polyurethane fibers) to achieve continuous drug release of
antibiotics to treat disease, their use as growth promoters enrofloxacin and flunixin meglumine lasting 50 h, showing
in livestock production, and inappropriate release in the strong antibacterial activity against Staphylococcus aureus
environment further exacerbate the emergence and spread and E. coli with inhibition efficiency of 99% (Fig. 15f and
of antibiotic-resistant pathogenic bacteria. Therefore, select- g) [202]. Similarly, levofloxacin-coupled Zn-nMOF con-
ing suitable and effective materials for bacterial removal is structed by Shakir et al. (Levo@Zn-nMOF) was used in
important. COF materials used in antibacterial, generally the removal of Pseudomonas aeruginosa, Escherichia coli,
13
Fig. 15 a and b Changes in the number of E. coli (a) and Staphylo- absence (d) and presence (e) of Ag/COFTET2 (scale bar: 2 µm) [198].
coccus aureus (b) samples in the presence of different COF nanoma- f and g Antibacterial activity against E. coli (f) and Staphylococcus
terials [196]. c Number changes in the of E. coli samples under differ- aureus (g) [202]. h Schematic illustration of enhanced bacterial inhi-
ent treatments [196]. d and e Morphological changes of E. coli in the bition by MOF@COF nanozyme [204]
Bacillus subtilis, and Staphylococcus aureus [203]. The water vapor under different conditions, as well as the syn-
removal efficiency of levofloxacin was increased by 1.03, thesis of novel nanomaterials with long-term use, improved
1.5, 1.71, and 1.65 times, respectively. Qu et al. constructed absorption properties, and recycling possibilities is one of
a MOF@COF nanozyme (NMCTP-TTA) for the first time to the hotspots of research [205]. The COF material is an effi-
enhance bacterial inhibition [204]. The topological interac- cient adsorbent for absorbing water vapor in the air because
tion between COF and bacteria is beneficial to the capture of of its strong porous adsorption force and stability under
bacteria. In addition, MOF grafting also effectively inhibited humid conditions [206]. Initially, Banerjee et al. constructed
bacterial growth (Fig. 15h). a series of COF materials through pore surface engineer-
ing and investigated their water vapor absorption properties
4.3 Atmospheric water capture [207]. Comparing with other reported COFs, TpPa-1 shows
the highest water uptake (368 cm3 g−1, about 17 mmol g−1,
Maintaining the right level of humidity in the air is essen- P/P0 = 0.3). Lotsch et al. precisely tuned the chemistry of
tial to protect the whole ecosystem. The development of the pore wall, explored water vapor absorption properties of
advanced environmentally friendly technology to adsorb COFs, and confirmed that COFs with high nitrogen content
13
has high hydrophilicity [208]. In the same year, they also small pore size and hydrophilic surface are conducive to the
performed the first atmospheric water harvesting using iso- use of COF for water vapor adsorption when at low relative
structural azine-linked COF (ATFG-COF and AB-COF; humidity. Since then, more and more studies conducted on
AB: azine-benzene; ATFG: azine-triformylphloroglucinol) the use of COF materials to adsorb water vapor.
as adsorbents [209]. AB-COF with lower polarity exhibits a Yaghi et al. report a novel porous imine-linked COF
reversible water capture-release process, with a water vapor (COF-432) with void square mesh topology that exhibits an
absorption capacity of 28 wt% at low pressure (0.3 pp0−1). S-shaped water absorption isotherm at low relative humidity
Li et al. then used grand canonical Monte Carlo (GCMC) and excellent hydrolytic stability (stable over 300 cycles),
simulations to study the water vapor adsorption behavior of meeting the requirements required to collect water from
COF materials [210]. The simulation results show that the air (Fig. 16a) [211]. Li et al. build a 3D layered structure
Fig. 16 a COF-432 water absorption isotherm at low relative humidity [213]. f Schematic diagram of DHTA-Pa COF for rapid adsorption of
(left) and hydrolytic stability (right) [211]. b The relationship between water and evaporation [214]. g Comparison of water adsorption and
outdoor solar exposure conditions, light duration, and pure water col- desorption of different adsorbents [214]. h Apparent water vapor des-
lection [212]. c and d Adsorption isotherm of AB-COF and COF- orption rates compared with multiple porous adsorbents [214]
480-hydrazide to water [213]. e Stability test of adsorbed water vapor
13
(COFHS: COF-based hierarchical structure), which is used trianiline; FMTA: 5′-(4-formyl-3-methoxyphenyl)-3,3″-

