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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 1: 67 - 80

DOI: https://doi.org/10.7536/PC230516

Review

Tetraphenylethene-Based Covalent Organic Frameworks (COFs): Design, Synthesis and Applications

  • Ziqing Wang 1 ,
  • Jinfeng Du 2 ,
  • Futai Lu , 1, 2, * ,
  • Qiliang Deng 1, 2, *
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  • 1 College of Sciences, Tianjin University of Science and Technology, Tianjin 300457, China
  • 2 College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300457, China
* e-mail:

Received date: 2023-05-17

  Revised date: 2023-07-28

  Online published: 2023-08-06

Supported by

National Natural Science Foundation of China(2190080961)

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Abstract

Covalent organic frameworks (COFs) as a new class of crystalline porous materials are assembled by appropriate building blocks through covalent bonds. COFs have been utilized in many fields such as storage and separation of gases, catalysis, proton conduction, energy storage, optoelectronics, sensing and biomedicine due to their regular channels, high thermal stability, high crystallinity and adjustable structure. In recent years, tetraphenylethylene-based covalent organic frameworks (TPE-based COFs) have attracted much attention due to their obvious aggregation induced luminescence effect, simple synthesis and easy functionalization. In this paper, the construction units, topological structures, synthesis strategies and application progress of TPE-based COFs in different fields are briefly reviewed. Finally, the development prospects and possible challenges of TPE-based COFs are pointed out.

Contents

1 Introduction

2 Construction unit and topological structure of TPE-based COFs

3 Synthesis strategy of TPE-based COFs

4 Applications

4.1 Catalysis

4.2 Adsorption

4.2.1 Ions adsorption

4.2.2 Gas adsorption

4.2.3 Biomolecule adsorption

4.3 Sensors

4.3.1 Sensors for detecting explosives

4.3.2 Ion sensors

4.3.3 Acid-base sensors

4.3.4 Enantioselective sensors

4.3.5 Biosensors

4.4 Optoelectronic

4.4.1 Light emitting diode

4.4.2 Electrochemical energy storage

4.4.3 Others

4.5 Bio-related applications

5 Prospects and challenges

Key words： tetraphenylethylene; covalent organic frameworks; building blocks; topology; applications

Cite this article

Ziqing Wang , Jinfeng Du , Futai Lu , Qiliang Deng . Tetraphenylethene-Based Covalent Organic Frameworks (COFs): Design, Synthesis and Applications[J]. Progress in Chemistry, 2024 , 36(1) : 67 -80 . DOI: 10.7536/PC230516

1 Introduction

Tetraphenylethylene (TPE) is a typical Aggregation induced emission (AIE) molecule. The vinyl group is connected with four benzene rings by single bonds, and the peripheral benzene rings are distributed in a propeller shape[1]. In the dilute solution state, the single molecule moves freely and can release energy through the non-radiative decay process of rotation or vibration of the benzene ring in the molecule, so no fluorescence can be seen, but when the molecule is in the aggregation state, the movement of the benzene ring is constrained, and the energy is emitted in the form of radiative transition, thus inducing the fluorescence of TPE to turn on. Tetraphenylethylene has attracted much attention from researchers because of its obvious AIE effect, simple synthesis, easy functionalization and high sensitivity, and has developed rapidly. In recent years, more and more tetraphenylethylene derivatives have been designed and developed, which play an important role in ion detection, bioimaging, biological and chemical sensing, light-emitting diodes, drug delivery and other fields[2,3][4⇓~6][7⇓~9][10,11][12,13][14,15].
In recent years, covalent organic frameworks (COFs), as a new type of porous materials, have attracted great attention due to their high crystallinity, low density, ordered pore structure, high chemical and thermal stability, large specific surface area, high porosity, tunable structure and easy functionalization.At present, it has shown excellent application prospects in the fields of gas storage and separation, catalysis, proton conduction, energy storage materials, optoelectronics, sensing and biomedicine[16⇓⇓~19][20⇓⇓⇓⇓⇓~26]. Tetraphenylethylene and its derivatives have also been used to construct covalent organic frameworks. In this paper, we review the progress in the construction and application of tetrastyryl-based COFs (TPE-COFs), including the design and synthesis of tetrastyryl-based COFs with different topologies, the reaction types of constructing tetrastyryl COFs, and the application progress of tetrastylyl COFs in catalysis, gas adsorption and storage, sensing, photoelectrochemistry, and biomedicine. Finally, the development prospects of tetrastyryl COFs, as well as the possible challenges and opportunities are pointed out.

2 Building Block and Topology of Tetrastyryl COFs

At present, there are mainly five kinds of tetrastyryl monomers used to construct COFs (Fig. 1): tetrakis (4-aminophenyl) ethylene (ETTA), tetrakis (4-formylphenyl) ethylene (ETBA), tetrakis- (4-aminobiphenyl) -ethylene (ETTBA), tetra (4-formylbiphenyl) ethene (ETBC) and tetra (4-boronatophenyl) ethene (TPEBA). The singleness of the tetraphenylethylene building unit makes the choice of another building unit more diversified. Through the screening and modification of ligand types (Figure 2), not only the diversity and controllability of the topological structure of tetraphenylethylene COFs are increased, but also the adjustability of the pore size of COFs materials is realized, and the application fields of materials are more extensive. As shown in Figure 2, these building blocks have been successfully reacted with tetrastyryl monomer to prepare tetrastyryl COFs. The structure of these building blocks is relatively simple, easy to synthesize, and rigid with large conjugated systems.
图1 用于合成四苯乙烯基COFs的单体

