A covalent organic framework material and a method of synthesizing the same

Abstract

The application belongs to the field of organic materials, and particularly relates to a kind of covalent organic framework materials and a synthesis method thereof.The method of the application uses metal-free organic phosphine as catalyst, and monomers containing amino functional groups and monomers containing aldehyde functional groups are obtained through condensation reaction to obtain the covalent organic framework materials.The method of the application can prepare a variety of aggregate states of COFs.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic materials, and particularly relates to a kind of covalent organic framework material and a synthesis method thereof. BACKGROUND

[0002] Covalent organic framework materials (COFs) are two-dimensional (2D) or three-dimensional (3D) porous crystalline organic polymer materials connected by covalent bonds between organic monomers, with advantages such as low density, large specific surface area, regular and stable structure, uniform pore size, and easy functionalization. Due to their highly ordered structure, high chemical stability, large specific surface area, and diverse functional properties, COFs have attracted extensive research interest. Unlike traditional metal-organic frameworks (MOFs), COFs are two-dimensional or three-dimensional crystalline porous polymers connected by covalent bonds between light elements such as C, O, N, and B. Their unique structural characteristics endow COF materials with great application potential in fields such as gas storage, separation, catalysis, sensing, and energy storage.

[0003] From the perspective of molecular design, COF materials can be precisely controlled in terms of pore size, shape, and chemical environment by selecting appropriate monomers and connection methods. This high degree of designability allows researchers to tailor COF materials with specific functions for specific application needs. In addition, the properties of COFs can be further enhanced and expanded through the introduction of functional monomers or subsequent modification methods, making them exhibit important application prospects in fields such as molecular recognition, drug release, and optoelectronic materials.

[0004] In recent years, the synthesis of various condensed COF-based materials (COF Gels) has also gradually attracted attention. Due to the covalent bonding of COFs, it is difficult to control the aggregation state of COFs prepared by traditional processes, and most of them are in powder form. In a few cases, COF gels can be obtained by selecting a mixed solvent for the reaction of multiple components. In practical applications, the amount and ease of obtaining condensed state are key factors in the application of COF materials. As an example, COF gels are a three-dimensional network structure with properties similar to solids but containing a large amount of solvent (or gas). This special condensed state material exhibits important value in fields such as materials science, environmental science, and biomedicine. On the one hand, the high porosity and functional surface of COF materials provide a guarantee for their high efficiency in catalysis and adsorption; on the other hand, the flexibility and formability of the gel state improve the application requirements of the material. On the other hand, continuous COF blocks theoretically have strong mechanical properties, and can have a longer service life in some application scenarios while retaining porosity. Therefore, it is urgent and practically significant to develop a simple, universal, green, and pollution-free synthesis method for preparing COF materials in gel, powder, and continuous block forms suitable for large-scale production.

[0005] Currently, the most commonly used catalyst for COF is an acid (such as acetic acid) or a base (such as sodium hydroxide) for synthesizing imine or olefin-bonded COFs. On the other hand, Lewis acids (such as scandium triflate and pentafluorophenylboron) and Lewis bases (including pyridine and isoquinoline) have also been reported as catalysts for COF synthesis. In addition to the above-mentioned catalysts, few new catalysts for COF synthesis have been reported. SUMMARY

[0006] In view of the problems existing in the prior art, the present application provides a covalent organic framework material and a synthesis method thereof. The synthesis method uses a metal-free organophosphorus compound as a catalyst to prepare COFs materials in various aggregate states such as blocks, powders or gels.

[0007] A first technical problem to be solved by the present application is to provide a synthesis method of a covalent organic framework material (COFs). The synthesis method comprises the following steps: obtaining the covalent organic framework material by condensation reaction of an organic monomer 1 and an organic monomer 2 under a catalyst; wherein the organic monomer 1 is a two-connected monomer containing an amino functional group or a three-connected monomer containing an amino functional group, the organic monomer 2 is a two-connected monomer containing an aldehyde group functional group or a three-connected monomer containing an aldehyde group functional group, and the catalyst is a metal-free organophosphorus compound.

