Chemosphere
Chemosphere
Chemosphere
Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
H I G H L I G H T S G R A P H I C A L A B S T R A C T
A R T I C L E I N F O A B S T R A C T
Handling Editor: Y Yeomin Yoon Covalent organic frameworks (COFs) are an emergent group of crystalline porous materials that have gained
incredible interest in recent years. With foreseeable controllable functionalities and structural configurations, the
Keywords: constructions and catalytic properties of these organic polymeric materials can be controlled to fabricate targeted
Environmental pollutants materials. The specified monomer linkers and pre-designed architecture of COFs facilitate the post-synthetic
Pharmaceuticals
modifications for introducing novel functions and useful properties. By virtue of inherent porosity, robust
Covalent organic frameworks
framework, well-ordered geometry, functionality, higher stability, and amenability to functionalization, COFs
Functionalization
Sustainability and COFs-based composites are regarded as prospective nanomaterials for environmental clean-up and reme
Photocatalysis diation. This report spotlights the state-of-the-art advances and progress in COFs-based materials to efficiently
Adsorption isotherm mitigate pharmaceutical-based environmental pollutants from aqueous solutions. Synthesis approaches, struc
Reproducibility ture, functionalization, and sustainability aspects of COFs are discussed. Moreover, the adsorptive and photo
catalytic potential of COFs and their derived nanocomposites for removal and degradation of pharmaceuticals
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (J. Gan), [email protected] (M. Bilal), [email protected] (H.M.N. Iqbal).
https://doi.org/10.1016/j.chemosphere.2021.131710
Received 8 June 2021; Received in revised form 24 July 2021; Accepted 27 July 2021
Available online 29 July 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
J. Gan et al. Chemosphere 286 (2022) 131710
are thoroughly vetted. In addition to deciphering adsorption mechanism/isotherms, the stability, regenerat
ability and reproducibility are also delineated. Lastly, the outcomes are summed up, and new directions are
proposed to widen the promise of COF-based smart materials in diverse fields.
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reactivity, and solvent. This method is very useful to synthesize some microwave-assisted synthesis of COFs, it has been noticed that the
COFs on a large scale. El-Kaderi et al. synthesized the first 2D COFs by microwave-assisted route is fast and superior in performance compared
solvothermal method with pore size 6–12 Å (El-Kdari et al., 2007). In to the conventional method. Diversified functional materials can be
addition to this, the microwave aid synthesis route helps to enhance the synthesized by photochemical approach. In 2017, Choi et al. used UV
yield and rate of reaction by controlling the low energy supply (De le hoz irradiation to synthesize UV-COF-5 with a high growth rate as compare
et al., 2005). to solvothermal method at room temperature (Zhao et al., 2018). The
A number of functional materials consist of metal oxides, metal- increase in growth rate corresponds to the effect of UV light on inter
organic framework (MOFs), organic molecules, and zeolites has been layer orbital coupling, well supported with density functional theory
prepared in an efficient way (Mirzaei et al., 2016; Li et al., 2020a, (DFT). Similarly, pyrazine fused COF was synthesized by the photo
2020b, 2020c). Likewise, Cooper et al. synthesized boronate ester-linked chemical method by using UV radiation from sunlight in just 3 h (Kim
COFs through microwave-assisted technique with 200 times faster than et al., 2019). Whereas, in the absence of light, only amorphous polymers
the classical solvothermal route. Bein et al. developed a rapid process for are produced.
the synthesis of highly crystalline mesoporous boronate cross-linked In ionothermal method, COFs are synthesized by using ionic liquids
COFs with a surface area of 1000 m2g-1 (Cote et al., 2005). The micro or salt in a molten state as a catalyst or solvent. The monomers used in
wave synthesis route is not only limited to boron-based COFs. The this technique are amorphous and do not have long-range molecular
β-ketoenamine and dioxin linked COFs have also been developed by ordering. This is a simple, green method used to synthesize COFs at high
microwave aid solvothermal method. Wei et al. synthesized β-ketoen temperatures (Bojdys et al., 2010). In order to synthesize COFs with a
amine based COFs by the solvothermal method using microwave in an green strategy, the mechanochemical route is owed the best place due to
hour with high yield, excellent crystallinity, high BET area and highest its ecofriendly nature, simplicity in operation and cost-effectiveness in
adsorption power of CO2 (Wei et al., 2015). Similarly, dioxin-linked COF starting material and operation (Zhang and Dai, 2017). Various mate
has been developed by microwave strategy through aromatic nucleo rials include porous carbon, MOFs, metal oxide, and
philic reaction in 30 min (Ji et al., 2020). Despite limited graphene-derivative, established by the mechanochemical route.
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Banerjee et al. firstly developed a solvent-free route for the synthesis of only been used for the synthesis of boron-based COFs.
COFs through manual grinding of precursor in mortar for 40 min at 25
o
C (Biswal et al., 2013). The COFs produced in this method have a low 5. Structure of COFs
surface area, good stability, and moderate crystallinity.