Fig. 1 Monomers for use in the synthesis of TPE-based COFs

图2 成功用于合成四苯乙烯基COFs的构筑单元

Fig. 2 Building units successfully used for the synthesis of TPE-based COFs

COFs are framework materials formed by covalent bonds, and the reaction follows the principle of dynamic covalent chemistry (DCC), which usually relies on the continuous "formation-breakage-reformation" of covalent bonds in the process of material preparation to achieve self-repair, thus obtaining an orderly structure[27]. At present, the bonding modes of tetrastyryl COFs materials are relatively limited, mainly including borate bond, imine bond, imide bond, hydrazone bond, azine bond and aminal bond (Figure 3). These bonding modes are all based on reversible reactions: boronic acid self-condensation reaction, aldehyde group and amino group condensation reaction to form imine bond, acid anhydride and amino group reaction to form imide bond, aldehyde group and hydrazide condensation reaction to form hydrazone bond, aldehydo group and hydrazine condensation to form azine bond, secondary amine and aldehyde condensation to form aminal bond.
图3 用于四苯乙烯基COFs的键连方式

Fig. 3 Linkages used in TPE-based COFs

Two-component tetrastyryl COFs are prepared by condensation of tetrastyryl units with C4 symmetry and linkers with C2, C3, or C4 symmetry via [4 + 2], [4 + 3], or [4 + 4] reactions to obtain 2D or 3D COFs. Two-dimensional COFs include kagome, sql, mtf, tth, bex, and cpi topologies, and three-dimensional COFs include ffc, fjh, and pts topologies[28]. Two topological types of tetrastyryl COFs, biporous kagome and uniporous sql, can be obtained by [4 + 2] condensation. For example, when Jin et al. Studied the strategy of topological template polymerization to synthesize crystalline porous covalent organic frameworks, they chose ETBA monomer and linear linker 4,4 ′ -biphenyldiacetonitrile to synthesize ETTF-DABP-COF, which has both triangular and hexagonal pores with two pore diameters of about 1.3 and 3.7 nm, respectively[29]. Chen et al. Designed and synthesized several groups of novel COFs based on the construction strategy of nonlinear edges and appropriate high-symmetry vertices. Among them, COFs with two sql topologies were synthesized with different tetrastyryl monomers, both of which had only diamond-shaped pores with pore diameters of 15.7 and 10.44 Å, respectively[30].
图4 四苯乙烯基COFs的拓扑结构

Fig. 4 Topological structures of TPE-based COFs

Tetrastyryl COFs obtained by [4 + 3] condensation possess the richest topology. In 2020, Nguyen et al. Synthesized COF-432 with ETTA and 1,3,5-triformylbenzene (TFB) as monomers. It has a void square grid mtf topology. The monolayer is two kinds of square pores with diameters of about 10.0 and 21.00 Å, and the layers are staggered to form a one-dimensional cylindrical pore structure with a diameter of about 7.55 Å[31]. In the same year, Xiong et al. Used ETBC and 2,4,6-tris (4-aminophenyl) -1,3,5-triazine (TAPT) as linker units to obtain a two-dimensional COF with a bex topology[32]. In addition to two-dimensional COFs, three-dimensional tetrastyryl COFs have been reported to be successfully obtained through the [4 + 3] reaction. As early as 2018, Lan et al. Used ETTA as one of the monomers to synthesize COF and 1,3,5-tris (p-formylphenyl) benzene (TFPB) or Tris (4-benzoyl) amine (TFPA) as the other monomer to synthesize two three-dimensional COFs with ffc topology[33]. This topology also appears in tetrastyryl COFs synthesized by Kang et al. With ETBC as the reactive monomer[34]. In 2020, Yaghi's research group integrated ETTA and 1,3,5-trimethyl-2,4,6-tris (4-formylphenyl) benzene (TTFB) into the same COF by designing a construction unit, and obtained COF-790 with a pore size of 21.55 Å and a fjh topology[35].
The [4 + 4] reaction usually uses ETTA, ETTBA, and ETBC as reactive monomers, which are condensed with another monomer to give tetrastyryl COFs with two-dimensional sql and kagome topologies and three-dimensional pts topologies. At present, ETBC can react with tetra (p-aminophenyl) -p-phenylenediamine, ETTBA can react with porphyrin-based monomers, ETTA and ETBC can not only react with each other, but also react with porphyrin-based and pyrenyl-based monomers, and ETTA can also react with carbazole-based monomers. The COFs prepared by the above methods have sql topology[36][37][38][37,39,40][39]. In addition, the two-dimensional COFs formed by the [4 + 4] reaction are also connected by borate bonds and have a kagome topology[41]. In 2019, Liu et al. Used ETTBA and o-phenanthroline complex as monomers to obtain COF-500 with interlocked structure and pts topology[42]. In 2022, Peng et al. Obtained the COF of pts topology by supercritical solvothermal synthesis[43].
Compared with two-component tetrastyryl COFs, the research on three-component tetrastyryl COFs is still relatively small, and there is a huge space for development. In 2015, Chen et al. Obtained a COF with a single-pore sql topology through the condensation of C4, C2 and C4 monomers, and its pore size distribution was 1.8 nm[44]. Later, Pang and Dong et al. Connected ETTA or ETBC as one of the monomers with two other monomers with C2 symmetry and different lengths through [4 + 2 + 2] reaction based on the heterostructure mixing method, and successively obtained multiple COFs with three-pore kagome topology[45][46]. In 2019, Yaghi's team made a new discovery. They connected hexagonal hexaphenylbenzene (HAPB), tetragonal ETTA and trigonal TFPB through imine bonds to prepare a two-dimensional porous COF with an unprecedented tth topology, called COF-346[47].