to efficiently collect solar steam [212]. The water collection dimethoxy-[1,1′:3′,1'' terphenyl]-4,4''-dicarbaldehyde;
device prepared by COFHS can achieve a high-water col- TMTA: 2,4,6-trimethoxybenzene-1,3,5-tricarbaldehyde)
lection efficiency (10.2 L m −2 day−1) that can be achieved constructed by Luo et al. by integrating methoxy functional
under natural solar irradiation (Fig. 16b). Yaghi et al. then groups into the network also obtained 5.07 and 3.21 g g−1
synthesized a series of COFs with two- and 3D hydrazine- adsorption capacity, respectively, due to the abundant het-
hydrazide connections [213]. Among these COFs, there are eroatoms and excellent porous structure in the pore chan-
hydrazine-hydrazide junction COFs that can collect water nels [122]. The adsorption of I2 vapor is not only related
from the air under dry conditions. The COF exhibited a to the pore size, but also affected by the binding energy of
characteristic S-shaped water absorption profile with a total I2 molecules [219]. For example, Liu et al. selected three
0.45 g g−1absorption capacity (Fig. 16c and d). The COF COFs (TFB-Td COF TFB-DB COF, and TFB-BD COF;
material remained stable for 85 cycles (Fig. 16e). Recently, Td: 4,4′-diamino-p-terphenyl; DB: 1,4-diaminebenzene)
Xiao et al. studied the water adsorption behavior and princi- connected by C=N as experimental subjects and found that
ple of DHTA-Pa COFs (DHTA: 2,4-dihydroxybenzene-1,3,5- the I2 capture capacity of TFB-DB COFs connected by C=N
tricarbaldehyde) [214]. At 2% relative humidity, the water reached 6.4 g g−1 (640% by mass) I2 vapor absorption [220].
absorption of DHTA-Pa COF can reach 1.0 g g−1, with an In the same year, Yu et al. constructed ionic COFs
adsorption rate of 48.30 L Kg−1 h−1 and a desorption rate (iCOFs) with high pore volume, abundant binding sites, and
of 72.298 L K g−1 h−1 (Fig. 16g). In addition, more than large specific surface area, for capturing I2 vapor [221]. The
333% adsorbed water was released within 90 min at 58 K optimized material iCOF-AB-50 exhibits a static I2 uptake
(Fig. 16h). The excellent water absorption characteristics capacity (75 °C, 10.21 g g−1) and dynamic uptake capacity
related to the hydrophobic skeleton of two-dimensional cova- (25 °C, 2.79 g−1, about 400 ppm I 2), which is much higher
lent COFs, appropriate hydrophilic point density, and one- than many current porous materials (Fig. 17d and e). Density
dimensional open channel significantly reducing the water functional theory (DFT) calculation confirmed that ionic
diffusion and desorption energy barrier (Fig. 16f). Compared modification brought more and stronger binding sites to I2
with other applications, the use of COF materials for atmos- and formed thermodynamically more stable complexes with
pheric water collection is still in the early stage of research, adsorbed I2 through coulomb interaction, thus adsorbing to
and more exploration is still needed [215, 216]. the COF framework, which was more favorable for the cap-
ture of I 2 (Fig. 17f). Later, they reported that a novel guani-
4.4 Adsorption of radioactive iodine vapor din-based COF (TGDM) achieved 30 wt% absorption under
industrial conditions (150 ℃, 150 ppmv). The excellent
The introduction of volatile iodine (I2) into the air can cause adsorption capacity is related to the increase of binding sites
radioactive environmental pollution lasting 100,000 years, by ion modification [222]. In addition, their further study
leading to an increased incidence of thyroid disease. Devel- found that adsorption I 2 can occur at various adsorption sites
oping materials that achieve zero emissions of radioactive and can be facilitated by intermolecular interactions (such as
steam is critical, but still challenging. In this respect, the Colombian force) [223]. The above adsorption principle was
construction of novel materials that effectively capture demonstrated by the effective increase of I 2 vapor adsorp-
iodine is necessary and urgent. COFs shown to be an effec- tion (3.73 g g−1) of NH2-UiO-66@Br-COFs hybrid material
tive platform for molecular adsorption and separation, and designed by Liu et al., compared with a single COF material
there have been many studies on I2 adsorption. Gao et al. [224]. In the same way, The sp2-carbon connected 2D sp2-c-
have designed 3D COF-DL229 material with a diamond COFs (COF-p-NEU2 and COF-p-NEU1) designed by Chen
(dia) topology that achieves better contact with I2 vapor et al. also showed excellent capturing ability (5.87 g g−1 and
(Fig. 17a) [217]. At 75 ℃ and ambient pressure, COF-DL229 4.58 g g−1) of I2 vapor in cyclohexane due to suitable pore
achieved the I2 adsorption capacity (4.7 g g−1) by forming a structure (4.93 nm and 4.82 nm) and abundant nitro (reac-