Mechanochemical method is superior to the solvothermal technique The combination of different rigid monomers having a symmetrical
due to the extra benefit of spontaneous delamination of COFs to a 2D reactive site as vertices through the condensation route are known as
nanosheets (Chandra et al., 2013). Rapid and universal synthesis of COFs. The structure of crystalline COFs mainly depends on the geometry
β-ketoenamine-linked COFs through mechanochemical strategy was of building blocks, which are generally comprised of multi-functional
reported by Banerjee and co-workers in 2017. The COFs synthesized monomers, with defined symmetry led to the formation of 2D or 3D
through this technique are employed in many applications due to its structures. Condensation of polymers of various geometries and sym
outstanding properties, including commercial zeolites. Nevertheless, the metries generate structures of variable topologies which may provide a
mechanochemical strategy of COFs is still new and need more effort. In varied range of shapes, dimensions, pore size within the material
the past, a high energy beam has been used to synthesize many func (Machado et al., 2021; Huang et al., 2016). The skeleton of resulted
tional materials. To keep this in mind, Wang et al. synthesize 2D COFs leads to different types of polygon (Fig. 3a). A hexagonal COF can
imine-linked COFs by employing electron beam radiations with an be prepared by combining 1,3,5-tri-(4-aminophenyl) benzene with
extraordinary rate of reaction and generality (Zhang et al., 2020). This C3-Symmetric vertices and 2,5-dimethoxyterephthalaldehyde having
imine-linked COF having flexible skeletons was synthesized in just 160 s C2-symmetric edge as shown in Fig. 3b (Xu et al., 2015). In order to
by using a high energy electron beam (1.5 MeV) at room temperature. synthesize well-ordered frameworks, the reaction should be reversible to
This strategy is highly universal and rapid. A COF material that was hard some extent to confirm their self-healing stability. The reaction of
to synthesize through the conventional method can be easily synthesized different types of monomers produced a number of linkages among COFs
by this electron beam-induce method. Due to the high synthetic rate, (Xiang et al., 2013). These linkages decide the different properties and
control of energy consumption of electron beam, this method is the stability of COFs (Fig. 3c). Such as, COFs synthesized by boroxine or
future of industrial production of COFs which are hard to prepare boronate-ester linkage could show luminescence up to some extent, but
through conventional method. The COFs need high crystallization rate they are unstable in the presence of water molecules due to the electron
can be synthesized by sonochemical method. This method has acoustic deficient nature of boron present inside of these linkages (Cote et al.,
cavitation in solution, which control the local temperature and pressure 2005). On the other hand, COFs with imine-based linkages are more
and acquire fast cooling and heating rates (Xu et al., 2013). This method stable, but most of the parts are non-luminescent due to the dissipation
is also low cost and control energy consumption due to less process time. of excitation energy by nitrogen atom for photochemical electron
Ahn and coworkers synthesized the boron-based COFs by developing the transfer (Huang et al., 2017). To get these properties together in COFs, a
first sonochemical route through ultrasonication for 1 h (Yang et al., C–– C bond linkage is required in the geometry (Jin et al., 2018).
2012). The large-scale production of COFs can be carried out by this Recently, a “two-in-one” strategy has been employed to synthesize
technique as compared to solvothermal method with high space-time three-dimensional (3D) COFs, which enables facile and easy preparation
yield. Sonochemical technique is still needed improvements and has of highly crystalline COFs. Two in one strategy involves integrating two
Fig. 3. (a) Topology diagrams of 2D COFs; (b) assembly of 2D hexagonal COFs (e.g. TPB-DMTP-COF); (c) COFs’ linkages; and (d) schematic representations of 3D
COFs (left) and 2D COFs (right). Reprinted from Wang and Zhuang (2019) with permission from Elsevier. License Number: 5115101478232.
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different functional moieties of co-monomers into a single molecule interaction among guest molecules and the luminescent part of COFs can
through self-polycondensation. High throughput COFs can be synthe be utilized as a detection unit (Dalapati et al., 2016).
sized through this approach. This synthetic approach has several ad
vantages: (i) during polymerization the stoichiometry could be 6. Functionalization of COFs
maintained perfectly, (ii) different solvent systems (DCM, THF, CH3OH
etc.) can be employed for COFs synthesis (iii) crystallinity and porosity To expand the applications and design of COFs through the use of
of COFs is not affected much. Moreover, COFs with different linkages different building blocks and functionalization of their backbone with
and various building blocks can be synthesized through this synthetic active functional moieties is a keyway. Meanwhile, the incorporation of
strategy (Li et al., 2019a, 2019b, 2021a, 2021b). A two-dimensional different functionalities into their porous structure is also tunable due to
(2D) and 3D COFs can be built according to the dimension of the their adjustable pore size during synthesis. The functionalization of
monomer used to synthesize. In 2D COFs, an atomic layer stacked with COFs material is divided into two types, first is the bottom-up approach
each other through covalent bonding or pi-pi stacking produces a in which a functionalized monomer is used to synthesized COFs, second
layered structure with a larger surface area. This layered structure of is post-treatment through the modification of COFs after synthesis, as
COFs formed through covalently bonded nano-sheets endow many ap illustrated in Fig. 4. COFs with required properties such as stability,
plications, including catalysis, purifying membrane, and detection (Da fluorescence, porosity, and crystallinity can be designed through these
et al., 2019). As compared to 2D COFs, 3D COFs are less common due to approaches.