3 Synthetic Strategy of Tetrastyryl COFs

The method for the synthesis of tetraphenylethylene-based COFs is similar to that for other COFs materials. There are mainly the following six methods: (1) One-step solvothermal method: put the monomer powder and appropriate solvent in a heat-resistant glass sealed tube, remove the air in the tube by three times of freezing-pumping method, then heat and seal the glass tube, heat it to a certain temperature in vacuum at high temperature, react for 1 to 10 days, and finally obtain the COFs material. (2) Two-step solvothermal method: The polycondensation of monomers and the crystallization of frameworks are divided into two steps under different solvent conditions. This method can improve the crystallinity of COFs, which is feasible for materials that are not easy to crystallize or have good crystallinity but are not easy to repeat[48]. (3) Alcohol-assisted hydrothermal polymerization: water and alcohol are used to replace the commonly used high-boiling point solvents and toxic catalysts, and the imine-based COFs are converted into imide-linked COFs by changing the chemical bonds, which is green and environmentally friendly[49]. (4) Supercritical solvothermal method: Abandoning the organic solvent used in the traditional solvothermal synthesis method, the supercritical CO2 with surface tension close to zero and extremely low viscosity was used as the solvent, and the micron-sized three-dimensional COF single crystal was generated ultra-rapidly within 1 – 5 min for the first time, which broke through the current dilemma that it is difficult to rapidly synthesize highly crystalline or even single crystal three-dimensional COFs[43]. (5) Room temperature solution synthesis method: The mixed system of monomer powder and solvent was allowed to stand at room temperature for 72 H to obtain SCOFs with diameters in the range of 200 – 300 μm[50]. The method is simple and direct, and the obtained SCOFs have high yield, good crystallinity, large and uniform size, and high thermal stability. (6) Heating reflux method: In 2022, Li et al. Added ETBC and 1,4-phenylenediacetonitrile (PDAN) into a mixed solvent of 1,4-dioxane and KOH, and then heated the mixture to 110 ℃ under argon atmosphere for reflux for 72 H to obtain a COF material with yellow luminescence[51].

4 Application

4.1 Catalyze

When COFs materials are used as catalysts, they have obvious advantages: the regular pores of COFs materials are beneficial to material transport[52]; COFs are easy to functionalize, and the introduction of various functional groups into the structure can increase the catalytic reaction sites. The applications of tetrastyryl COFs in catalysis mainly focus on photo-/electro-catalytic hydrogen evolution reaction, photo-/electro-catalytic CO2 reduction reaction, and photocatalytic organic reaction.
Photocatalytic water splitting for hydrogen production can achieve low-cost, large-scale, efficient and clean conversion of solar energy into hydrogen energy[53,54]. Using ETBC and porphyrin-based as building units, Xu et al. Prepared a highly crystalline TP-COF (Fig. 5) with a hydrogen evolution rate of 58.4μmol·g−1·h−1 under visible light with Pt (5 wt%) as the co-catalyst and TEOA (20 vol%) as the sacrificial agent[55]. The catalytic activity of the COF did not change significantly after 30 H of recycling experiment, and the stability was good. In 2017, Sick et al. First reported a compact and oriented BDT-ETTA COF membrane prepared by the condensation of ETTA and benzo [1,2-b: 4,5-b ′] dithiophene-2,6-dicarboxaldehyde (BDT) as a photoelectrode for water splitting without the use of auxiliary catalysts or sacrificial agents[56]. The resulting COF film thickness was 100 nm, and the current density was 1.5μA·cm−2 at 0.2 V (vs RHE). In addition, when the surface of the COF film was coated with Pt nanoparticle catalyst, the current density was 1.1μA·cm−2 at 0.1 V, while the current density measured at 0.3 V was 4.3μA·cm−2, which was a four-fold increase in photocurrent compared with the COF film without catalyst at the same potential. In 2019, Rotter et al., a member of the research group, proposed a new improved method to prepare films with/without Pt nanoparticle catalysts by electrophoretic deposition (EPD), and compared the performance with the COF films prepared in 2017[57]. The results show that the current density of the film prepared by EPD method increases by 117 times with the addition of catalyst, reaching the 128.9μA·cm−2. The improvement of optoelectronic properties intuitively shows that electrophoretic deposition is an important complementary method for COF thin film preparation. In 2022, Yu et al. Designed and synthesized a D-A type COF, which is widely used for catalytic degradation, and the hydrogen evolution rate of the COF is as high as 7204.3μmol·g−1·h−1, which is more than 10 times that of PEBP-COF（217.1μmol·g−1·h−1） without D-A structure in the control group[58].
图5 TP-COF的合成路线及可见光下光催化析氢过程[55]

Fig. 5 The synthetic route of TP-COF and the process of photocatalytic H2 evolution under visible light[55]

Metalloporphyrin-based monomers have been reported to react with different types of tetrastyryl monomers in both visible-light-driven and electro-driven catalytic CO2 reduction.The reason is that the metalloporphyrin-based monomer has high catalytic site density and strong coupling ability, and electrons can be quickly and effectively transferred from the tetrastyryl unit to the metalloporphyrin unit in the catalytic process to promote the conversion of CO2 into CO[37,59]. The COFs materials based on this not only have excellent catalytic performance, but also have excellent durability.
In addition, tetrastyryl COFs have also been used to catalyze organic reactions. Kang et al. Synthesized two kinds of three-dimensional COFs, namely COF-1 synthesized from ETTA with Tris (4-bibenzoyl amine) (NBC) and COF-2 synthesized from ETBC with Tris (4-aminophenyl) amine (BADA)[34]. In the cross-dehydrogenative coupling (CDC) reaction between phenyltetrahydroisoquinoline and CH3NO2, the yields of the reaction catalyzed by the two COFs were in the range of 50% -85%. Secondly, these two COFs have also been used to catalyze asymmetric α-alkylation reactions, and their ability to recognize chiral molecules has been learned. The results showed that the yield of the target chiral molecule was close to 85%, and the enantiomeric excess was as high as 94%, which was comparable to the reaction using metal complexes or organic dyes as photosensitizers. He et al. Reported the first carbon dioxide-masked non-heterocyclic carbene (NHC) modified COF containing tetraphenylethylene unit, and studied the hydrosilylation of CO2 with diphenylsilane.Diphenylsilane was completely consumed within 6 H to promote the next step of hydrolysis to methanol, and the total methanol yield was as high as 90%, which is also one of the best heterogeneous catalysis for CO2 hydrosilylation under alkali-free conditions[60]. It is worth noting that it can also efficiently catalyze the formylation of amines with CO2, and the conversion rate can reach up to 98%. The above results show that the COF catalyst has excellent CO2 masking effect and is an effective method for fixing the CO2.