[0008] Specifically, in the above synthesis method, the organic monomer 1 is selected from 1,3,5-tris(4-aminophenyl)benzene, 2,4,6-tris(4-aminophenyl)pyridine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, tris(4-aminophenyl)amine or [1,1'-biphenyl]-4,4'-diamino, benzidine, p-phenylenediamine, 4,4'-diaminomethyl biphenyl.

[0009] Specifically, in the above synthesis method, the organic monomer 2 is selected from 1,3,5-tris(p-formylphenyl)benzene, 1,3,5-tris(2-formylpyridin-5-yl)benzene, 1,3,5-tris(3'-aldehyde-4'-hydroxyphenyl)benzene, 2,4,6-tris(4-formylphenyl)pyridine, trimesaldehyde, triformylphloroglucinol, 2,4,6-tris(4-formylphenyl)-1,3,5-triazine, tris(4-formylphenyl)amine, 2,5-dihydroxy-p-xylene dicarboxaldehyde, 1,4-dialdehyde-2,5-divinylbenzene, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 6-(4-formylphenyl)pyridine-3-carboxaldehyde or 3,3'-dimethoxybiphenyl-4,4'-diacetaldehyde.

[0010] Specifically, in the above synthesis method, the catalyst is selected from a phosphine compound containing a phenyl group or a phosphine compound containing an alkyl chain.

[0011] Further, in the above synthesis method, the catalyst is selected from triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, trioctylphosphine, trioctylphosphine oxide or diphenylphosphine.

[0012] Preferably, in the above synthesis method, the molar ratio of the organic monomer 1 and the organic monomer 2 is 1:4 to 4:1. More preferably, it is 2:3 to 3:2.

[0013] Preferably, in the above synthesis method, the molar ratio of the catalyst and the organic monomer 1 is 0.625:1 to 10:1. More preferably, it is 3:1 to 5:1.

[0014] Preferably, in the above synthesis method, the condensation reaction temperature is 70-200℃. Preferably, it is 80-120℃. More preferably, it is 80℃.

[0015] Preferably, in the above synthesis method, the condensation reaction time is 3-5 days. Preferably, it is 5 days.

[0016] Preferably, in the above synthesis method, the condensation reaction is carried out in a solvent-free system or in a solvent system.

[0017] Further, in the above synthesis method, the solvent is selected from dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide, mesitylene, n-butanol or o-dichlorobenzene.

[0018] The second technical problem to be solved by the present application is to provide a covalent organic framework material synthesized by the above synthesis method.

[0019] Preferably, in the above covalent organic framework material, the morphology of the covalent organic framework material is block, powder or gel.

[0020] Preferably, in the above covalent organic framework material, the pore size of the covalent organic framework material is 1.8-4.9nm. More preferably, it is 2.95-3.62nm.

[0021] The present application mainly uses metal-free organic phosphine as a catalyst, and dehydrates and condenses two building units to prepare a covalent organic framework material with uniform pore size, high crystallinity and high specific surface area. The present application can prepare various aggregate COF products, such as block, powder and gel, and can be prepared under normal pressure and incomplete sealing. Moreover, the present application can prepare a block COF gel product with certain strength. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 Product photo of Example 1

[0023] Figure 2 XRD spectrum of product of Example 1

[0024] Figure 3 Product mechanical diagram of Example 1

[0025] Figure 4 Product XRD spectrum of Example 2

[0026] Figure 5 Product photo of Example 3

[0027] Figure 6 Product XRD spectrum of Example 3

[0028] Figure 7 Product mechanical diagram of Example 3

[0029] Figure 8 Product photo of Example 4

[0030] Figure 9 Product XRD spectrum of Example 4

[0031] Figure 10 Product XRD spectrum of Comparative Example 1

[0032] Figure 11 Product XRD spectrum of Comparative Example 2

[0033] Figure 12 Product XRD spectrum of Comparative Example 3 DETAILED DESCRIPTION

[0034] The present application provides a kind of covalent organic framework material and synthesis method thereof.The synthesis method includes the following steps: organic monomer 1 and organic monomer 2 are obtained by condensation reaction under catalyst to obtain the covalent organic framework material;Wherein, the organic monomer 1 is the amino functional group-containing two-linking monomer or the amino functional group-containing three-linking monomer, the organic monomer 2 is the aldehyde group-containing two-linking monomer or the aldehyde group-containing three-linking monomer, and the catalyst is a metal-free organic phosphine compound.