complex through charge transfer. Li et al. then constructed a tion site) [225].
stable nitrogen-containing COF (TAPA-PDA COF) for effi- Recently, Li et al. constructed defects 4F-iCOF-
cient and reversible capture of volatile I 2 [218]. TAPA-PDA TpBpy-I (Bpy: 5,5′-diamino-2,2′-bipyridine) and
COF has an extremely high capture rate of up to 5.09 g g−1 4 CH 3 -iCOF-TpBpy-I by manipulating two adsorption
for I2 and maintains good stability over 5 cycles (Fig. 17b). sites located in adjacent spatial locations (Lewis’s binding
The formation of polyiodide compounds by charge transfer sites and ion-binding sites). The 4 CH3-iCOF-TpBpy-I and
between the adsorbent and iodine molecules was confirmed 4F-iCOF-TpBpy-I provide ultra-high I 2 absorption of 34.8
by the Raman spectroscopy, thus showing high adsorption wt% and 37 wt% (> 150 °C, < 150 ppMV-i), respectively
capacity (Fig. 17c). Similarly, the TTA-FMTA-COF and [226]. The good amount of I 2 absorption is the result
TTA-TMTA-COF (TTA: 4,4′,4″-(1,3,5-triazine-2,4,6-triyl) of synergies between adsorbed I2 and the interaction of
13
Fig. 17 a Adsorption of I2 vapor by 3D COF-DL-229 [217]. b The ties of iCOF [221]. f Comparison of DFT calculation of iCOF-AB-50
amount of iodine absorbed changes with time [218]. c Raman char- and COF-OH-50 [221]. g Interaction of I2 and pyridine N sites in
acteristic of TAPA-PDA COF before and after multiple I2 adsorption 4F-iCOF-TpBpy-I [226]. h Schematic illustration of COF hybrid
cycles [218]. d and e Static (d) and dynamic (e) I2 adsorption proper- aerogel for I2 capture [227]
pyridine N (as IBS) through coulomb forces and with pyr- 4.5 Control of air pollutants
idine N (as LBS) through electron transfer (Fig. 17g). In
addition to composite materials, Wang et al. will encapsu- The increase in energy consumption by industrial produc-
late nanoscale COF particles into functionalized cellulose tion has led to the release of a great deal of C
O2 into the
and then freeze-dry to create mixed aerogels for efficient atmosphere and caused a sudden rise in the Earth’s temper-
I2 capture and recovery (Fig. 17h) [227]. ature [228, 229]. Reducing its impact on the environment
13
can be achieved by developing cost-effective and relatively beneficial to the separation of wet flue gas by using machine
simple techniques for separating C O2 from flue gas [230]. learn-assisted Monte Carlo computation to screen 516
Researchers have done extensive research on C O2 capture experimental COFs [236]. The “electron-donating-induced
materials [231], CO2 reduction [232], and efficient mem- vdW interaction” effect is conducive to the construction
brane separation of C O2 [233]. Solid adsorption is consid- of COFs with better performance, which can achieve high
ered an economical and least intrusive method for capturing CO2 uptake (4.4 mmol g–1) and the selectivity of C O2/N2
CO2, as it can achieve the goal of little energy loss and few (104.8) (Fig. 18a). Similarly, Smet et al. used functionalized
modifications to power plants. Among them, COF material (with Me, OMe, Cl, F, N O2, CF3) amine regulators to study
is a highly efficient adsorbent for flue gas separation [234]. the influence of COF functional groups on the selectivity
Molecular simulations are beneficial to study the applica- of CO2/N2 gas separation in flue gas [237]. Benzidine has
tion of COFs in flue gas separation [235]. Tong et al. con- the highest reactivity of all functionalized COFs (Fig. 18b).
firmed that COFs with tetraphenyl porphyrin units are more Li et al. designed a porous composite bimetallic organic
Fig. 18 a Schematic diagram of COF material used for capturing C O2 ethylenepentamine) at different temperatures at 1 bar (c) and 0.1 bar
in wet flue gas by computer-aided design [236]. b Selectivity of func- (d) [239]. e Flue gas separation properties of the original iCOF and
tionalized COF with different functional groups for C O2/N2 gas sepa- iCOF@PEI membranes (PEI: polyethylenimide) [240]. f Schematic
ration in industrial flue gas [237]. c and d Adsorption and desorption diagram of CO2 adsorption separation on the iCOF@PEI membrane
isotherms of C O2 by COF-1 and TEPA(n)-COF-1 (TEPA: tetra- surface [241]
13
framework-derived magnetic catalyst (Ni/Fe@COF) show- structure, host, and guest composition of COF materials
ing a high CO2 desorption rate of 1.88 mmol min−1 g−1 from play an important role in the properties and application
industrial flue gas at 290 ℃, which is significantly improved principles of COF nanomaterials. By introducing special
by 540% compared with traditional thermal desorption [238]. active sites or surface modification of special functional
Zhao et al. found the COF-1 modified with oligoamine groups, the adsorption capacity of COF materials can be
(TEPA) not only to improve its water stability, but also to improved. However, more advanced characterization meth-