limited tetrahedron diversity but shows high surface area. COFs quality Firstly, a bottom-up approach involved the use of monomer having
mainly depends on the pore size and crystalline nature of the skeleton. In required functionalities or pretreated for those kinds of properties. Later
addition, it is hard to synthesized single crystal COFs; powder XRD is on, this predesigned monomer is used for the synthesis of COFs. Wang
used to analyze their crystal structure (Cote et al., 2005; Xu et al., 2015; and coworkers synthesize a 2D mesoporous chiral covalent organic
Sun et al., 2017). Furthermore, an N2 sorption isotherm is used to framework through a bottom-up approach (Xu et al., 2016). A chiral
measure the pore size and surface area of COFs. To measure the exact pyrrolidine was used to generate chirality on diamino-p-terphenyl
value of these properties, the modeling result can be compared to the building unit for COFs having chirality inside. In this way, COFs with
ratio of simulated surface area and experimental value. different types of functionalities like thiol and sulfonic acid have been
The applications of COFs, mainly triggered by their thermal stability prepared (Chandra et al., 2016; Lu et al., 2017). Protection of active
and the effect of water, acidic and basic solution on their structure. parts of monomer is required during modification to avoid side reaction
Normally, they show good thermal stability but are unstable in water and rapture of COFs active terminals. Besides this, it is hard to synthesize
and acidic/basic solution. The change in structure skeleton in water monomers with different functionalities in a bottom-up approach.
mainly due to the change in crystallization and porosity of the material. Similarly, sometimes functionalization of building blocks destroyed the
This instability renders their applications as a water purification mem regularities of COFs due to their bulky nature and difficulty in incor
brane. There are two main factors that control the structure stability of poration. Thus, these defects make the bottom-up approach less
COFs, one is the strength of covalent linkage, and the second is the important and applicable.
interaction among layers (Chen et al., 2013). Several strategies have The post-synthetic strategy gains a lot of importance to overcome
been employed to enhance the structural stability through linkers these issues due to its ease in functionalization and versatile nature. In
modification, blending and linkage conversion (Chen et al., 2013; Wang this route, the functionalization does not affect the skeleton of COFs
et al., 2019). Similarly, a luminescent COF can be synthesized by the monomer and control the side reactions occurred. This treatment in
incorporation of a luminescent unit during their construction. Despite volves the generation of different types of forces among the functional
this, so far, it is a great challenge to synthesize COFs with luminescence group and COFs skeleton. It can involve host-guest treatment, linkage
due to the absence of luminescent part and the loss of energy of lumi functionalization and pendant group and skeleton modification. The
nescent part by the p-p structure of linkage. This quenching of lumi COFs material having a highly porous structure can be act as a host for
nescence can be controlled by aggregation-induced emission incoming guest molecules and responsible for host-guest interaction.
components incorporation inside the skeleton. In this way, the This host-guest interaction is comparatively week and includes
Fig. 4. Structural functionalization approaches in COFs. (a) Bottom-up approach and (b) post synthetic functionalization approach (Yusran et al., 2020; an Open
Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/)).
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J. Gan et al. Chemosphere 286 (2022) 131710
hydrophobic and hydrophilic interaction, van der Waals forces and pi-pi conditions used for their synthesis and their required applications
interaction (Atwood and Steed, 2009). Such as a photo-responsive C60 (Banerjee et al., 2017). If the conditions applied on materials during
molecule were added into the skeleton of 2D phenazine-linked COF applications are mild compared to their synthesis, make them more
through host-guest interaction. This incorporation under sublime con stable and less reversible. In this case, COFs synthesis through reversible
ditions generates a COF s molecule with donor-acceptor characteristics reactions occurred at higher temperature are more stable and useful. On
applicable to photovoltaic cells and photoswitches (Guo et al., 2013). the other hand, synthesis at higher temperatures limits the functional
Similarly, an electron acceptor molecule was loaded in boronate COF to ities which can be decomposed at these harsh conditions (Stewart et al.,
make a hybrid with electron heterojunction (Dogru et al., 2013). This 2017; Kuhn et al., 2008). So, a triangle is existing among stability,
incorporation occurred by van der Waals forces. Furthermore, a crystallinity, and complexity (like multiple functionalities). Three main
biomolecule having catalytically active structure is engaged into porous routes followed in breakage of COFs include bond breakage, porosity
COF (Sun et al., 2018). This technique was further employed to 3D COFs and order loss and collapse of flexible pore or stacking breakdown (Sick
to explore their property change. et al., 2019). This can be minimized by several conformers and a perfect
Functionalization of COFs through linkage is stable but somehow design to control stacking interaction.
reactive towards certain groups. This strategy is applicable to certain Generally, COFs contains two types of linkage, C–N and B–O. A
reactions such as ring fusion and oxidation-reduction reactions nucleophile can easily attack B, which is a Lewis site and poor stability
(Mohamed et al., 2009; Waller et al., 2016). The COFs formed through towards water and pH in these linkages. On the other hands, COFs with a
this strategy shows relatively higher stability toward certain chemicals C–N bond are electron-rich and make the attack of water easy (Guo
as compared to pristine COFs. It was reported that an imine-linked COFs et al., 2013). In order to reduce these possibilities, an alkyl group attach
can be transformed into ring fused COF with thiazole group by con with B–O linkage to push electron towards them and resist the attack of
trolling its crystalline state (Haase et al., 2017, 2018). Elemental sulfur water. This solution is not sustaining long time to control hydrolysis
was used to oxidized imine group and later cyclized into thioamide by (Sick et al., 2019). Similarly, COFs contain intramolecular hydrogen
oxidation. This linkage functionalization involved initialization by a bonding with C–N linkage retains their sustainability in acidic water.
