CN114478970A - Precursor composition of covalent organic framework material and application thereof - Google Patents

Precursor composition of covalent organic framework material and application thereof Download PDF

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CN114478970A
CN114478970A CN202011158566.9A CN202011158566A CN114478970A CN 114478970 A CN114478970 A CN 114478970A CN 202011158566 A CN202011158566 A CN 202011158566A CN 114478970 A CN114478970 A CN 114478970A
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organic framework
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CN114478970B (en
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王昱
冯亮
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Dalian Institute of Chemical Physics of CAS
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Abstract

The application discloses a precursor composition of a covalent organic framework material and application thereof. The precursor composition of the covalent organic framework material comprises the following components: a: the A contains more than 2 functional groups I; the functional group I comprises any one of amino, hydroxyl and sulfydryl; and B: the B contains more than 2 functional groups II; the functional group II comprises any one of carboxyl, aldehyde group and hydroxyl; the A and the B are different substances. The raw materials of the precursor composition of the covalent organic framework material are scientifically selected and matched, and the corresponding covalent organic framework material can be synthesized only by simple steps. The covalent organic framework material has good physical and chemical stability and good crystal structure, and has great application value in various fields.

Description

Precursor composition of covalent organic framework material and application thereof
Technical Field
The application relates to a precursor composition of a covalent organic framework material and application thereof, belonging to the field of chemical materials.
Background
Covalent Organic Frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. One of the notable features of COFs, unlike other polymers, is that their structure can be pre-designed, synthetically controllable, and functionally controllable. The topological design diagram provides geometric guidance for the structural tiling of the expanded porous polygons, and the polycondensation reaction provides a synthetic method for the pre-designed primary and high-order structures. Due to the availability of organic units and the diversity of topological structures and connections, COFs have become a new field of organic materials, providing a powerful molecular platform for complex structural design and customized functional development. However, the classical methods for preparing COFs often require long reaction times and complicated procedures, and the crystal structure of the product requires strict control over the reaction steps. Meanwhile, in the prior art, the preparation of the COFs usually requires the addition of a solvent, and the solvent molecules may react with the precursor in the reaction process or the thermal movement thereof causes the product crystallization to have defects. How to develop a brand-new preparation method of COFs can realize high-efficiency preparation of COFs on the one hand, and can effectively improve the crystal quality of products on the other hand, and is one of the problems to be solved urgently in the preparation process of COFs.
Disclosure of Invention
According to one aspect of the application, the application provides a precursor composition of a covalent organic framework material, the raw materials of the precursor composition are scientifically selected and proportioned, and the corresponding covalent organic framework material can be synthesized only through simple steps.
A precursor composition for a covalent organic framework material, comprising the following components:
a: the A contains more than 2 functional groups I; the functional group I comprises any one of amino, hydroxyl and sulfydryl; and
b: the B contains more than 2 functional groups II; the functional group II comprises any one of carboxyl, aldehyde group and hydroxyl;
the A and the B are different substances.
Optionally, the precursor composition does not include the following combinations:
a is any one of p-phenylenediamine, biphenyldiamine, 5 '-diamino-2, 2' -bipyridine and 1,3, 5-tri (4-aminophenyl) benzene, and B is any one of 1,3, 5-triacyl phloroglucinol and terephthalaldehyde; or
A is p-phenylenediamine and B is 2,4, 6-trimethyloylphloroglucinol; or
A is 1,3, 5-tris- (4-aminophenyl) benzene or 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, and B is 2, 5-divinylterephthalaldehyde; or
A is hydrazine and B is triformyl phloroglucinol.
Optionally, a and B are independently selected from any one of chain organic matter and cyclic organic matter.
Optionally, the chain organic matter is selected from straight-chain alkanes, and the cyclic organic matter is selected from cycloalkanes or aromatic ring-containing compounds.
Optionally, the chain organic matter is any one selected from C2-C6 straight-chain alkanes substituted by functional groups;
the cyclic organic matter is selected from cyclic hydrocarbon of C4-C6 substituted by functional group or cyclic organic matter with less than 2 aromatic rings substituted by functional group;
the functional group comprises at least one of a functional group I and a functional group II.
Optionally, the A contains any one or more substituents of halogen, nitro, nitroso, sulfonic acid, methyl, ethyl, methoxy and ethoxy besides the functional group I;
the B contains one or more substituents selected from halogen, nitro, nitroso, sulfonic acid, methyl, ethyl, methoxy and ethoxy besides the functional group II.
Optionally, a contains a functional group X and a functional group Y;
a is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group I; the functional group Y is substituted on a carbon atom at the beta, gamma or delta position of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
Optionally, a contains a functional group X and a functional group Y;
a is selected from any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran substituted by functional group I; the functional group Y is substituted on the carbon atoms at the ortho position, the meta position or the para position of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
Optionally, a contains a functional group X and a functional group Y;
a is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group I; the functional group Y and the functional group X are substituted on the ring of any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene by 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
Optionally, a contains a functional group X and a functional group Y;
a is selected from any one of naphthalene, quinoline, isoquinoline and indole substituted by functional group I; the functional group Y and the functional group X are substituted on the ring of any one of naphthalene, quinoline, isoquinoline and indole;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
Optionally, a contains a functional group X and a functional group Y;
a is selected from any one of bipyridyl, bithiophene, bifuran, biphenyl and dipyrrole substituted by functional group I; the functional group Y and the functional group X are respectively substituted on different rings of any one of bipyridine, bithiophene, bifuran, biphenyl and dipyrrole;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
Optionally, the B contains a functional group L and a functional group M;
b is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group II; the functional group M is substituted on a carbon atom at the beta position, the gamma position or the delta position of the functional group L;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde and hydroxyl.