[0035] The synthesis method of the present application can be carried out in a solvent-free system or in a solvent system.The solvent can be dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide, mesitylene or n-butanol or o-dichlorobenzene, etc.When using a solvent-free system, the product prepared is in block form;when using a traditional mixed solvent system (for example, n-butanol and o-dichlorobenzene mixed solvent), the product prepared is in powder form;when using a single dipolar aprotic solvent system (for example, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide), the product prepared is in gel form.

[0036] The synthesis method of the present application can be carried out under vacuum, or under normal pressure or pressurized conditions.The vacuum is generally controlled to a system pressure of 0-1 atm.

[0037] The synthesis method of the present application can be carried out under closed conditions or under non-closed conditions. The closed reaction container can be one of a threaded sample bottle, a Pyrex tube resistant to high temperature and high pressure, a flame-sealed ampoule, and a steel high-pressure reaction kettle with a polytetrafluoroethylene liner.

[0038] The synthesis method of the present application further includes a post-treatment step after the condensation reaction: using solvent A to wash away the unreacted monomers, then using solvent B to wash away the catalyst, and finally using solvent C to wash again and dry; or for gel products, without using solvent C to wash, but directly replacing the solvent with the corresponding application environment. The solvent A is selected from DMF, dimethyl sulfoxide, N,N-dimethylformamide or DMI. The solvent B is selected from ethanol, methanol, isopropanol, n-propanol or n-butanol. The solvent C is selected from anhydrous tetrahydrofuran, ethyl acetate, acetonitrile or dichloromethane. Further, the Soxhlet extraction method is used when washing with solvent C.

[0039] Further, the synthesis method of the covalent organic framework material of the present application includes the following steps: placing organic monomer 1, organic monomer 2 and catalyst into a container with or without solvent, under normal pressure or under vacuum (vacuum to a pressure of 2×10 -5 MPa, for half an hour, by flame sealing), placing the reaction container into an oven at 70-200°C for 3-5 days, after the reaction is completed, washing the obtained material with solvent A (such as DMF, dimethyl sulfoxide, N,N-dimethylformamide, DMI, etc.) to remove unreacted monomers, then washing with solvent B (such as ethanol, methanol, isopropanol, n-propanol, n-butanol, etc.) to remove the catalyst, and then Soxhlet extracting the obtained material in solvent C (such as anhydrous tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, etc.) to remove the unreacted small molecules in the pores, and finally heating and drying the obtained material in a vacuum oven at 80-150°C (preferably 100°C) for 12-24h (preferably 12h) to remove the residual solvent in the pores, or for gel products, the solvent in the pores can be directly replaced with the corresponding application required solvent environment (such as replacing with an organic solvent containing an organic substrate for organic catalysis experiments, or directly replacing the solvent with water for photocatalytic hydrogen production experiments, etc.), to obtain a covalent organic framework material with high crystallinity.

[0040] Example 1

[0041] Weigh 1,3,5-tris(4-aminophenyl)benzene (TAPB) (0.08 mmol, 28.1 mg), 2,5-dimethoxybenzene-1,4-dicarbaldehyde (DMTA) (0.12 mmol, 23.3 mg), and triphenylphosphine (0.4 mmol, 104.9 mg) and carefully place them into a high-temperature and high-pressure thick-walled glass tube. Evacuate the powder until the pressure in the tube reaches 2×10 -5 MPa, the glass tube was removed from the vacuum line and sealed with a flame generated by a butane torch to isolate the air. The sealed glass tube was placed in an 80°C oven for 3 days. After the reaction, a hard yellow-brown block was obtained. After soaking it in DMF and ethanol, Soxhlet extraction was continued in tetrahydrofuran solvent for 48 hours to obtain a hard yellow-brown block (see Figure 1 ), the mass is about 39 mg, and the yield is about 78%-83%. Figure 2 As shown in FIG, powder X-ray testing revealed that the powder sample of the product prepared by the phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a solvent-free environment was crystalline. Figure 3 As shown, the compression test revealed that the powder sample of the product prepared by phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a solvent-free environment has a certain strength, which can reach 1-2MPa, proving to be a continuous block.