linker, oxidation-reduction, and cyclization through one pot system. Many functionalities are used in this regard, like hydrozone-linked COFs
This method is mainly applied for imine linkage. containing hydrogen bonding among hydrogen of –CONH- and oxygen
A number bond formation involved in the functionalization of atom at alkoxy chains make them chemically and thermally stable
pendant group and skeleton of COFs. It involved covalent bond, coor (Jiang et al., 2019; Schoedel et al., 2016). As the extent of hydrogen
dinate bond, ionic bond and oxidation-reduction reaction depending on bonding increased in COFs their stability enhanced significantly.
the functionality and reaction conditions. The pore channel contains a Another route to enhanced stability is the attachment of bulky groups on
pendant group is available for incoming functionalities for covalent secondary nitrogen of enamine-linked and imine-liked covalent organic
linkage. Practically a bridge was developed among functionality and frameworks. Banerjee and coworkers synthesized TpPa-1 and TpPa-2
pendant group at COFs skeleton. A number of COFs with good crystal COFs with enamine linked functionality. The latter on becoming very
linity, performance as catalyst and adsorption applications has been stable in acidic solution due to the presence of methyl group near to
functionalized through the triazole linkage route (Xu et al., 2014; Roy secondary nitrogen, whereas former is unstable and lost its crystallinity
uela et al., 2018). Meanwhile, C60 bucky-ball has also been incorpo in 9 N HCl solution in 24 h (Zhao et al., 2018). Similarly, the strategy of
rated at porous surface of COFs to enhance their energy storage attachment of bulky group near to active linkage can also apply to B–O
performance. In the same way, amide bonds incorporation in COFs linked COFs. COFs with the alternate conjugated system are also very
makes them highly stable material with a number of active sites. This stable as conjugation provide protection towards active groups. As a
interaction generates through the reaction of primary amine and conclusion, COFs with B–O linkage are less stable due to ease in
carbonyl group. A covalent organic nanosheet can also be formed breakage of bond toward nucleophile attack, on the other hand presence
through post-synthetic treatment. Through this strategy, a solid sorbent of intramolecular hydrogen bonding make them more stable toward
for nuclear waste was synthesized. These dioxins linked COFs can also be hydrolysis and pH. The attachment of bulky group near to active part
used to absorb metal pollutants (Zhang et al., 2018). and introduction of conjugation system also enhanced their stability
The covalent linkage functionalization of COFs is a very wide and (Rao et al., 2017; Liu et al., 2018, 2020a, 2020b).
most applicable strategy. On the other hand, an electron donor-acceptor
coordinate covalent bond formed between COF and incoming func 8. Application of COF for removal of pharmaceuticals
tionality (Liu, 2004). An ionic interaction also occurred among the
dipolar region of COF and active site of functional groups. These two 8.1. Adsorption potential of COFs for removal of pharmaceuticals
interactions mostly happened when a metal ion or molecular ion was
incorporated into the COFs cage. This happened when an electron-rich s Rapid development in the pharmaceutical industries has occurred
or p-type pf orbital is present in COFs to facilitate the covalent formation and consumption of pharmaceuticals is increasing day by day for
bond. For example, COFs with imine linkage can be able to form a co healthy life. But improper discharge of pharmaceuticals into aqueous
ordinate covalent bond (Corma et al., 2010). The COFs with ionic system is destroying our ecosystem. The toxic, teratogenic and muta
skeleton can form an ionic linkage with molecular ions. In this direction, genic effects associated with pharmaceuticals (ampicillin, diclofenac,
inorganic salts, ionic liquids, organic salt and other molecular ions have sulfamethazine etc.) are severely threatening for human health. During
been used in COFs channel (phosphoric acid deposition in 2D COFs) recent decades, COFs have been reported to have ability to adsorb
(Chandra et al., 2014). pharmaceuticals. COFs have hydrophobic nature so they have affinity
towards organic materials (Wang et al., 2018a, 2018b). Different
7. Sustainability of COFs adsorption mechanisms may be involved between COF and pharma
ceuticals in adsorption approach like hydrogen bonding, π- π in
The sustainability of COFs is mainly inter-connected with crystal teractions, pore size effect, electrostatic interactions and hydrophobic
linity and functionalities present at their surface. The family of COFs interaction etc (Li et al., 2020a, 2020b, 2020c; Mondal et al., 2019)
synthesized by the reversible method are inversely related to crystal (Fig. 5). Mellah and coworkers synthesized the fluoro incorporated COF;
linity and stability. It means that, by increasing the reversibility, the TpBD-(CF3)2 through covalent bonding between 3,3′ -bis(tri
crystallinity of COFs increases, whereas their stability reduces directly. fluoromethyl)benzidine and triformylphloroglucinol and then used it to
This instability is due to the cleavage of linkage toward reverse reaction adsorb ibuprofen from aqueous medium. At neutral pH, Fluoro based
through hydrolysis. The sustainability of COFs evaluates by the COF showed adsorption capacity of 119 mg/g for ibuprofen (120 min).