Optionally, the B contains a functional group L and a functional group M;
b is selected from any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran substituted by functional group II; the functional group M is substituted on the ortho-position, the meta-position or the para-position carbon atom of the functional group L;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde and hydroxyl.
Optionally, the B contains a functional group L and a functional group M;
b is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group II; the functional group M and the functional group L are substituted on the ring of any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran by 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde and hydroxyl.
Optionally, the B contains a functional group L and a functional group M;
b is selected from any one of naphthalene, quinoline, isoquinoline and indole substituted by functional group II; the functional group M and the functional group L are substituted on the ring of any one of naphthalene, quinoline, isoquinoline and indole;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl.
Optionally, the B contains a functional group L and a functional group M;
b is selected from any one of bipyridyl, bithiophene, bifuran, biphenyl and dipyrrole substituted by functional group II; the functional group M and the functional group L are respectively substituted on different rings of any one of bipyridine, bithiophene, bifuran, biphenyl and dipyrrole;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl.
Optionally, the B contains a functional group R, a functional group S and a functional group T;
b is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group II; the functional group S or the functional group T is substituted on a carbon atom at the beta, gamma or delta position of the functional group R;
the functional group R, the functional group S and the functional group T comprise any one of carboxyl, aldehyde group and hydroxyl.
Alternatively, said a is selected from: o-phenylenediamine, catechol, resorcinol, p-phenylenediamine, 3, 4-diaminopyridine, 5-ethoxy-1, 4-diaminobenzene, 5-bromo-1, 4-diaminobenzene, 5-nitro-1, 3-diaminobenzene, 5-fluoro-1, 3-diaminobenzene, 5-sulfo-1, 2-diaminobenzene, 5-chloro-1, 4-diaminobenzene, m-xylene, m-5-fluoro-1, 3-diaminobenzene, m-xylene, m-n-xylene, m-n-xylene, m-n-xylene, m-n-p-n,
5-nitro-1, 2-diaminobenzene, 3, 5-diaminopyridine, 2, 5-diamino-piperidine, and mixtures thereof,
2, 6-diaminopyrane, 3, 4-dimercapto-tetrahydropyran, 3, 5-diaminothiopyran, 2, 3-diamino-tetrahydrothiopyran, 2, 4-diaminopyrimidine, 2, 6-diaminopyrazine, 3, 5-diaminopyridazine, 2, 6-dimercapto-1, 4-dioxane, 3, 4-diaminopyrazine, 3, 5-dihydroxypyridazine, 2, 5-diaminopyrrole, 3, 4-dihydroxythiophene, 2, 3-diaminofuran, 3, 4-diaminopyrroline, 2, 7-diaminonaphthalene, 2, 5-diaminoquinoline, 1, 5-diaminoisoquinoline, 4 ' -diamino-2, 2' -bipyridine, 3 ' -dihydroxy-2, 2' -bipyridine, 5' -diamino-2, 2' -dipyrrole, 3 ' -diamino-2, 2' -bithiophene, 4 ' -diamino-2, 2' -bifuran, 4 ' -diaminobiphenyl, 3 ' -diaminobiphenyl, 2' -dihydroxybiphenyl, and 3,3 ' -dimercaptobiphenyl.
Alternatively, said B is selected from: oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, phthalic acid, methoxy-1, 2-phthalic acid, 4-methyl-1, 3-phthalic acid, 5-ethyl-1, 2-phthalic acid, 2, 5-dibromo-terephthalic acid, 5-ethoxy-1, 4-phthalic acid, 2-nitroso-1, 4-phthalic acid, 5-sulfo-1, 3-phthalic acid, 5-hydroxy-1, 2-phthalic acid, 2, 6-pyridinedialdehyde, 2, 4-dicarboxy-hexahydropyridine, 2, 3-pyrandicarboxylic acid, 2, 5-dicarboxy-tetrahydropyran, 2, 6-thiopyran-dicarboxylic acid, 3, 4-dicarboxy-tetrahydrothiopyran, 2, 5-pyrimidinedialdehyde, 2, 6-pyrazinedicarboxylic acid, 3, 4-pyridazindicarboxylic acid, 2, 6-dihydroxy-1, 4-dioxane, 3, 5-pyridazindicarboxylic acid, 3, 5-pyridazindialdehyde, 2, 3-dialopyrrole, 3, 4-dihydroxythiophene, 2, 3-furandicarboxylic acid, 2, 5-pyrrolinedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 7-quinolinedicarboxylic acid, 1, 4-isoquinolinedicarboxylic acid, 2, 5-quinolinedicarboxylic acid, 2' -bipyridine-4, 4 ' -dicarboxylic acid, 2' -bipyridine-3, 3 ' -dicarboxylic acid, 2' -bipyridine-4, 5' -dicarboxylic acid, 2' -bithiophene-5, 5 '-dicarboxylic acid, 2' -furan-4, 4 '-dicarboxylic acid, biphenyl-2, 2' -dicarboxylic acid, biphenyl-3, 4 '-dialdehyde, biphenyl-3, 4' -dicarboxylic acid.