[0042] Example 2

[0043] Weigh 1,3,5-tris(4-aminophenyl)benzene (TAPB) (0.08 mmol, 28.1 mg), 2,5-dimethoxybenzene-1,4-dicarbaldehyde (DMTA) (0.12 mmol, 23.3 mg), and triphenylphosphine (0.4 mmol, 104.9 mg), carefully place them into a high temperature and high pressure resistant thick-walled glass tube, add 2 mL of mixed organic solvent (V 正丁醇 :V 邻二氯苯 =1:1), freeze with liquid nitrogen, and evacuate the tube to a pressure of 2×10 -5 MPa, it was removed from the vacuum line and sealed with a flame generated by a butane torch to isolate the air. The sealed glass tube was placed in a 120°C oven for 3 days. After the reaction, a yellow-brown solid powder was obtained. After soaking it in DMF and ethanol, Soxhlet extraction was carried out in tetrahydrofuran solvent for 48 hours to obtain a yellow-brown powder with a mass of about 41 mg and a yield of about 78%-83%. Figure 4As shown, powder X-ray testing revealed that the powder sample prepared by phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a conventional solvent system (mixed solvent system) was crystalline.

[0044] Example 3

[0045] Weigh 1,3,5-tris(4-aminophenyl)benzene (TAPB) (0.08mmol, 28.1mg), 2,5-dimethoxybenzene-1,4-dicarbaldehyde (DMTA) (0.12mmol, 23.3mg), and triphenylphosphine (0.4mmol, 104.9mg), carefully put them into a glass tube, add 2mL of dipolar aprotic solvent (dimethylformamide), mix well and add them into a 5mL plastic syringe, seal it with plastic film and place it in an 80℃ oven to react for 3 days. After the reaction, a yellow-brown organic solvent gel is obtained. After washing it in DMF and ethanol, the corresponding liquid gel ( Figure 5 ).like Figure 6 As shown in FIG, powder X-ray analysis revealed that the liquid gel sample prepared by the phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a dipolar aprotic solvent system was crystalline. Figure 7 As shown, rheological tests revealed that the gel product prepared by phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a dipolar aprotic solvent system has a certain strength, which can reach 1-2MPa, proving to be a continuous block.

[0046] Example 4

[0047] The other operations were the same as those in Example 3. Furthermore, the obtained liquid gel was treated with supercritical carbon dioxide (8 MPa, 35° C.) to obtain a yellowish-brown aerogel ( Figure 8 ), the mass is about 43 mg, and the yield is about 78%-83%. Figure 9 As shown, powder X-ray analysis revealed that the gel sample prepared by the phosphine-catalyzed reaction of 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarbaldehyde in a dipolar aprotic solvent environment was crystalline.

[0048] Example 5

[0049] Tri-aldehyde resorcinol (0.08 mmol), 3,3'-dihydroxybenzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully charged into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and loaded into a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days. After reaction, a reddish-brown organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel.

[0050] Example 6

[0051] Tri-aldehyde resorcinol (0.08 mmol), 2,2,5,5-tetrachlorobenzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully charged into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and loaded into a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days. After reaction, a reddish-brown organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel.

[0052] Example 7

[0053] Tri-aldehyde resorcinol (0.08 mmol), 3,3',5,5'-tetramethylbenzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully charged into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and loaded into a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days. After reaction, a reddish-brown organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel.