4.2 Adsorption

Adsorption and separation depend on the pore size, pore type and pore environment of COFs. COFs can be designed into specific materials to achieve the adsorption and separation of specific molecules. The adsorption of gases, organics, metal ions, etc. Proves that COFs materials are powerful tools used to alleviate environmental and energy problems.

4.2.1 Ion adsorption

In 2019, Liu et al. Designed and synthesized a COF-ETTA-2,3-Dha integrating ETTA and 2,3-dihydroxyterephthalaldehyde (2,3-Dha)[61]. It shows very good stability in neutral, acidic, and alkaline solutions, and the intramolecular hydrogen bonding interaction gives it this high stability against hydrolysis. Because there are a large number of accessible ortho-dihydroxy binding sites in COF, it can better adsorb Cd2+ in aqueous solution. From the adsorption capacity versus time curve, it can be seen that the adsorption capacity in neutral solution increases rapidly in the early stage, and the absorption capacity of cadmium is 39.6 mg·g−1 at 1 min and 95.6 mg·g−1 at 20 min. After 60 min, it tends to be stable, reaching the saturated adsorption capacity of 116 mg·g−1, and the absorption effect is significant, which is better in alkaline solution (when pH = 12, the adsorption capacity is close to 120 mg·g−1）, and the effect is the worst in acidic solution). This was one of the highest values of adsorbed Cd2+ reported at that time.

4.2.2 Gas adsorption

Hydrocarbons such as CO2, H2, volatile organic compounds (VOCs), and methane （CH4） are the main gases used in porous organic materials for gas adsorption and storage.
In the research of Gao et al., the TPE-COF-I obtained by imine condensation with ETBA and ETTA as monomers has a complete network structure because the amino and aldehyde groups of the two monomers participate in the reaction.However, TPE-COF-II is a hindered network structure with a larger specific surface area and a CO2 adsorption capacity of 118.8 cm3·g−1 because two aldehyde groups of monomer ETBA did not participate in the reaction, which is one of the COFs with the strongest ability to adsorb carbon dioxide reported at that time[62]. The COFs mentioned by Tian et al. Have two kinds of micropores with different shapes and sizes: quadrilateral micropores and inequilateral hexagonal micropores, which have good adsorption capacity for CO2 and H2, with the CO2 absorption rate of 19.8 wt% (273 K, 1 bar) and the H2 absorption rate of 1.79 wt% (77 K, 1 bar)[63].
In addition, sulfur hexafluoride （SF6） G as is commonly used as a gas insulator in power equipment such as radars and transformers, but under the action of electric arc, sulfur hexafluoride gas decomposes to produce more than a dozen toxic and highly corrosive components such as HF and SO2, resulting in a stronger and longer-lasting greenhouse effect. MOFs are the most effective adsorbents for SF6 gas. Considering that both COFs and MOFs are porous materials and have the characteristics of low density, high heat and chemical stability, Zhang first used COFs for the adsorption of SF6 gas[64]. He used 2,4,6-tris (4-formylphenyl) -1,3,5-triazine (TFPT) as one of the monomers to undergo [4 + 3] condensation with ETTA and ETBC, respectively, to obtain two kinds of COFs. The COF obtained from ETBC has superior adsorption performance because of its larger specific surface area and pore size, and the adsorption capacity of SF6 gas is 4.4 mmol·g−1. In order to further illustrate the adsorption performance, five cycles of SF6 gas adsorption-desorption experiments were also carried out, and the results showed that the adsorption capacity did not decrease significantly. His study was the first to demonstrate the feasibility of COFs materials as SF6 adsorbents.
Li et al. Prepared NAT-COF using ETTA and N-2-aryl substituted triazole derivative (NAT-CHO) as building units[65]. The COF has good stability, moderate specific surface area and good adsorption performance for alkane and olefin gases. The adsorption trend at 273 and 298 K is C3H8>C2H6>C2H4>CH4（ Fig. 6a), where C3H8 has the highest adsorption value at 273 and 298 K, 109.8 and 90.4 cm3·g−1, respectively. They also further examined the gas selectivity, which was 200 and 190 at 273 and 298 K for C3H8 and CH4, respectively; The selectivity between CO2/CH4 is moderate (4 at 273 K and 2.8 at 298 K); The selectivity for CO2 and N2 was 49.1 at 273 K and 13.1 at 298 K. Chen et al. Selected ETTA and TPB monomers to synthesize two-dimensional COF by [4 + 4] reaction design, and the adsorption capacity of this COF for C2H2, CO2, and CH4 was 77.8, 39.4, and 9.6 cm3·g−1, respectively[66].
图6 （a）273 K时NAT-COF C3H8, C2H6, C2H4和CH4的气体吸附[65]；（b）SCU-COF-2粉末填充柱穿透实验示意图[69]

Fig. 6 (a) Gas adsorption of C3H8, C2H6, C2H4 and CH4 for NAT-COF at 273 K[65]; (b) The schematic diagram of breakthrough experiments in the columns packed with SCU-COF-2 powder[69]

In 2021, Cui et al. Used the COF synthesized by ETBC and ETTA as precursors to test the adsorption of volatile organic compounds such as benzene and toluene, and the adsorption capacity of benzene and toluene vapor was 5.8 and 5.20 mmol·g−1 at 293 K/1.0 bar, respectively. This high adsorption capacity also shows that TTPE-COF is a good adsorbent for waste gas[67].
In addition to the above gases, tetrastyryl COFs can also be used to capture and adsorb iodine and iodide vapors. Iodine is a radioactive substance associated with nuclear fission, so the capture of iodine and its compounds is essential for environmental protection and human health. In order to evaluate whether the dual-pore COFs with mesopores and micropores can provide good pore space for iodine absorption, Wang et al. Used kagome type tetrastyryl COFs as an example to study, and the results showed that its adsorption capacity for iodine was 4.79 g·g−1, which was the same as the theoretical value, and the pore occupancy was 100%[68]. In 2021, He et al. Specially designed and developed a nitrogen-rich COF that dynamically captures iodine and methyl iodide at the same time, namely SCU-COF-2. Based on the strong affinity between the nitrogen atom in pyridine and iodine molecules, they chose the electron-rich 2,2 '-bipyridine-5,5' -dicarboxaldehyde as the functional ligand (Fig. 6B)[69]. SCU-COF-2 has a hypervelocity absorption capacity of 6.0 g·g−1 for I2 gas under static adsorption conditions, and SCU-COF-2 has reached a record level in two aspects: one is that the adsorption value for methyl iodide is 1.45 g·g−1; Second, the I2 gas adsorption capacity under dynamic conditions is 0.98 g·g−1.