Optionally, the mass ratio of A to B is 0.0005-120: 1.
Optionally, the upper limit of the mass ratio of A to B is selected from: 0.001: 1. 0.005:1, 0.01: 1. 0.075: 1. 0.1: 1. 1.6:1, 2.8:1, 3:1, 50:1, 65:1, 120: 1; the lower limit is selected from 0.0005, 0.001: 1. 0.005:1, 0.01: 1. 0.075: 1. 0.1: 1. 1.6:1, 2.8:1, 3:1, 50:1, 65: 1.
According to another aspect of the present application there is provided a covalent organic framework material prepared by subjecting a precursor composition of the covalent organic framework material according to any of the preceding claims to a condensation reaction.
Optionally, the covalent organic framework material has solid fluorescence emission properties from near ultraviolet to near infrared;
the wavelength range from near ultraviolet to near infrared is 390 nm-700 nm.
According to another aspect of the present application, there is provided a method of preparing a covalent organic framework material as defined in any one of the preceding claims, said method comprising the steps of: carrying out condensation reaction on the precursor composition of the covalent organic framework material to obtain the covalent organic framework material.
Alternatively, the conditions of the condensation reaction are: under the condition of inactive gas, the reaction temperature is 60-300 ℃, and the reaction time is 1-720 minutes.
Optionally, the upper limit of the reaction temperature is selected from 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃; the lower limit is selected from 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C, 270 deg.C, 280 deg.C, 290 deg.C, 300 deg.C.
Optionally, the upper limit of the reaction time is selected from 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 160 minutes, 180 minutes, 210 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, 390 minutes, 420 minutes, 450 minutes, 480 minutes, 510 minutes, 540 minutes, 570 minutes, 600 minutes, 630 minutes, 660 minutes, 690 minutes, 720 minutes; the lower limit is selected from 1 minute, 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, 390 minutes, 420 minutes, 450 minutes, 480 minutes, 510 minutes, 540 minutes, 570 minutes, 600 minutes, 630 minutes, 660 minutes, 690 minutes.
Optionally, the inert gas is selected from at least one of nitrogen and an inert gas.
Optionally, the inert gas is selected from at least one of argon, helium, neon.
Optionally, the preparation method further comprises a separation and purification step: after the condensation reaction is finished, a recrystallization step is also included.
Optionally, the solvent used for recrystallization is at least one selected from water, methanol, ethanol, propanol, butanol, ethyl acetate, acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, N-methylpyrrolidone, ethylene glycol monomethyl ether, N-hexane, and toluene.
Optionally, the recrystallization conditions are: heating to reach the boiling point of the solvent, and cooling for 1-168 hours.
Optionally, the upper limit of the cooling time is selected from 6 hours, 8 hours, 12 hours, 20 hours, 24 hours, 68 hours, 80 hours, 96 hours, 90 hours, 108 hours, 120 hours, 148 hours, 168 hours; the lower limit is selected from 1 hour, 6 hours, 8 hours, 12 hours, 20 hours, 24 hours, 68 hours, 80 hours, 96 hours, 90 hours, 108 hours, 120 hours, 148 hours.
Optionally, the heating to reach the boiling point of the solvent is specifically: heating to reach the boiling point of the solvent, and preserving the heat for 0.1-10 hours.
Optionally, the upper limit of the incubation time is selected from 0.2 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours; the lower limit is selected from 0.1 hour, 0.2 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours.
Optionally, the cooling is specifically: and naturally cooling at the temperature of-20-30 ℃.
Optionally, the upper cooling temperature limit is selected from 25 ℃, 30 ℃; the lower limit is selected from-20 deg.C, -10 deg.C, 0 deg.C, 10 deg.C, 15 deg.C.
Optionally, the preparation method further comprises the following steps: the precursor compositions are mixed prior to reaction.
Alternatively, the mixing method is not limited, and the mixing may be performed by a person skilled in the art using an existing method.
Optionally, the mixing method is: and uniformly mixing the precursor composition and then grinding.
Alternatively, the condensation reaction in the method of preparing the covalent organic framework material does not require the participation of a solvent.
The beneficial effects that this application can produce include:
(1) the raw materials of the precursor composition of the covalent organic framework material are scientifically selected and proportioned, and the corresponding covalent organic framework material can be synthesized only by simple steps.
(2) The covalent organic framework material provided by the application has good physical and chemical stability and good crystal structure, and has great application value in various fields.
(3) According to the preparation method of the covalent organic framework materials (COFs), the precursor composition of the covalent organic framework materials is subjected to molten-state condensation reaction under the protection of inactive gas, and no solvent is required to participate. The preparation method can greatly shorten the preparation time of the COFs material, and simultaneously purify the crystal of the COFs product by using a recrystallization mode, so that the purity and the quality of the COFs crystal can be greatly improved. The preparation method is simple and easy to implement, simple in operation method, low in cost, free of large instruments or processing equipment and high in application value.
4) The preparation method of the covalent organic framework material can realize preparation on a hectogram scale to a kilogram scale, and has a good industrialization prospect.
Drawings
FIG. 1 shows that in one embodiment of the present application, the 1 st substituent I (R1) and the 2 nd substituent I (R2) can form at the aromatic ring position 3 or more of naphthalene, quinoline, isoquinoline and indole positions as shown in FIG. 1 (the double bond and heteroatom structure are not shown), wherein the position of R2 is any position except the position of R1 as shown in the figure.