increase CO2/N2 selectivity and C O2 adsorption capacity in ods are still needed to further clarify the unclear structural
test flue gas [239]. Compared with COF-1, the CO2 adsorp- composition and principles.
tion capacity of TEPA(10)-COF-1 at 1 bar increased by The performance of COFs in environmental remedia-
34.3% at 273 Kand 74.6% at 298 K (Fig. 18c). What is more, tion needs to be improved. Many COFs exhibit higher
the effect of increase at 0.1 bar is more obvious compared performance compared to conventional materials such as
with that of 1 bar, and it has a better CO2 absorption capac- GO and activated carbon. There is limited research on the
ity in industrial flue gas (Fig. 18c and d). Jiang et al. then investigation and evaluation of the performance of COF in
combined iCOFs with cationic polyethylenimide (PEI) to practical applications. At present, the performance evalu-
form ultra-thin COF films [240]. The iCOF@PEI membranes ation of COFS is carried out under laboratory conditions,
show CO2/N2 selectivity of 33 and high CO2 permeances which cannot accurately describe the practical application.
(1371 GPU) for stimulated flue gas (Fig. 18e). The high sepa- Therefore, the cost, reusability, stability, and selectivity
ration performance related to the defect-free membrane struc- of COFs need to be further improved in practical environ-
ture and the affinity for amino group enrichment (Fig. 18f). mental remediation.
Li et al. designed a new Me3TFB-(NH2)2BD, which achieves The toxicity caused by the massive use of COF nano-
high CO2/N2 selectivity (273 K: 83 ± 11, 295 K: 47 ± 11) materials needs attention. COFs are organic porous crys-
under flue gas conditions because of its high specific surface talline nanomaterials formed by covalent bonding of light
area (1624 ± 89 m2 g−1) in the same year [241]. elements (C, O, N, B, etc.), which have good stability and
are difficult to be decomposed in the environment. When
a large number of COF materials are used, environmen-
5 Conclusion and outlook tal toxicity due to discharge into the environment should
be noted; otherwise, the COFs that cannot be decom-
Environmental remediation has attracted great attention in posed will cause great harm to the safety of a variety of
the study of microporous materials. Non-thermodynamic organisms.
porous materials are being explored to replace traditional To sum up, COF materials have been widely used and
environmental remediation technologies that consume high continuously developed. Based on the structure-activity
energy. In this context, the selection of adsorbents and mem- relationship between structure and properties, the applica-
branes is the key to enhance adsorptive separation. Covalent tions of COFs in the field of environmental remediation
organic framework (COF) materials have great potential in were reviewed. It aims to provide theoretical guidance for
environmental remediation due to their adjustable pore size, the design and development of COF materials with high
high porosity, diverse and designable structures, and uniform efficiency and selectivity.
pore structure. Their application fields will be expanded
with the gradual deepening of research.
Author contribution Kun Hou wrote the main manuscript text. Yafeng
So far, COFs with large specific surface area and zero Yang and Haiping Gu prepared all the figures. Su Shiung Lam, Chris-
defects designed by machine learning and artificial intelli- tian Sonne, and Hui Ouyang wrote, edited, and reviewed the main
gence are often excellent adsorbents, but they are often dif- manuscript text. Hanyin Li and Xiangmeng Chen revised and supported
ficult to prepare or synthesize in practical applications. The funding. All authors reviewed the manuscript.
industrial synthesis of COF nanomaterials with low price and Funding This work was financially supported by the Key R&D and
good performance is still difficult. In addition, compared with Promotion Special Project of Henan Province (232102230108) and
resource-rich natural materials, the raw materials of COFs Young Talents Program of Henan Agricultural University (30501360).
are expensive, which leads to the production of COFs is not
Data availability The data presented in this study are available on
suitable for large-scale production and is not conducive to request from the corresponding author.
industrialization. Therefore, mild, green, and efficient reaction
conditions are the first choice for future development. Declarations
The structure, composition, and application principle of
COF nanomaterials are not fully understood. The atomic Competing interests The authors declare no competing interests.
13
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Synthesis of COF - 3