4.2.3 Biomolecular adsorption

The adsorption of ions and gases by tetrastyryl COFs is relatively common, while the adsorption application in biology is almost absent. In 2019, Lu et al. Prepared TPE-TAP-COF through the condensation reaction between ETBA and TAPP. From the scanning electron microscope (SEM) and transmission electron microscope (TEM) images, it can be seen that the COF is assembled into a microcapsule structure. The microcapsule is a hollow cavity with a very unique structure. COFs materials self-assembled into a hollow capsule structure have not been reported before[70]. It has a significant adsorption effect on hemoglobin (Hb), and the adsorption capacity of Hb in 8 H is 550.82 mg·g−1, which is the highest adsorption capacity of Hb in the known COFs at that time, and the adsorption principle between them is the surface electrostatic interaction. This work provides a certain reference value for the adsorption of biomolecules on porous materials with specific morphology.

4.3 Sensor

The tetrastyryl COFs sensor overcomes the aggregation-induced fluorescence quenching caused by electrostatic interaction and other factors, has high quantum yield in the aggregation state, can emit strong fluorescence, has the advantage of detecting various substances with naked eyes, and also improves the sensitivity of analysis and testing.

4.3.1 Explosive sensor

Nitro explosives, such as 2,4,6-trinitrophenol (TNP), 2,6-dinitrotoluene (DNT) and 2-nitrophenol (NP), are commonly used in pharmaceutical industry, fireworks and military, which not only cause environmental pollution, but also cause strong irritation to the eyes, skin and organs of workers, resulting in irreversible damage. Therefore, it is of great practical significance to detect explosives quickly, efficiently and sensitively for environmental protection, anti-terrorism and stability maintenance, national defense and military industry.
In 2012, Zhang et al. First reported the synthesis of highly fluorescent COF for explosive sensing using a microwave-assisted method[71]. By this method, terephthalaldehyde and melamine were polycondensed to form COF nanoparticles, called SNW-1. Its fluorescence can be rapidly quenched by nitroaromatic explosives such as TNP, DNT and nitrobenzene (NB), among which the quenching effect on TNP is the strongest, and the detection limit of the sensor is as low as ppb level. Since then, there have been more and more studies on the application of COFs in the field of explosive sensing. In 2018, Gao et al. Selected ETBA and 1,3,6,8-tetrakis (4-aminophenyl) pyrene units to synthesize a tetrahydrofuran solution of Py-TPE COF nanoparticles, which exhibited the highest photoluminescence quantum yield (PLQY) of 21.1% among the imine-based COFs reported at that time[72]. Under the same conditions, its quenching percentage for TNP reaches 95.5%, while its quenching degree for PL of other explosives is very small, which shows that the COF has excellent selectivity for TNP (Fig. 7). In 2019, Faheem et al. Assembled ETTA and conjugated planar 9,10-anthracene dialdehyde as monomers to synthesize dual-fluorescent DL-COF[73]. It has high sensitivity and excellent selectivity for nitroaromatic explosives, with a detection limit of ppb level, which is superior to many nitroaromatic fluorescent sensors based on COFs and MOFs.
图7 丙酮中加入TNP （0~25 ppm）后Py-TPE-COF的荧光猝灭实验[72]

Fig. 7 Fluorescence quenching experiments of the Py-TPE-COF upon addition of TNP (0-25 ppm) in acetone[72]

There is π-π stacking between the layers of two-dimensional COFs, which will affect the fluorescence properties of COFs and the interaction between COFs and guest molecules. Therefore, fluorophores were introduced into three-dimensional COFs and then applied to explosive sensing. In 2018, in Ding's research, 3D-TPE-COF was prepared from ETBC and tetrakis (p-aminophenyl) methane (TAPM) by Schiff base reaction[74]. When TNP with a concentration of 1×10−2mol·L−1 was added to the uniformly dispersed COF solution, the fluorescence quenching effect on the COF became more and more obvious with the increase of TNP concentration, and the quenching constant was 3.3×10−4mol−1, which was equivalent to the quenching efficiency （3.1×10−4mol−1） of three-dimensional pyrenyl COF obtained by the research group in 2016.

4.3.2 Ion sensor

COFs can be designed, and the sensing of corresponding ions can be realized by introducing functional groups that can interact with ions into the pores of COFs. Tetrastyryl COFs are mainly used for sensing metal ions such as Al3+, Fe3+, Hg+, and Hg2+.
In 2021, Xiu et al. Constructed COF-DHTA based on ETTA and 2,5-dihydroxyterephthalaldehyde (Dha) as a fluorescent chemosensor (Fig. 8A)[75]. When COF was uniformly dispersed in DMF solution, the obtained suspension showed moderate fluorescence emission. After adding various metal ions to the suspension, only the addition of Al3+ significantly enhanced the fluorescence intensity by more than one time, while the addition of other metal ions slightly quenched the fluorescence. The fluorescence intensity of the suspension at 352 nm showed a good linear relationship with the concentration of Al3+, and the detection limit was 0.927μmol·L−1. The sensing mechanism is that the Al3+ coordinates with the N and O atoms on the COF, and the interaction inhibits the light-induced electron transfer on the N atom.
图8 （a） COF-DHTA的Al3+传感过程[75]；（b） TTPE-COF在293 K下对水、苯和甲苯的吸附等温线，以及在365 nm紫外灯下的荧光照片[67]