FIG. 2 shows that the 1 st substituent II (R1) and the 2 nd substituent II (R2) in one embodiment of the present application can form at least 3 of naphthalene, quinoline, isoquinoline and indole positions on the aromatic ring as shown in FIG. 2 (the double bond and heteroatom structure are not shown), wherein the position of R2 is any position except the position of R1 as shown in the figure.
FIG. 3 is an X-ray diffraction spectrum of COFs obtained in example 6 of the present application.
FIG. 4 is an infrared spectrum of COFs obtained in example 6 of the present application.
FIG. 5 is a spectrum of photoelectron spectra of COFs obtained in example 6 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially.
The analysis method in the examples of the present application is as follows:
fluorescence spectroscopy was performed using a PerkinElmer LS 55 fluorescence spectrophotometer.
Transmission electron microscopy analysis using JEM-2100.
Infrared spectroscopic analysis was performed using Nicolet iS 50.
The room temperature described herein is 25 ℃.
Example 1:
1g of oxalic acid and 1g of o-phenylenediamine are uniformly mixed, heated to 160 ℃ under the protection of nitrogen and reacted for 60 minutes. And dissolving the product in methanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 24 hours, and filtering to obtain the COFs product crystal.
Example 2:
10g of tricarballylic acid and 0.1g of catechol are uniformly mixed, heated to 120 ℃ under the protection of nitrogen and reacted for 120 minutes. And dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 12 hours, and filtering to obtain COFs product crystals.
Example 3:
0.05g of 1, 4-succinic acid and 6g of catechol are uniformly mixed, heated to 180 ℃ under the protection of argon and reacted for 180 minutes. And dissolving the product in propanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 2 hours, standing at room temperature for 36 hours, and filtering to obtain the COFs product crystal.
Example 4:
after 20g of 1, 5g of glutaric acid and 60g of resorcinol were mixed homogeneously, they were heated to 280 ℃ under neon conditions and reacted for 30 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 10 hours, and filtering to obtain COFs product crystals.
Example 5:
160g of 1, 6-hexanedioic acid and 460g of p-phenylenediamine were mixed homogeneously, heated to 90 ℃ under helium protection and reacted for 360 minutes. And dissolving the product in ethyl acetate and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing at room temperature for 8 hours, and filtering to obtain the COFs product crystal.
Example 6:
0.07g of phthalic acid and 0.2g of 3, 4-diaminopyridine were mixed homogeneously, heated to 260 ℃ under nitrogen protection and reacted for 160 minutes. And dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 8 hours, and filtering to obtain the COFs product crystal.
Example 7:
0.01g of 4-methoxy-1, 2-phthalic acid was mixed homogeneously with 0.05g of 5-ethoxy-1, 4-diaminobenzene, heated to 260 ℃ under helium protection and reacted for 240 minutes. And dissolving the product in N, N-dimethylformamide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 18 hours, and filtering to obtain COFs product crystals.
Example 8:
1g of 4-methyl-1, 3-phthalic acid and 0.6g of 5-bromo-1, 4-diaminobenzene were mixed homogeneously, heated to 70 ℃ under helium protection and reacted for 150 minutes. And dissolving the product in diethyl ether and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 2 hours, standing at room temperature for 90 hours, and filtering to obtain COFs product crystals.
Example 9:
0.001 mol (0.194g) of 5-ethyl-1, 2-phthalic acid was mixed uniformly with 0.0001g of 5-nitro-1, 3-diaminobenzene, heated to 170 ℃ under neon protection, and reacted for 390 minutes. And dissolving the product in acetonitrile, recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 68 hours, and filtering to obtain the COFs product crystal.
Example 10:
1.6g of 2, 5-dibromo-terephthalic acid and 105g of 5-ethoxy-1, 4-diaminobenzene were uniformly mixed, heated to 190 ℃ under nitrogen protection, and reacted for 480 minutes. And dissolving the product in acetone and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 2 hours, standing at room temperature for 48 hours, and filtering to obtain the COFs product crystal.
Example 11:
0.8g of 5-ethoxy-1, 4-phthalic acid and 2.3g of 5-fluoro-1, 3-diaminobenzene were mixed homogeneously, heated to 110 ℃ under argon protection and reacted for 720 minutes. And dissolving the product in n-hexane and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 10 hours, standing at room temperature for 6 hours, and filtering to obtain the COFs product crystal.
Example 12:
360g of 2-nitroso-1, 4-phthalic acid and 2g of 5-sulfo-1, 2-diaminobenzene were mixed uniformly, heated to 220 ℃ under the protection of nitrogen, and reacted for 600 minutes. And dissolving the product in N-methyl pyrrolidone and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 2 hours, standing at room temperature for 108 hours, and filtering to obtain COFs product crystals.
Example 13:
after 1000g of 5-sulfonic acid-1, 3-phthalic acid and 1g of 5-chloro-1, 4-diaminobenzene were mixed uniformly, the mixture was heated to 80 ℃ under the protection of nitrogen and reacted for 660 minutes. Dissolving the product in ethylene glycol monomethyl ether and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 0.5 hour, standing at room temperature for 168 hours, and filtering to obtain COFs product crystals.