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Advanced Composites and Hybrid Materials (2023) 6:199

Recent progress in advanced covalent organic framework composites

1 Introduction pollution, resource shortage, and ecological destruction

health problems, among others [6, 7]. Therefore, there is 3000

insulation, sound insulation, and other advantages [11],

2.3 Mechanochemical synthesis 2.4 Room temperature chemical synthesis

Table 1 Summary of COF materials for wastewater treatment

eO4− and TcO4−, ReO4− is used as a non-radioactive sub-

Fig. 14 a Schematic diagram of

(COFHS: COF-based hierarchical structure), which is used trianiline; FMTA: 5′-(4-formyl-3-methoxyphenyl)-3,3″-

References 15. He Y, Sun M, Zhao Q, Shang J, Tian Y, Xiao P, Gu Q, Li L,

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Synthesis of COF - 3

Uploaded by

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Synthesis of COF - 3

Uploaded by

Document Information

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Copyright

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Did you find this document useful?

Is this content inappropriate?

Copyright:

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Synthesis of COF - 3

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Copyright:

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Advanced Composites and Hybrid Materials (2023) 6:199

Recent progress in advanced covalent organic framework composites

1 Introduction pollution, resource shortage, and ecological destruction

health problems, among others [6, 7]. Therefore, there is 3000

insulation, sound insulation, and other advantages [11],

2.3 Mechanochemical synthesis 2.4 Room temperature chemical synthesis

Table 1 Summary of COF materials for wastewater treatment

­ eO4− and ­TcO4−, ­ReO4− is used as a non-radioactive sub-

Fig. 14 a Schematic diagram of

(COFHS: COF-based hierarchical structure), which is used trianiline; FMTA: 5′-(4-formyl-3-methoxyphenyl)-3,3″-

References 15. He Y, Sun M, Zhao Q, Shang J, Tian Y, Xiao P, Gu Q, Li L,

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2.3 Mechanochemical synthesis 2.4 Room temperature chemical synthesis

eO4− and TcO4−, ReO4− is used as a non-radioactive sub-