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Fig. 5. Major interaction mechanisms involved between adsorbate and COF. Reprinted from Ahmed and Jhung (2021) with permission from Elsevier. License
Number: 5115110282245.
Isopropanol can be used to regenerate COF used. Hydrophobic in sulfamethazine. They showed adsorption potential of 109 mg/g for
teractions were involved for adsorption of ibuprofen on COF (Mellah diclofenac and 113.2 mg/g for sulfamethazine in 50 and 80 min
et al., 2018a). respectively. The magnetic COF showed good separation capability from
A sulfonamide containing drug named Sulfamerazine is used as anti- solution. Adsorption phenomena was attributed to C–H⋅⋅⋅π interaction
infective agent in clinical practices. Zhuang and colleagues synthesized between COF and both drugs (Shuting Zhuang, Rong Chen, Yong Liu, &
TPB-DMTP-COF for potential removal of Sulfamerazine from aqueous Jianlong Wang, 2020a, 2020b, 2020b).
media. Highly crystalline structure, significant specific area and chan Tetracycline and cefotaxime are present in an aqueous system and
nels endow this COF high capacity to adsorb 209 mg/g sulfamerazine in are difficult to remove. Li and coworkers synthesized a COF material
80 min. The dissociation constant, pH dependency and zeta potential called NCCT, and this composite film was used further to eliminate
showed that electrostatic interactions were involved in the removal of antibiotics by using the MSPE approach (Li et al., 2020a, 2020b; 2020c).
sulfamerazine (Zhuang, Liu, & Wang, 2020a, 2020b, 2020b). DFT cal Fig. 6 shows the synthesis and removal efficiency of NCCT. The various
culations reveled that compounds could adsorb on COFs pore sites via functional moieties on NCCT enhanced the adsorption of antibiotics. The
CH2 … π interaction. Triazine based COFs have been reported to have pseudo-second-order kinetics showed the adsorption of antibiotics on
potential role in the removal of antibiotics from aqueous solution. NCCT. The adsorption capacity for tetracycline and cefotaxime was
Triazine COF removed the sulfamethoxazole from water with an found to be 388.52 mg/g and 309.26 mg/g, respectively. The film also
adsorption capacity of 483 mg/g (Akpe et al., 2020). π-π and hydro showed reproducibility after six cycles of adsorption. Cation exchange,
phobic interactions were dominant for adsorption. COFs with two surface complexation, electrostatic attraction, π–π interaction and
different functionalities nitro (COF–NO2) and amino Two different COFs hydrogen bonding were found involved in adsorption of tetracycline on
with NO2 (COF–NO2) and –NH2 (COF–NH2) functionalities were found NCCT while electrostatic interaction, condensation reaction, hydrogen
potent to remove various antiinflammatory drugs (ketoprofen, bonding and π–π interactions played a role for adsorption of cefotaxime.
ibuprofen, and naproxen) (Liang et al., 2021). Amine based COF showed These nanocomposite films can be separated from the aqueous system
more potential to adsorb drugs in comparison of nitro functionalized safely. The adsorption of β-agonists and fluoroquinolones from milk and
COF. pork meat through magnetic sulfonated COFs ((Fe3O4@SiO2–NH2/1,3,
COFs have micro-crystalline structure, and after adsorption, it be 5-triformylphloroglucinol/2,5- diaminobenzene-sulfonic acid) have
comes difficult to separate them from the solution. To overcome this been reported. The adsorption was attributed to hydrogen bonding,
problem, Magnetic COFs have been synthesized by incorporation of electrostatic interaction, π–π interaction and hydrophobicity (Hu et al.,
magnetic particles in the structure of COFs. This can be done by blending 2021). COFs has great potential to adsorb and reusability of antibiotics
magnetic particles with COFs and magnetic particles are encapsulated (Xu et al., 2020). Composite of COF with β-cyclodextrin was fabricated
by COF shell. In a latest report magnetic COF was synthesized by and the as-prepared COF showed high surface area, uniform pore size
immersing TPB-DMTP-COFs in Fe3+/Fe2+ containing solution. This as- and great crystallinity. The composite COF adsorbed the naproxen and
prepared COF was used for adsorption of diclofenac and ibuprofen with adsorption potential of 25 mg/g and 17 mg/g
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J. Gan et al. Chemosphere 286 (2022) 131710
Fig. 6. Synthesis and antibiotic removal efficiency of NCCT. Reprinted from (Li et al., 2020c) with permission from Elsevier. License Number: 5115110504119.