[0054] Example 8

[0055] Tri-aldehyde resorcinol (0.08 mmol), 3,3-dimethoxybenzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully weighed into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and then added to a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days after a simple seal was made using plastic film. After the reaction, an orange organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel.

[0056] Example 9

[0057] Tri-aldehyde resorcinol (0.08 mmol), benzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully weighed into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and then added to a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days after a simple seal was made using plastic film. After the reaction, a red organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel.

[0058] Comparative Example 1

[0059] Tri-aldehyde resorcinol (0.08 mmol), 3,3-dimethoxybenzidine (0.12 mmol), and one of triphenylphosphine (0.4 mmol), triphenyl phosphine oxide (0.4 mmol), triphenyl phosphine sulfide (0.4 mmol), trioctyl phosphine oxide (0.4 mmol), diphenyl phosphine (0.4 mmol) were carefully weighed into a glass tube, 2 mL of a dipolar aprotic solvent (one of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoramide) was added, mixed well and then added to a 5 mL plastic syringe, which was then placed in an 80 °C oven for 3 days after a simple seal was made using plastic film. After the reaction, an orange organic solvent gel was obtained, which was washed in DMF, ethanol, and solvent exchanged into one of water, acetone, acetonitrile, etc. to obtain the corresponding liquid gel. 正丁醇 :V 邻二氯苯 = 1 : 1), frozen using liquid nitrogen, and the pressure inside the tube was vacuumed to 2 x 10 -5MPa, the glass tube was removed from the vacuum line and sealed by a flame from a butane torch to exclude air. The sealed glass tube was placed in a 120 °C oven for 3 days. After the reaction, a yellow-brown powder was obtained, which was soaked in DMF, ethanol, and then Soxhlet extracted in tetrahydrofuran solvent for 48 h to obtain a yellow-brown powder with a mass of about 37 mg and a yield of about 78-83%, as shown in Figure 10 X-ray tests revealed that the powder sample prepared using 1,3,5-tris(4- aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde in the presence of acetic acid was also crystalline, but Example 2 had better crystallinity than Comparative Example 1.

[0060] Comparative Example 2

[0061] A high-temperature and high-pressure thick-walled glass tube was carefully charged with 1,3,5-tris(4-aminophenyl)benzene (TAPB) (0.08 mmol, 28.1 mg), 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTA) (0.12 mmol, 23.3 mg), and aqueous acetic acid (6M, 0.1 mL), cooled with liquid nitrogen, and vacuumed to 2x10 -5 MPa, the glass tube was removed from the vacuum line and sealed by a flame from a butane torch to exclude air. The sealed glass tube was placed in a 120 °C oven for 3 days. After the reaction, a yellow-brown powder was obtained, which was soaked in DMF, ethanol, and then Soxhlet extracted in tetrahydrofuran solvent for 48 h to obtain a yellow-brown powder with a mass of about 37 mg and a yield of about 78-83%, as shown in Figure 11 X-ray tests revealed that the powder sample prepared using 1,3,5-tris(4- aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde in the presence of acetic acid was also crystalline, but Example 2 had better crystallinity than Comparative Example 1.

[0062] Comparative Example 3

[0063] A high-temperature and high-pressure thick-walled glass tube was carefully charged with 1,3,5-tris(4-aminophenyl)benzene (TAPB) (0.08 mmol, 28.1 mg), 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTA) (0.12 mmol, 23.3 mg), and aqueous acetic acid (6M, 0.1 mL), cooled with liquid nitrogen, and vacuumed to 2x10 -5MPa and removed from the vacuum line, the glass tube was sealed by a flame from a butane torch to exclude air. The sealed glass tube was placed in an 80 °C oven for 3 days. After the reaction, a yellow powder was obtained, which was soaked in DMF, ethanol and then Soxhlet extracted in tetrahydrofuran solvent for 48 h to obtain a yellow powder with a mass of about 13 mg and a yield of about 21% to 27%, as shown in Figure 12 powder sample prepared from 1,3,5-tris(4-aminophenyl)benzene and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde in acetic acid catalyzed reaction has no crystallinity, as revealed by powder X-ray test.