Example 14:
0.0001 mol (0.0182g) of 5-hydroxy-1, 2-phthalic acid and 1g of 5-nitro-1, 2-diaminobenzene were mixed uniformly, heated to 80 ℃ under the protection of nitrogen, and reacted for 660 minutes. And dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing at room temperature for 148 hours, and filtering to obtain the COFs product crystal.
Example 15:
9.8g of 2, 6-pyridinedialdehyde were mixed homogeneously with 30g of 3, 5-diaminopyridine, heated to 210 ℃ under argon protection and reacted for 570 minutes. And dissolving the product in acetonitrile, recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 2 hours, standing at room temperature for 126 hours, and filtering to obtain COFs product crystals.
Example 16:
40g of 2, 4-dicarboxy-piperidine and 3g of 2, 5-diamino-piperidine were mixed uniformly, heated to 220 ℃ under the protection of argon and reacted for 510 minutes. And dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 3 hours, standing at room temperature for 48 hours, and filtering to obtain COFs product crystals.
Example 17:
450g of 2, 3-pyran dicarboxylic acid and 330g of 2, 6-diaminopyrane are mixed homogeneously, heated to 140 ℃ under argon protection and reacted for 270 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 4 hours, standing at room temperature for 120 hours, and filtering to obtain COFs product crystals.
Example 18:
700g of 2, 5-dicarboxy-tetrahydropyran and 690g of 3, 4-dimercapto-tetrahydropyran were mixed homogeneously, heated to 140 ℃ under argon protection and reacted for 270 minutes. And dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 1 hour, standing at room temperature for 120 hours, and filtering to obtain the COFs product crystal.
Example 19:
890g of 2, 6-thiopyran dicarboxylic acid and 689g of 3, 5-diaminothiopyran were uniformly mixed, heated to 150 ℃ under the condition of neon protection, and reacted for 330 minutes. And dissolving the product in N-methyl pyrrolidone and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 120 hours, and filtering to obtain COFs product crystals.
Example 20:
328g of 3, 4-dicarboxy-tetrahydrothiopyran were homogeneously mixed with 565g of 2, 3-diamino-tetrahydrothiopyran, heated to 240 ℃ under protection of helium and reacted for 390 minutes. And dissolving the product in N, N-dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 2 hours, standing at room temperature for 148 hours, and filtering to obtain the COFs product crystal.
Example 21:
68g of 2, 5-pyrimidine dialdehyde and 239g of 2, 4-diaminopyrimidine are mixed uniformly, heated to 290 ℃ under the protection of argon and reacted for 540 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 3 hours, standing at room temperature for 112 hours, and filtering to obtain COFs product crystals.
Example 22:
760g of 2, 6-pyrazine dicarboxylic acid and 250g of 2, 6-diaminopyrazine were uniformly mixed, heated to 60 ℃ under the protection of helium, and reacted for 720 minutes. And dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 108 hours, and filtering to obtain the COFs product crystal.
Example 23:
589g of 3, 4-pyridazinedicarboxylic acid were mixed homogeneously with 144g of 3, 5-diaminopyridazine, heated to 100 ℃ under nitrogen protection and reacted for 690 minutes. And dissolving the product in acetonitrile, recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 72 hours, and filtering to obtain the COFs product crystal.
Example 24:
125g of 2, 6-dihydroxy-1, 4-dioxane and 1.6g of 2, 6-dimercapto-1, 4-dioxane are uniformly mixed, heated to 100 ℃ under the protection of neon and reacted for 690 minutes. Dissolving the product in ether and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 0.1 hour, standing at room temperature for 80 hours, and filtering to obtain COFs product crystals.
Example 25:
920g of 3, 5-pyridazinedicarboxylic acid and 6.9g of 3, 4-diaminopyrazine were mixed homogeneously, heated to 100 ℃ under nitrogen protection and reacted for 690 minutes. Dissolving the product in ethylene glycol monomethyl ether and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 0.5 hour, standing at room temperature for 96 hours, and filtering to obtain COFs product crystals.
Example 26:
0.56g of 3, 5-pyridazinedialdehyde was mixed homogeneously with 0.06g of 3, 5-dihydroxypyridazine in moles, heated to 230 ℃ under nitrogen protection and reacted for 480 minutes. And dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 2 hours, standing at room temperature for 12 hours, and filtering to obtain the COFs product crystal.
Example 27:
8g of 2, 3-dialdehyde pyrrole and 0.9g of 2, 5-diamino pyrrole are mixed evenly, heated to 130 ℃ under the protection of argon and reacted for 90 minutes. And dissolving the product in acetonitrile, recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 8 hours, and filtering to obtain the COFs product crystal.
Example 28:
after 56g of 3, 4-dihydroxythiophene and 69g of 3, 4-dihydroxythiophene were mixed uniformly, they were heated to 140 ℃ under nitrogen protection and reacted for 690 minutes. And dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 20 hours, and filtering to obtain the COFs product crystal.
Example 29:
891g of 2, 3-furandicarboxylic acid and 578g of 2, 3-diaminofuran were mixed homogeneously, heated to 190 ℃ under helium protection and reacted for 720 minutes. And dissolving the product in acetone and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 120 hours, and filtering to obtain the COFs product crystal.