Fig. 8 (a) Al3+ sensing mechanism of COF-DHTA[75]; (b) Water, benzene, and toluene adsorption isotherms of the TTPE-COF at 293 K, and the fluorescence photographs under a 365 nm UV lamp[67]

Fe3+ is also an important biological metal ion, which is the main component of hemoglobin and participates in the transport of oxygen in the human body. Iron deficiency can easily lead to anemia. The COF constructed by Cui et al. Not only can effectively adsorb CO2 and volatile organic compounds, but also has the ability to specifically sense Fe3+ ions[67]. Its fluorescence intensity showed almost no fluorescence emission after the addition of Fe3+, the quenching percentage was close to 99.6%, and the detection limit was 3.07μmol·L-1. At the same time, the cycle performance and stability are excellent. After five cycles, the quenching percentage does not change much, and the morphology and structure of COF remain unchanged before and after cycling (Fig. 8B).
Hg is a highly toxic element, if absorbed by the human body, it will lead to chronic poisoning, causing substantial damage to organs, nervous system and endocrine system. Zheng et al. Synthesized sulfur-containing COF with ETBC and 4,4 ′ -dithioaniline, and the sulfur active sites were embedded in the pore wall and distributed uniformly[76]. As a sensitive sensor for the selective detection of toxic mercury ions, its response to Hg+ and Hg2+ can be directly observed with the naked eye, and the detection limits for both are 1.22 and 38.7 ppb, respectively.

4.3.3 Acid-base sensor

Acids and alkalis in gaseous and liquid States are harmful to human body mainly because of their strong irritation and corrosiveness. In 2019, Cui et al. Prepared yellow COF-ETA-DAB by Schiff base condensation of ETBA and 1,4-diaminobenzene (DAB)[77]. A distinct color change from yellow to red occurs upon exposure to HCl gas with a response time of less than 1 s, which is faster than most HCl gas sensors reported before. The COF treated by HCl can return to its original yellow color after exposure to ammonia vapor, which has good reversibility. After 10 cycles of alternate treatment of HCl and ammonia, the reversible change of color between yellow and red was always observed, the tolerance was good, and the trace HCl in 1,4-dioxane could be accurately detected. This COF makes a good chemical sensor for spectroscopic and naked-eye detection of gaseous HCl due to the rapid, distinct color change that is visible to the naked eye.
When Gong et al. Studied the application of solid-state highly luminescent COFs in the field of fluorescence sensing, the response of tetrastyryl COF linked by hydrazone bond to TFA vapor was taken as the research object (Fig. 9)[78]. When exposed to TFA vapor, the fluorescence intensity of the COF decreased rapidly within 3 s, and the fluorescence was basically quenched after 6 s. The COF has the characteristics of fast response, good stability and good repeatability. The large-sized spherical COF material synthesized by Li et al. Can also be used as a visual indicator of acid. When the COF material is added to an acid solution (HCl, H2SO4, or HNO3）), the color quickly changes from orange to red, and the color will deepen to dark red with the increase of the concentration of the acid solution[50]. Interestingly, the color of spherical COF eventually changes back to orange in highly acidic solution. The more acidic the solution, the less time it takes for the color to change. The acidity of the solution can be evaluated semi-quantitatively according to the color change of the solution and the time for the recovery of orange. Another COF synthesized by ETBA and TAPP showed pH dependence in a certain pH range: the fluorescence intensity decreased gradually with the decrease of pH from 4.15 to 2.01, and was completely quenched at pH = 2.01[79]; When pH ≤ 2, the color change from dark red to bright green is very clearly observed; When pH ≥ 3, the color change is less obvious. This particularly sensitive response indicates that the COF is a good material for pH sensing and is expected to play a potential role in water quality monitoring.
图9 TFA熏蒸不同时间后试纸的荧光发射光谱以及TFA蒸气和TEA蒸气（λex = 365 nm）作用下试纸的光学照片[78]

Fig. 9 Fluorescence emission spectra of test paper fumigated by TFA at different times and optical photographs of test paper upon exposure to TFA vapour and TEA vapour (λex= 365 nm)[78]

In 2016, Dalapati et al. Reported that TPEBA and monomeric THB synthesized COF containing boric acid bond[41]. Because boric acid and ammonia are a Lewis acid-base pair and can interact with each other, boric acid and ammonia can be used as a fluorescent sensor for NH3. The addition of NH3 to the toluene solution of this COF can rapidly reduce its luminescence, the Stern-Volmer plot is an almost linear curve, and the fluorescence quenching constant Kq is 4.1×1014M−1·s−1. Reducing the amount of COF to 0.25 mg (2 mL toluene), 1 ppm NH3 was still able to reduce the fluorescence intensity by 30%. When the toluene solution is changed to cyclohexane solution, the same （Kq=1.4×1014M−1·s−1） of NH3 sensing level can also be obtained. From these two extremely high Kq values, it can be proved that TPE-Ph COF has a highly sensitive detection ability for sub-ppm levels of ammonia.