respectively (Wang, Wei, & Feng, 2018a, 2018b, 2018b). great surface area and porosity and were found efficient in removing
A group of scientists synthesized two different magnetic COFs for the tetracycline from an aqueous solution with an adsorption potential of
removal of diclofenac, one magnetic COF was incorporated with hy 285 mg/g. Great adsorption was attributed to hydrogen bonding, π-π
droxyl moieties named OH-MCOF. The hydroxyl-containing OH-MCOF interactions and hydrophobic interactions. The heat-treated (1000 ◦ C)
showed great adsorption potential for diclofenac. According to the COF sample was denoted as TpPa-1-1000, and it showed great stability
Langmuir model, the OH-MCOF adsorbed 203.4 mg/g of diclofenac in and reusability (Huang et al., 2021). Flower shape TAPA-TFPB-COFs
30 min. The hydroxyl COF was used five times, and still it showed the were synthesized through easy method at room temperature. This
same adsorption capacity for DCF. The reusability and stability of OH- as-synthesized COF showed great adsorption potential towards quino
MCOF made them valuable to the removal of pharmaceutical-based lone based drugs, including norfloxacin, ciprofloxacin, enrofloxacin,
contaminants (Mi et al., 2020). In the latest study COF template was gatifloxacin and cinoxacin (Xu et al., 2020). In another study, the hollow
employed to fabricate porous carbons (PCs). Porous carbons showed covalent organic framework was synthesized by use of TAPB and DMTP
Fig. 7. Fabrication of laccase immobilized COF for degradation of Tetracycline. Reprinted from Tang et al. (2021) with permission from Elsevier. License Number:
5115110772463.
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J. Gan et al. Chemosphere 286 (2022) 131710
by following emulsion polymerization. The Laccase enzyme was a covalent fashion. In COFs, the building blocks are connected in layers
immobilized on synthesized COF and further used to adsorb and degrade through π- π interactions and in some COFs, extended networks are
Tetracycline. The as-prepared H–COF–OMe showed hollow structure, found. They are porous materials with high surface area, tunable pore
good surface area and it contained great loading capacity and recover of size, highly stable, and these properties made them potential photo
laccase. The synthesized Lac@H–COF–OMe enhanced the tetracycline catalysts (You et al., 2021). Presence of moderate band gap and π
diffusion and the shortening of reaction pathway made them eligible to conjugation in COFs made them responsive to visible light (Banerjee
increase the degradation of tetracycline (Fig. 7). The 99 % tetracycline et al., 2017). Band gap can be obtained by changing conjugation and
was degraded in 100 min approximately. So this study showed that incorporation of various functionalities. COF has the advantage over
composite of COF with enzymes would be promising for degradation of other catalysts for their capability to separate photo-generated charges
pollutants (Tang et al., 2021). Table 1 explains role of various COF via π arrays and pores enable the transport of matter (You, Zhao, Wang,
materials for removal of different pharmaceuticals from aqueous me Bao, & He, 2020a, 2020b, 2020b). Triazine building blocks in COFs
dium through adsorption approach. perform as centers of light-harvesting that enhance electrons’ release
and decrease recombination of electrons-holes (Wan et al., 2011).
8.2. Photocatalytic potential of COFs for removal and degradation of Additionally, associated classes olefins, benzimidazole, amides, dioxin
pharmaceuticals with COFs provides great delocalization of electrons (Xu et al., 2019).
Photoexcitation of COFs led to the generation of various
Photodegradation of various pharmaceutical-based contaminants reactive-intermediates for organic molecules activation under mild re
has been carried out by using different photocatalytic systems (Ashraf action conditions. Transfer of electrons is usually involved between
et al., 2021; Cen et al., 2020; Yang, Aqeel Ashraf, Fakhri, Kumar Gupta catalyst and substrate. Many organic reactions take place via redox re
and Zhang, 2021a). But several restrictions are associated with photo actions. Recently magnetic covalent organic frameworks (Fe2O3@COFs)
catalysts, like less surface area, poor stability and quick recombination was synthesized by heating 1,3,5-tri-(4-aminophenyl)benzene and 2,
of the holes and electrons (Ong et al., 2016; You et al., 2021). Recently 5-dimethoxyterephthalaldehyde in o-dichlorobenzene, n-BuOH and
COFs have been used for photocatalytic degradation of pollutants (Chen HAc. After synthesis, COF was treated with Fe2(SO4)3 solution for
et al., 2019). COFs are porous polymeric molecules, crystalline in na incorporating magnetic features in COF structure. The synthesized COF
ture, and their structure consists of various elements which are linked in was used as Fenton like catalyst for degradation of sulfamethazine
Table 1
COF-based nanomaterials for the removal of pharmaceuticals.
Sr COFs materials Pharmaceuticals Adsorption/degradation Mechanism COF recyclability Ref
# potential mg/g
Abbreviations: HcOPs = porous hydrogen-bonding covalent organic polymers; TPB-DMTP-COF = TPB (triphenylbenzene) – DMTP (dimethoxyterephthaldehyde)
–COF; Magnetic; TPB-DMTP-COFs = Magnetic TPB (triphenylbenzene) – DMTP; (dimethoxyterephthaldehyde) –COF; TpBD-(CF3)2 = fluorine-bearing covalent
organic framework; β –CD = β-cyclodextrin; NCCT (COF) = NiFe2O4–COF-chitosan-terephthalaldehyde nanocomposite.