Example 30:
452g of 2, 5-pyrroline dicarboxylic acid and 752g of 3, 4-diaminopyrroline are uniformly mixed, heated to 70 ℃ under the protection of nitrogen and reacted for 660 minutes. And dissolving the product in n-hexane and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 3 hours, standing at room temperature for 98 hours, and filtering to obtain COFs product crystals.
Example 31:
8g of 1, 8-naphthalenedicarboxylic acid and 13g of 2, 7-diaminonaphthalene were uniformly mixed, heated to 110 ℃ under the protection of argon, and reacted for 210 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 4 hours, standing at room temperature for 64 hours, and filtering to obtain COFs product crystals.
Example 32:
1000g of 2, 7-quinolinedicarboxylic acid and 800g of 2, 5-diaminoquinoline are mixed homogeneously, heated to 170 ℃ under nitrogen protection and reacted for 390 minutes. And dissolving the product in propanol and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 6 hours, standing at room temperature for 20 hours, and filtering to obtain COFs product crystals.
Example 33:
69g of 1, 4-isoquinoline dicarboxylic acid and 68g of 1, 5-diaminoisoquinoline were uniformly mixed, heated to 300 ℃ under the protection of argon, and reacted for 90 minutes. And dissolving the product in methanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 10 hours, standing at room temperature for 88 hours, and filtering to obtain the COFs product crystal.
Example 34:
93g of 2, 5-quinolinedicarboxylic acid are reacted with 106g of 2, 5-diaminoquinoline under nitrogen protection at 280 ℃ for 450 minutes. And dissolving the product in ethyl acetate and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 0.1 hour, standing at room temperature for 80 hours, and filtering to obtain COFs product crystals.
Example 35:
668g of 2,2 '-bipyridyl-4, 4' -dicarboxylic acid was mixed uniformly with 635g of 4,4 '-diamino-2, 2' -bipyridyl, and then heated to 250 ℃ under the protection of helium gas, and reacted for 420 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing at room temperature for 95 hours, and filtering to obtain COFs product crystals.
Example 36:
after 235g of 2,2 '-bipyridine-4, 4' -dicarboxylic acid and 180g of p-phenylenediamine were uniformly mixed, the mixture was heated to 130 ℃ under the protection of neon gas, and reacted for 330 minutes. Dissolving the product in N, N' -dimethylformamide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 60 hours, and filtering to obtain COFs product crystals.
Example 37:
118g of 2,2 '-bipyridyl-3, 3' -dicarboxylic acid and 260g of 3,3 '-dihydroxy-2, 2' -bipyridyl were mixed uniformly, heated to 160 ℃ under the protection of argon, and reacted for 480 minutes. And dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 1 hour, standing at room temperature for 70 hours, and filtering to obtain COFs product crystals.
Example 38:
78g of 2,2 '-dipyrrole-4, 5' -dicarboxylic acid and 98g of 5,5 '-diamino-2, 2' -dipyrrole are mixed uniformly, heated to 120 ℃ under the protection of nitrogen and reacted for 540 minutes. And dissolving the product in ethyl acetate and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing at room temperature for 20 hours, and filtering to obtain the COFs product crystal.
Example 39:
864g 2,2 '-bithiophene-5, 5' -dicarboxylic acid and 835g 3,3 '-diamino-2, 2' -bithiophene were mixed uniformly, heated to 140 ℃ under neon protection, and reacted for 240 minutes. And dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 0.5 hour, standing at room temperature for 144 hours, and filtering to obtain COFs product crystals.
Example 40:
978g of 2,2 '-difuran-4, 4' -dicarboxylic acid and 942g of 4,4 '-diamino-2, 2' -difuran are mixed homogeneously, heated to 280 deg.c under argon protection and reacted for 60 minutes. And dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 2 hours, standing at room temperature for 120 hours, and filtering to obtain the COFs product crystal.
Example 41:
356g of biphenyl-2, 2 '-dicarboxylic acid and 428g of 4, 4' -diaminobiphenyl were mixed homogeneously, heated to 150 ℃ under argon protection and reacted for 90 minutes. And dissolving the product in N-methyl pyrrolidone and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 7 hours, standing at room temperature for 20 hours, and filtering to obtain COFs product crystals.
Example 42:
856g of biphenyl-3, 4 '-dialdehyde and 835g of 3, 3' -diaminobiphenyl were uniformly mixed, heated to 80 ℃ under the protection of neon, and reacted for 630 minutes. And dissolving the product in N, N-dimethylformamide and recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 6 hours, standing at room temperature for 36 hours, and filtering to obtain the COFs product crystal.
Example 43:
10g of biphenyl-3, 4 '-dicarboxylic acid and 12g of 2,2' -dihydroxybiphenyl are uniformly mixed, heated to 230 ℃ under the protection of nitrogen, and reacted for 150 minutes. And dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 10 hours, standing at room temperature for 168 hours, and filtering to obtain COFs product crystals.
Example 44:
110g of biphenyl-2, 2 '-dicarboxylic acid and 148g of 3, 3' -dimercaptobiphenyl were uniformly mixed, heated to 260 ℃ under the protection of argon, and reacted for 90 minutes. And dissolving the product in acetonitrile, recrystallizing, specifically heating to the boiling point of the solvent, keeping the temperature for 5 hours, standing at room temperature for 12 hours, and filtering to obtain the COFs product crystal.