4.3.4 Enantioselective sensor

Chiral discrimination is an important research, which plays a vital role in the fields of chemistry and biology. In 2019, Wu et al. Synthesized a binaphthol-based chiral dialdehyde compound (BINOL-DA) through a five-step reaction using binaphthyl with axial chirality as the starting chiral molecule, and constructed a two-dimensional layered tetragonal chiral binaphthol CCOF-7 with ETTA monomer (Fig. 10)[80]. It can be easily exfoliated into ultrathin 2D nanosheets and electrospun into free-standing nanofiber membranes. In solution and film systems, the fluorescence of COF nanosheets is quenched by the same terpenoid in a gas atmosphere, and the film can recognize the chiral terpenoid in a gas atmosphere according to the different fluorescence quenching rates of the chiral terpenoids with different configurations. Compared with homogeneous and membrane systems based on BINOL, COF nanosheets exhibit great sensitivity and enantioselectivity due to the constraint effect and conformational rigidity of the sensing BINOL group in the framework.
图10 7@PVDF暴露于α-蒎烯后的下降百分比[80]

Fig. 10 Decrease percentage upon exposure to α-pinene for 7@PVDF[80]

Song et al. Designed and synthesized COF linked by aminal bond with ETBC and piperazine, which had higher electrochemiluminescence signal compared with single component, single pore or double pore imine-based COF, and was used to selectively identify L-phenylalanine and D-phenylalanine[81]. The ECL sensor was used to detect L-phenylalanine in a mixture system containing different concentrations of L-phenylalanine and a fixed concentration of D-phenylalanine, and the recoveries were 92. 3% -103. 2%, and the recoveries were 96. 9% -107. 2% in human serum.

4.3.5 Biosensor

In addition, COFs have also been applied to biosensing signal amplification technology. For example, for the first time, Dong et al. Successfully prepared ultrathin two-dimensional nanosheets by using the variable temperature gas stripping method and applied them to the recognition of biomolecules, which significantly amplified the signal of fluorescence sensing (Fig. 11)[82]. In this work, three highly crystalline 2D COFs (NUS-30 ~ 32) were obtained by condensation of ETBC with hydrazine and p-phenylenediamine. When the prepared nanosheets were used to detect various amino acids, the fluorescence was quenched rapidly, and the affinity with amino acids decreased with the increase of azine groups in COF. In addition, L-DOPA was also tested, and the fluorescence intensity of NUS-30 nanosheets gradually decreased during the titration. The biggest advantage of this ultrathin nanosheet is that it does not need to pretreat the sample, and the analyte can be detected almost immediately after the biomolecule is mixed with the nanosheet, which is significantly more sensitive than the small molecule sensor, and has great potential in drug detection.
图11 用L-苯丙氨酸滴定NUS-30纳米片的Stern-Volmer图和NUS-30纳米片的AFM图像[82]

Fig. 11 Stern-Volmer plots of NUS-30 nanosheets being titrated with L-phenylalanine and AFM images of NUS-30 nanosheets[82]

Nanomaterials with enzyme-like properties, called nanozymes, have the potential to be an alternative to natural enzymes. As metal-free nanoenzymes, COFs have flexible molecular design and synthesis strategies, porous and chemically stable structures. In 2022, Li et al. Designed and synthesized two D-A type COFs, namely ETTA-Tz COF and ETTA-Td COF[83]. By incorporating the electron acceptor 4,4 ′- (thiazolo [5,4-d] thiazole-2,5-binaphthyl) dibenzaldehyde (Tz) or 4,4 ′- (benzo [C] [1,2,5] thiadiazole-4,7-binaphthyl) dibenzaldehyde (Td) with the electron donor ETTA into the framework. The two functionalized D-A COFs showed excellent oxidase-like activity under illumination and could catalyze the oxidation of chromogenic substrate (TMB) to dark blue in the presence of dissolved oxygen. ETTA-Tz COF was used to detect sulfide ions in biological samples based on its efficient enzyme activity and typical color change. After adding S2− to complex biological samples, the absorption intensity of TMB oxidized by ETTA-Tz COF was significantly inhibited. With the increase of concentration,The color change from dark blue to colorless was clearly observed by the naked eye, with a linear range of 1~50μmol·L-1 and a detection limit of 0.27μmol·L-1 within 3 min, indicating that the COF is a sensitive and effective biosensor for the visual detection of S2−. The colorimetric method was also successfully used for the detection of sulfide ions in human serum.

4.4 Optoelectronic application

4.4.1 Light emitting diode

The light-emitting diode coating made of tetraphenylethylene-based COFs has the advantages of stability and no rare earth or transition metal ions. In their research, Li et al. Used ETBC and p-phenylenediacetonitrile as raw materials to prepare yellow light-emitting COF by condensation, which has good thermal stability in the working temperature range of LEDs and is suitable for metal-free phosphors of LEDs to prepare cold/neutral/warm white and yellow LEDs with excellent luminous performance[51]. Ding et al. Used ETBC and tetrakis (p-aminophenyl) methane (TAPM) as reaction monomers to obtain 3D-TPE-COF[84]. The activated COF solid powder, epoxy resin and mortar were mixed to obtain a uniform slurry, which was uniformly coated on the blue LED. The yellow COF powder combined with the blue light emitted nearly pure white light, and the light intensity remained basically unchanged even after continuous electrification for 1200 H, with good stability.

4.4.2 Electrochemical energy storage

Supercapacitors and solar cells are suitable devices to store energy. Supercapacitor has the advantages of good conductivity, high stability, fast charge and discharge, and periodic structure, which is a sustainable energy storage device.
The COF synthesized by EL-Mahdy et al. Has a high specific surface area （1067 m2·g−1） and pore volume （0.84 cm3·g−1）, and a specific capacitance of 237.1 F·g−1 at a current density of 2 A·g−1. In addition, it shows good cycling stability at 10 A·g−1, with a capacitance retention of 86.2% after 5000 cycles[36]. Patra et al. Also used PT-COF synthesized by ETBC and TAPP as an ultracapacitor energy storage system with a combination of electrochemical double-layer capacitor and pseudo-capacitor (Fig. 12A)[40]. In 0.5 mol·L-1H2SO4, this COF showed a maximum specific capacitance of 1443 F·g−1 at a current density of 1 A•g−1 with 91% capacitance retention after 3000 cycles. Due to the presence of porphyrin units in the framework, it has excellent redox activity in acidic medium and can act as an energy storage material for supercapacitors under acidic conditions, with storage performance superior to most electrode materials based on COFs (power density of 7.3 kW·kg−1）).
图12 （a）PT-COF的电容储存过程[40]；（b）钙钛矿电池的能级图和示意图[39]