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J. Gan et al. Chemosphere 286 (2022) 131710
(SMT). The photocatalyst showed great crystallinity, flower like photocatalysis. Fig. 11 represents the general proposed mechanism of
morphology, porosity and iron magnetic particles were encapsulated in photocatalytic degradation of pharmaceuticals through COFs.
channels of COFs. Magnetic COFs adsorbed the SMT and catalyzed the
Fenton degradation of SMT in hydrogen peroxide around 100 % removal 9. Adsorption mechanism/adsorption isotherm/kinetic models
efficacy. Acidic media enhanced the SMT degradation in Fe2O3@COF
s/H2O2. Catalyst exhibited great reusability and stability after 5 cycles To explain the removal strategy of pollutants, it is important to
with great removal potential around 96 %. Hydroxyl radicals were main explore the mechanism of action of pollutant which is mandatory to
reactive species that were generated for degradation of SMT in explore the conditions required for adsorption, desorption and re-
Fe2O3@COFs/H2O2 system (Fig. 8). Generation of OH radicals was generation. After theoretical calculations, experimental observations
confirmed through Electron spin resonance where 5,5-dimethyl-1-pyrro and spectroscopic analysis, the interactive mechanisms are carried out.
line N-oxide (DMPO) was employed as the trapping agent. Enhanced van der Waals interactions, electrostatic interactions, hydrophobicity,
Fenton like catalytic activity of COF was attributed to Fe2O3 NPs hydrogen bonding, hydrophilicity largely affects adsorption phenom
because simple COF did not show enhanced removal potential. ena. Various other features like shape, crystallinity, functional moieties,
Fe2O3@COFs is potential catalyst for degradation of SMT nad can be the surface area of adsorbents also affect the adsorption performances
used to degrade other pharmaceuticals as well (Zhuang and Wang, (Yanxia Li et al., 2019a, 2019b, 2019c, 2019b). Thereof different
2021). In another study, CHACF-JUC-505 system was developed via mechanisms controlled the adsorption of pollutants simultaneously.
incorporation of H2 and Pd/JUC-505 in Fenton system. The activated H2 Adsorption mechanism may be attributed to different interactions which
facilitated the reduction of JUC-505. The SMT removal was facilitated can be explored by determining reaction conditions. Furthermore, Time,
through the degradation of hydroxyl radical. The S–N cleavage was pH, temperature determinations may be useful to determine removal
found major degradation pathway of SMT. Removal efficacy was found strategies. Interactions between adsorbent and adsorbate are greatly
to be approximately 96.77 % (Fig. 9) (Yang et al., 2021b). affected by pH. Solution pH may influence adsorption by manipulating
Triazine based COF composite was synthesized by combining BiOBr the distribution of pollutants, alterations in functional moieties by
nanoflake with covalent triazine framework (CFT-3D) through co- protonation, or altering the surface (Zhong et al., 2020a, 2020b). The
precipitation approach. The composite (CFT-3D/BiOBr) showed activ charge of the surface of adsorbents depends on pH as well, and it affects
ity as photocatalyst and potentially degrade the tetracycline and cipro the adsorption potential of COF based materials. At less than pHzpc
floxacin under light irradiations. The presence of 2 % CFT-3D in values, the surface of the adsorbent gets protonated, and improving
composite showed excellent photocatalytic potential. Intermediates positive charge may increase the electrostatic interaction between
trapping strategy showed that superoxides radicals were active species adsorbate and adsorbent. On the contrary, the surface charge of the
in degradation phenomena. The enhanced photocatalytic efficacy was adsorbent becomes negative at greater pH > pHzpc, which may cause
due to a large range of optical adsorption. The potentially separated electrostatic repulsion between contaminant and adsorbent (Afshari and
generated photoactively electrons and holes and enhanced adsorption Dinari, 2020). At pH 1, the NH2 moieties of TpPa-1 and Fe3O4@TpPa-1
and transfer of antibiotics in synergistic photocatalytic process (Fig. 10). change to positive NH+ 3 after protonation and then it may potentially
This study showed that composite of COFs with inorganic materials attract the negative adsorbates through electrostatic interactions (Zhong
might open new sources for degradation of pollutants (Zhu et al., 2018). et al., 2020a, 2020b). So this can be concluded that electrostatic in
Recently AgI modified COF-PD/AgI photocatalyst was fabricated to teractions play great role in adsorption phenomena. Adsorption of
degrade acetaminophen and intermediate radicals; superoxides, hy contaminants on COF is influenced by temperature as well. Various
droxyls and holes were involved in photocatalytic activity. The photo isotherm models as Temkin, Freundlich, Langmuir and
catalyst sustained its activity for consecutive four cycles (F. Liu et al., Dubinin-Radushkevich are applied to explore the interaction (Ya Li
2020a, 2020b). Table 1 explains the role of various COF materials for the et al., 2019a, 2019b, 2019c, 2019b). For adsorption simulations the
removal of different pharmaceuticals from aqueous medium through Langmuir and Freundlich models are utilized widely. The isotherm
applicability is compared through recognizing the coefficient correla
tions and analysis of error (Firoozi et al., 2020). The accurate model can
explore the adsorption approaches and assess bonding features between
COF and adsorbate (Gao et al., 2019). If by assuming consider that no
interaction occurs between adsorbates and all adsorption sites on the
solid surface are the same and uniformly scattered, then Langmuir
Model would be suitable to explain the monolayer adsorption. If sup
posed that adsorbate comes at the non-uniform surface of adsorbents
from the liquid phase and adsorbent contains various sorption sites on
the surface, which lead to various adsorption energies and non-uniform
distributed surface sorption heat, then Freundlich model describes the
non-uniform multilayer adsorption (Z. You et al., 2020a, 2020b).