Claims

1. A method for synthesizing a covalent organic framework material, characterized in that: The following steps are involved: The covalent organic framework material is obtained by a condensation reaction of organic monomer 1 and organic monomer 2 in the presence of a catalyst; wherein the organic monomer 1 is a di-linked monomer containing an amino functional group or a tri-linked monomer containing an amino functional group, the organic monomer 2 is a di-linked monomer containing an aldehyde functional group or a tri-linked monomer containing an aldehyde functional group, and the catalyst is a metal-free organic phosphine compound, and the catalyst is selected from a phosphine compound containing a phenyl group or a phosphine compound containing an alkyl chain.

2. The synthesis method according to claim 1, wherein: The organic monomer 1 is selected from 1,3,5-tris(4-aminophenyl)benzene, 2,4,6-tris(4-aminophenyl)pyridine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, tris(4-aminophenyl)amine, [1,1'-biphenyl]-4,4'-diamino, benzidine, p-phenylenediamine or 4,4'-diaminomethylbiphenyl.

3. The synthesis method according to claim 1, wherein: The organic monomer 2 is selected from 1,3,5-tris(p-formylphenyl)benzene, 1,3,5-tris(2-formylpyridin-5-yl)benzene, 1,3,5-tris(3'-formyl-4'-hydroxybenzene)benzene, 2,4,6-tris(4-formylphenyl)pyridine, trimesicaldehyde, trialdehyde phloroglucinol, 2,4,6-tris(4-formylphenyl)-1,3,5-triazine, tris(4-formylphenyl)amine, 2,5-dihydroxyterephthalaldehyde, 1,4-dialdo-2,5-divinylbenzene, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 6-(4-formylphenyl)pyridine-3-carboxaldehyde or 3,3'-dimethoxybiphenyl-4,4'-diacetaldehyde.

4. The synthesis method according to any one of claims 1 to 3, characterized in that: The catalyst is selected from triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, trioctylphosphine, trioctylphosphine oxide or diphenylphosphine.

5. The synthesis method according to any one of claims 1 to 3, characterized in that: The molar ratio of the organic monomer 1 to the organic monomer 2 is 1:4 to 4:

1.

6. The synthesis method according to claim 5, characterized in that: The molar ratio of the organic monomer 1 to the organic monomer 2 is 2:3 to 3:

2.

7. The synthesis method according to any one of claims 1 to 3, characterized in that: The molar ratio of the catalyst to the organic monomer 1 is 0.625:1 to 10:

1.

8. The synthesis method according to claim 7, wherein: The molar ratio of the catalyst to the organic monomer 1 is 3:1 to 5:

1.

9. The synthesis method according to any one of claims 1 to 3, characterized in that: The condensation reaction temperature is 70-200°C.

10. The synthesis method according to claim 9, characterized in that: The condensation reaction temperature is 80-120°C.

11. The synthesis method according to claim 10, characterized in that: The condensation reaction temperature is 80°C.

12. The synthesis method according to any one of claims 1 to 3, characterized in that: The condensation reaction time is 3-5 days.

13. The synthesis method according to claim 12, characterized in that: The condensation reaction time is 5 days.

14. The synthesis method according to any one of claims 1 to 3, characterized in that: The condensation reaction is carried out in a solvent-free system or in a solvent system.

15. The synthesis method according to claim 14, characterized in that: The solvent is selected from dimethylformamide, dimethyl sulfoxide, dimethylacetamide, hexamethylphosphoric triamide, mesitylene, n-butanol or o-dichlorobenzene.

16. A covalent organic framework material synthesized by the synthesis method according to any one of claims 1 to 15.

17. The covalent organic framework material according to claim 16, characterized in that: The covalent organic framework material is in the form of block, powder or gel.

18. The covalent organic framework material according to claim 16 or 17, characterized in that: The pore diameter of the covalent organic framework material is 1.8-4.9 nm.

19. The covalent organic framework material according to claim 18, characterized in that: The pore diameter of the covalent organic framework material is 2.95-3.62 nm.

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