Fig. 12 (a) The capacitor storage process of PT-COF[40]; (b) The energy-level diagram and schematic illustration of the PVSCs[39]

In 2020, Mohamed et al. Realized the application of tetrastyryl COFs in solar cells. They coupled 3,3 ', 6,6' -tetraformyl-9,9 '-dicarbazole (Car-4CHO) monomer and 1,3,6,8-tetrakis (4-formylphenyl) pyrene (TFPPy) monomer with ETTA through [4 + 4] condensation reaction to obtain Car-ETTA COF and TFPPy-ETTA COF (Figure 12b)[39]. The energy level alignment at the HTL/perovskite interface can be well tuned by using COF as a surface modifier for the HTL in perovskite solar cells (PVSCs). In addition, the introduction of hydrophobic medium between COF and perovskite can improve the crystallinity of perovskite layer, showing defect passivation ability. The results show that the photoelectric conversion efficiency of the COF-modified device can be increased from 17. 40% to 19. 80%.

4.4.3 Other

The rigid structure and regular pores of COFs endow them with excellent optoelectronic properties. However, due to the anisotropic growth of COFs, they usually exist in the form of solid powder and can not be well processed into optoelectronic devices. In 2020, Xiong et al. Selected monomeric ETBC and monomeric TAPT with photoelectric activity to synthesize Cu-based monolayer graphene by chemical vapor deposition, and grew COF in situ to form an ordered COF-graphene heterostructure, and used the COF-graphene heterostructure to prepare a photoelectric detector with excellent performance, with a photoresponsivity of up to 3.2×107A·W−1 at 473 nm and a response time of about 1.14 ms[32].
Peng et al. Successfully synthesized a series of three-dimensional single crystal COFs by supercritical solvothermal method, including sc-COFTPE synthesized by ETBC and tetrakis (4-aminophenyl) methane (TAM), and applied them to the field of polarization optics[43].

4.5 Biological application

Bio-nanopore analysis technology has a wide range of applications in biology and medicine, including DNA sequencing, single molecule detection and so on. Two-dimensional COFs have atomically controlled pores, and the affinity between biomolecules and two-dimensional COFs is higher than that of two-dimensional inorganic materials, so COFs nanopores have advantages and potentials in single molecule detection. Xing et al. Synthesized two tetrastyryl COFs with different pore sizes according to the literature method, and they studied the transport process of long (calf thymus DNA) and short (DNA-80) DNA molecules.It was found that the small pore size of COF-1.1 nanopores increased the current blockage to some extent and prolonged the residence time. The passage speed of DNA-80 molecules was 270 μs/base, which was the slowest speed observed so far compared with two-dimensional inorganic nanomaterials[38]. This study proves that two-dimensional COFs nanoporous materials can be applied to single-molecule DNA analysis, which broadens the application field of COFs materials.
Enzyme is a natural catalyst with high catalytic activity, but its activity is easily affected by pH, temperature and other factors. Immobilization can improve the stability of enzyme. COFs can be used as a feasible carrier for immobilized enzymes because their structure is easy to be functionalized, which helps to maintain the interaction between COFs and enzymes. Sun et al. Compared the performance of the immobilized enzyme between a two-pore tetrastyryl COF containing ETTA monomer and another one-pore COF containing pyrenyl as a control[85]. The results showed that the immobilized enzyme in the double-pore COF not only had higher reactivity, but also had stronger ability to resist the blockage of catalyst pores caused by excessive by-products, which made the reaction more thorough. The molecular units used to construct COFs are various, and the development of new framework structures or the modification of existing frameworks as scaffolds for immobilized enzymes in the future is still the focus of research in this field.
You et al. Synthesized AIEgen sp2c-COF（ by Knoevenagel condensation of ETBC with 1,4-phenylenediacetonitrile (PDAN) (Fig. 13)[86]. Tannic acid (TA) is bonded to the surface of COF, and when there is a Fe3+, they are coordinated and crosslinked to form a FeIIITA network, which can quench the high luminescence of COF. When the COFTFBE-PDAN@FeIIITA nanocomposite is put into tumor cells, the high concentration of glutathione (ROS) environment and acidic lysosomes in the cells will decompose the FeIIITA network into Fe3+ and TA, and successfully turn on luminescence. GSH and TA can convert Fe3+ into Fe2+, which can react with H2O2 in tumor cells to produce ROS, and lead to lipid peroxide (LPO) mediated iron death under the dual effects of ROS production and RSH consumption. This study shows that COFs based on tetrastyryl luminescence play an important role in cell imaging probes and medical therapy, and greatly broadens the potential applications of COFs in the biological field.
图13 COFTFBE‑PDAN@FeIIITA-PEI的制备和用于目标肿瘤细胞的发光成像和铁死亡的示意图[86]

Fig. 13 Schematic illustration of the preparation of COFTFBE‑PDAN@FeIIITA-PEI for luminescence imaging and ferroptosis in target tumor cells[86]

5 Prospects and Challenges

Tetrastyryl compounds provide unique building blocks for the synthesis of COFs and enrich the field of COFs. This review summarizes the development of tetrastyryl COFs and their applications in adsorption, catalysis, sensing, photoelectrochemistry, and biomedicine.
At present, the monomer types of tetrastyryl COFs are still relatively scarce, and most of the tetrastyryl COFs are two-component, and the three-component monomer COFs developed are very few, which to some extent limits the development of different tetrastyrylCOFs. As mentioned above, introducing functional groups or substituents and changing solvent conditions are flexible strategies to develop tetrastyryl COFs with novel topology and porous structure, and the development of more diverse tetrastyryl COFs in the future is still a key point to be broken through[87][88,89][90]. Since the two monomers used have been reported to contain tetrastyryl, whether there is an interaction or synergistic effect between the two monomers, so as to construct tetrastyryl COFs with mixed bonds and their application properties still need further study.
To sum up, tetrastyryl COFs have shown strong application potential and development prospects in various fields. In the future, attention should be paid to enrich the structural diversity of tetrastyryl COFs and improve their application performance.

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