Langmuir model assumes surface mono-layer coverage (homogeneous)
while Freundlic explains empirical adsorption model (multilayer)
(Yiqun Liu and Landskron, 2017). Dubinin-Radushkevich explores the
kind of adsorption like chemical or physical related to adsorption, which
means free-energy (Zhong et al., 2020a, 2020b). In a recent study sul
fonic acid functionalized COF was synthesized and used for removal of
diclofenac and maximum adsorption potential was found 770 mg/g.
Mechanistically π–π interactions and hydrogen bonding were found
involved in adsorption. Diclofenac adsorption followed the pseudo
second-order kinetics, and thermodynamic values (ΔH < 0, ΔG < 0)
exhibited exothermic nature and spontaneous adsorption. This experi
Fig. 8. Possible reaction mechanism of SMT removal in the Fe2O3@COFs/H2O2 ment to understand interaction between adsorbent and adsorbate four
system Reprinted from Zhuang and Wang (2021) with permission from Elsevier. different Temkin, Langmuir, Freundlich, and Dubinin–Radushkevich
License Number: 5115111128109. isothermal models were applied. In Langmuir, it was assumed that
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J. Gan et al. Chemosphere 286 (2022) 131710
Fig. 9. Possible reaction mechanism of SMT removal in the CHACF-JUC-505 system. Reprinted from (Yang et al., 2021b) with permission from Elsevier. License
Number: 5115111398777.
Fig. 10. Plausible Mechanism for Photocatalytic Degradation of BiOBr/CTF-3D-2% under Visible Irradiation. Reprinted from Zhu et al. (2018) with permission from
American Chemical Society, Copyright © 2018.
adsorption takes place at the homogeneous surface area of adsorbent pharmaceutical based contaminants through COFs.
and all adsorption sites are even while in Freundlich it was supposed
that all sites are uneven. Diclofenac adsorption on SO3H–COF was well 10. Regeneration, stability, and reproducibility
explained by langmuir model in this experimental data. And it proved
from coefficients correlation (0.9996, 0.9996 and 0.9836) that COF has The regeneration and recyclability of adsorbent is vital for their use
even binding sites for the diclofenac adsorption (Hao et al., 2019). at commercial sacle and for cost effectiveness. Previously various
Fig. 12 presents the proposed mechanism of adsorption for removal of organic solvents methanol, isopropanol, ethanol, THF are reported for
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J. Gan et al. Chemosphere 286 (2022) 131710
Fig. 12. Proposed mechanism of adsorption for removal of pharmaceutical contaminants through COFs.
desorption of organic contaminates to regenerate respective COF based adsorbent (Hao et al., 2019). Mellah and his colleague regenerate the
materials (Hashemzadeh and Raissi, 2018; Wang et al., 2018a, 2018b). COF (TpBD-(CF3)2) by using isopropanol, and ibuprofen was efficiently
Hao and his colleagues regenerated respective SO3H–COF by using desorbed, and respective COF was obtained (Mellah et al., 2018a). THF
simple solvent elution process to remove diclofenac. Four-time COF was are reported for desorption of organic contaminates to regenerate
recycled in the presence of water, and excellent removal of DCF was respective COF based materials (Hashemzadeh and Raissi, 2018; Wang
maintained. Thus sulfonic acid based COF proved an effective recyclable et al., 2018a, 2018b). COF based adsorbent (NCCT) (used to remove
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J. Gan et al. Chemosphere 286 (2022) 131710
tetracycline and cefotaxime) was washed several times with water and environmentally-related contaminants with rising toxicity concerns. Sci. Total
Environ. 779, 146465.
then placed in 0.01 M NaOH solution, which leads regeneration of
Aguilar-Pérez, K.M., Heya, M.S., Parra-Saldívar, R., Iqbal, H.M., 2020b. Nano-
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2020a, 2020b; 2020c). Magnetic COFs can be easily separated from the Stud. Chem. Environ. Eng. 2, 100055.
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Declaration of competing interest Bisaria, K., Sinha, S., Singh, R., Iqbal, H.M., 2021. Recent advances in structural
modifications of photo-catalysts for organic pollutants degradation–A
The authors declare that they have no known competing financial comprehensive review. Chemosphere 284, 131263.
Biswal, B.P., Chandra, S., Kandambeth, S., Lukose, B., Heine, T., Banerjee, R., 2013.
interests or personal relationships that could have appeared to influence Mechanochemical synthesis of chemically stable isoreticular covalent organic
the work reported in this paper. frameworks. J. Am. Chem. Soc. 135 (14), 5328–5331.
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Cen, S., Lv, X., Jiang, Y., Fakhri, A., Gupta, V.K., 2020. Synthesis and structure of
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heterogeneous catalyst for a Fenton-based reaction. Catal. Sci. Technol. 10 (19),
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