Example 45: characterization of
The COFs obtained in examples 1 to 44 were subjected to X-ray diffraction spectroscopy. A typical X-ray diffraction spectrum is shown in FIG. 3, which corresponds to COFs in example 6. FIG. 3 shows that example 6 synthesizes the corresponding COFs, and the crystal structure is good. Other examples are similar to example 6, and the corresponding COFs are synthesized, and the crystal structure is better.
Infrared spectroscopy was performed on the COFs obtained in examples 1 to 44. A typical infrared spectrum is shown in FIG. 4, corresponding to the COFs in example 6. FIG. 4 shows that example 6 synthesizes the corresponding COFs. Other examples also synthesized the corresponding COFs.
The COFs obtained in examples 1 to 44 were subjected to photoelectron spectroscopy. A typical photoelectron spectrum is shown in FIG. 5, corresponding to COFs in example 6. FIG. 5 shows that example 6 synthesizes the corresponding COFs. Other examples also synthesized the corresponding COFs.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A precursor composition for a covalent organic framework material, comprising the following components:
a: the A contains more than 2 functional groups I; the functional group I comprises any one of amino, hydroxyl and sulfydryl; and
b: the B contains more than 2 functional groups II; the functional group II comprises any one of carboxyl, aldehyde group and hydroxyl;
the A and the B are different substances.
2. Precursor composition of a covalent organic framework material according to claim 1, characterized in that said a and said B are independently selected from any of chain organics, cyclic organics;
preferably, the chain organic matter is any one selected from linear alkanes of C2-C6 substituted by functional groups;
the cyclic organic matter is selected from cyclic alkane of C4-C6 substituted by functional group or cyclic organic matter with less than 2 aromatic rings substituted by functional group;
the functional group comprises at least one of a functional group I and a functional group II.
3. Precursor composition of a covalent organic framework material according to claim 1, characterized in that said a contains, in addition to functional group I, any one or more substituents of halogen, nitro, nitroso, sulfonic, methyl, ethyl, methoxy, ethoxy;
the B contains one or more substituents of halogen group, nitro group, nitroso group, sulfonic group, methyl group, ethyl group, methoxy group and ethoxy group besides the functional group II;
preferably, said a contains a functional group X and a functional group Y;
a is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group I;
the functional group Y is substituted on a carbon atom at the beta, gamma or delta position of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl;
preferably, said a contains a functional group X and a functional group Y;
a is selected from any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran substituted by functional group I;
the functional group Y is substituted on the carbon atoms at the ortho position, the meta position or the para position of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl;
preferably, said a contains a functional group X and a functional group Y;
a is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group I;
the functional group Y and the functional group X are substituted on the ring of any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene by 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl;
preferably, a contains a functional group X and a functional group Y;
a is selected from any one of naphthalene, quinoline, isoquinoline and indole substituted by functional group I;
the functional group Y and the functional group X are substituted on the ring of any one of naphthalene, quinoline, isoquinoline and indole;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl;
preferably, a contains a functional group X and a functional group Y;
a is selected from any one of bipyridyl, bithiophene, bifuran, biphenyl and dipyrrole substituted by functional group I;
the functional group Y and the functional group X are respectively substituted on different rings of any one of bipyridine, bithiophene, bifuran, biphenyl and dipyrrole;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfydryl.
4. Precursor composition of a covalent organic framework material according to claim 1, characterized in that B contains a functional group L and a functional group M;
b is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group II;
the functional group M is substituted on a carbon atom at the beta, gamma or delta position of the functional group L;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl;
preferably, said B contains a functional group L and a functional group M;
b is selected from any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran substituted by functional group II;
the functional group M is substituted on the ortho-position, the meta-position or the para-position carbon atom of the functional group L;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl;
preferably, said B contains a functional group L and a functional group M;
b is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group II;
the functional group M and the functional group L are substituted on the ring of any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, cyclohexane, piperidine and tetrahydropyran by 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl;
preferably, said B contains a functional group L and a functional group M;
b is selected from any one of naphthalene, quinoline, isoquinoline and indole substituted by functional group II;
the functional group M and the functional group L are substituted on the ring of any one of naphthalene, quinoline, isoquinoline and indole;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl;
preferably, said B contains a functional group L and a functional group M;
b is selected from any one of bipyridyl, bithiophene, bifuran, biphenyl and dipyrrole substituted by functional group II;
the functional group M and the functional group L are respectively substituted on different rings of any one of bipyridine, bithiophene, bifuran, biphenyl and dipyrrole;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde group and hydroxyl;
preferably, B contains a functional group R and a functional group S and a functional group T;
b is selected from any one of ethane, propane, butane, pentane and hexane substituted by functional group II;
the functional group S or the functional group T is substituted on a carbon atom at the beta, gamma or delta position of the functional group R;
the functional group R, the functional group S and the functional group T comprise any one of carboxyl, aldehyde group and hydroxyl.
5. Precursor composition of covalent organic framework material according to claim 1, characterized in that said a is selected from: o-phenylenediamine, catechol, resorcinol, p-phenylenediamine, 3, 4-diaminopyridine, 5-ethoxy-1, 4-diaminobenzene, 5-bromo-1, 4-diaminobenzene, 5-nitro-1, 3-diaminobenzene, 5-fluoro-1, 3-diaminobenzene, 5-sulfo-1, 2-diaminobenzene, 5-chloro-1, 4-diaminobenzene, 5-nitro-1, 2-diaminobenzene, 3, 5-diaminopyridine, 2, 5-diamino-hexahydropyridine, 2, 6-diaminopyrane, 3, 4-dimercapto-tetrahydropyran, 3, 5-diaminothiopyran, 2, 3-diamino-thiopyran, 2, 4-diaminopyrimidine, 2, 6-diaminopyrazine, p-phenylenediamine, p-phenylene-amide, p-phenylene-1, p-phenylene-amide, 5-ethoxy-1, 4-diaminobenzene, 5-nitro-1, 2-diaminobenzene, 3-diaminophenyl, 3-diaminopyridine, 2, 3-diamino-tetrahydropyran, 2, 6-diamino-tetrahydropyran, 2,3, 4-thiopyran, 3, 5-diaminopyridazine, 2, 6-dimercapto-1, 4-dioxane, 3, 4-diaminopyrazine, 3, 5-dihydroxypyridazine, 2, 5-diaminopyrrole, 3, 4-dihydroxythiophene, 2, 3-diaminofuran, 3, 4-diaminopyrroline, 2, 7-diaminonaphthalene, 2, 5-diaminoquinoline, 1, 5-diaminoisoquinoline, 4 ' -diamino-2, 2' -bipyridine, 3 ' -dihydroxy-2, 2' -bipyridine, 5' -diamino-2, 2' -bipyridine, 3 ' -diamino-2, 2' -bithiophene, 4 ' -diamino-2, 2' -difuran, 2' -bipyridine, 2,3, 5' -diaminonaphthalene, 2' -bipyridine, 2,3 ' -dipyridine, 2' -bipyridine, 2, or mixtures thereof, At least one of 4,4 '-diaminobiphenyl, 3' -diaminobiphenyl, 2 '-dihydroxybiphenyl and 3, 3' -dimercaptobiphenyl;
preferably, said B is selected from: oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, phthalic acid, methoxy-1, 2-phthalic acid, 4-methyl-1, 3-phthalic acid, 5-ethyl-1, 2-phthalic acid, 2, 5-dibromo-terephthalic acid, 5-ethoxy-1, 4-phthalic acid, 2-nitroso-1, 4-phthalic acid, 5-sulfo-1, 3-phthalic acid, 5-hydroxy-1, 2-phthalic acid, 2, 6-pyridinedialdehyde, 2, 4-dicarboxy-hexahydropyridine, 2, 3-pyrandicarboxylic acid, 2, 5-dicarboxy-tetrahydropyran, 2, 6-thiopyran-dicarboxylic acid, 3, 4-dicarboxy-tetrahydrothiopyran, 2, 5-pyrimidinedialdehyde, 2, 6-pyrazinedicarboxylic acid, 3, 4-pyridazindicarboxylic acid, 2, 6-dihydroxy-1, 4-dioxane, 3, 5-pyridazindicarboxylic acid, 3, 5-pyridazindialdehyde, 2, 3-dialopyrrole, 3, 4-dihydroxythiophene, 2, 3-furandicarboxylic acid, 2, 5-pyrrolinedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 7-quinolinedicarboxylic acid, 1, 4-isoquinolinedicarboxylic acid, 2, 5-quinolinedicarboxylic acid, 2' -bipyridine-4, 4 ' -dicarboxylic acid, 2' -bipyridine-3, 3 ' -dicarboxylic acid, 2' -bipyridine-4, 5' -dicarboxylic acid, 2' -bithiophene-5, at least one of 5 '-dicarboxylic acid, 2' -bifuran-4, 4 '-dicarboxylic acid, biphenyl-2, 2' -dicarboxylic acid, biphenyl-3, 4 '-dialdehyde, and biphenyl-3, 4' -dicarboxylic acid;
preferably, the mass ratio of A to B is 0.0005-120: 1.
6. A covalent organic framework material, characterized in that it is prepared by condensation reaction of a precursor composition of the covalent organic framework material according to any of claims 1 to 5.
7. The covalent organic framework material of claim 6, having solid fluorescence emission properties in the wavelength range of 390nm to 700 nm.
8. Process for the preparation of a covalent organic framework material according to claim 6 or 7, characterized in that it comprises the following steps: carrying out condensation reaction on a precursor composition containing the covalent organic framework material of any one of claims 1 to 5 to obtain the covalent organic framework material.
9. A method of preparing a covalent organic framework material as claimed in claim 8, wherein the conditions of the condensation reaction are: under the condition of inactive gas, the reaction temperature is 60-300 ℃, and the reaction time is 1-720 minutes;
preferably, the reaction time is 60-180 minutes;
preferably, the inert gas is selected from at least one of nitrogen and an inert gas;
preferably, the preparation method further comprises the steps of separation and purification: after the condensation reaction is finished, a recrystallization step is also included;
preferably, the solvent used for recrystallization is at least one selected from the group consisting of water, methanol, ethanol, propanol, butanol, ethyl acetate, acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, N-methylpyrrolidone, ethylene glycol monomethyl ether, N-hexane, and toluene.
10. The method of claim 9, wherein the conditions for recrystallization are: heating to reach the boiling point of the solvent, and cooling for 1-168 hours;
preferably, the heating to reach the boiling point of the solvent is in particular: heating to reach the boiling point of the solvent, and preserving the heat for 0.1-10 hours;
preferably, the cooling is specifically: and naturally cooling at the temperature of-20-30 ℃.
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