CN114478970B - 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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CN114478970B
CN114478970B CN202011158566.9A CN202011158566A CN114478970B CN 114478970 B CN114478970 B CN 114478970B CN 202011158566 A CN202011158566 A CN 202011158566A CN 114478970 B CN114478970 B CN 114478970B
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CN114478970A (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 sulfhydryl; and B: the B contains more than 2 functional groups II; the functional group II comprises any one of carboxyl, aldehyde and hydroxyl; the A and the B are different substances. The precursor composition raw materials of the covalent organic framework material are selected and proportioned scientifically, and the corresponding covalent organic framework material can be synthesized only through simple steps. The covalent organic framework material has good physical and chemical stability and a 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, and belongs 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 structure. Unlike other polymers, one notable feature of COFs is that its structure can be pre-designed, synthetically controlled and functionally controlled. The topology design provides geometric guidance for the tiling of the structure of the expanded porous polygon, and the polycondensation reaction provides a synthetic method for the pre-designed primary and higher order structures. Due to the availability of organic units and the diversity of topological structures and connections, COFs has become a new field of organic materials, providing a powerful molecular platform for complex structural design and custom functional development. However, classical COFs preparation methods often require long reaction times and complex procedures, and the product crystal structure requires strict control of the reaction steps. Meanwhile, in the prior art, the preparation of COFs generally requires the addition of a solvent, and there are defects in crystallization of the product due to the possible reaction of solvent molecules with precursors during the reaction, or thermal movement thereof. How to develop a brand-new preparation method of the COFs, on one hand, the high-efficiency preparation of the COFs can be realized, and on the other hand, the product crystal quality can be effectively improved, so that the method is one of the problems to be solved in the preparation process of the COFs.
Disclosure of Invention
According to one aspect of the application, the application provides a precursor composition of a covalent organic framework material, wherein the precursor composition is scientific in raw material selection and proportioning, and the corresponding covalent organic framework material can be synthesized 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 sulfhydryl; and
b: the B contains more than 2 functional groups II; the functional group II comprises any one of carboxyl, aldehyde 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, biphenyl diamine, 5 '-diamino-2, 2' -bipyridine and 1,3, 5-tri (4-aminophenyl) benzene, and B is any one of 1,3, 5-trimethyl phloroglucinol and terephthalaldehyde; or (b)
A is p-phenylenediamine and B is 2,4, 6-trimethylphloroglucinol; or (b)
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-divinyl terephthalaldehyde; or (b)
A is hydrazine and B is trimethylphloroglucinol.
Alternatively, the a and the B are independently selected from any one of a chain organic matter and a cyclic organic matter.
Alternatively, the chain organic is selected from linear alkanes and the cyclic organic is selected from cycloalkanes or aromatic-containing ring compounds.
Optionally, the chain organic matter is selected from any one of C2-C6 linear alkane substituted by functional groups;
the cyclic organic is selected from cyclic organics with less than 2 aromatic rings substituted by functional groups or cyclic organics with less than 2 aromatic rings substituted by functional groups of C4-C6 cycloalkanes;
the functional group comprises at least one of functional group I and functional group II.
Optionally, the A contains any one or more substituents of halogen groups, nitro groups, nitroso groups, sulfonic acid groups, methyl groups, ethyl groups, methoxy groups and ethoxy groups besides the functional group I;
the B contains any one or more substituents selected from halogen groups, nitro groups, nitroso groups, sulfonic acid groups, methyl groups, ethyl groups, methoxy groups and ethoxy groups in addition to the functional group II.
Optionally, the a contains a functional group X and a functional group Y;
the 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 the beta, gamma or delta carbon atom of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfhydryl.
Optionally, the a contains a functional group X and a functional group Y;
the 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 ortho, meta or para carbon atom of the functional group X;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfhydryl.
Optionally, the a contains a functional group X and a functional group Y;
the A is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group I; 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-substitution of the functional group Y and the functional group X on the ring of any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran, tetrahydrothiophene;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfhydryl.
Optionally, the a contains a functional group X and a functional group Y;
the 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 sulfhydryl.
Optionally, the a contains a functional group X and a functional group Y;
the A is selected from any one of bipyridine, 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, dithiophene, furan, biphenyl and dipyrrole;
the functional group X and the functional group Y comprise any one of amino, hydroxyl and sulfhydryl.
Optionally, the B contains a functional group L and a functional group M;
the B is any one of ethane, propane, butane, pentane and hexane substituted by functional group II; the functional group M is substituted on the beta, gamma or delta 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;
the 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, meta or para 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;
the B is selected from any one of pyrrole, thiophene, furan, pyrroline, cyclopentane, tetrahydropyrrole, tetrahydrofuran and tetrahydrothiophene substituted by functional group II; 2,3-, 2,4-, 2,5-, 3,4-, 3,5-, 2, 6-substitution of the functional group M and the functional group L on the ring of any one of benzene, pyridine, pyran, thiopyran, pyrimidine, pyrazine, pyridazine, 1, 4-dioxane, piperidine, tetrahydropyran;
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;
the 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 and hydroxyl.
Optionally, the B contains a functional group L and a functional group M;
the B is any one selected from bipyridine, 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, dithiophene, furan, biphenyl and dipyrrole;
the functional group L and the functional group M comprise any one of carboxyl, aldehyde and hydroxyl.
Optionally, the B contains a functional group R and a functional group S and a functional group T;
the B is 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 the beta, gamma or delta carbon atom of the functional group R;
the functional groups R, S and T comprise any one of carboxyl, aldehyde and hydroxyl.
Alternatively, the 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-piperidine,
2, 6-diaminopyran, 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' -bipyrrole at least one of 3,3 '-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, tricarballylic 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-sulfonic acid-1, 3 phthalic acid, 5-hydroxy-1, 2 phthalic acid, 2, 6-pyridinedialdehyde, 2, 4-dicarboxyl-hexahydropyridine, 2, 3-pyrandicarboxylic acid, 2, 5-dicarboxyl-tetrahydropyran, 2, 6-thiopyrandicarboxylic acid, 3, 4-dicarboxyl-tetrahydrothiopyran, 2, 5-pyrimidinedialdehyde, 2, 6-pyrazinedicarboxylic acid 3, 4-pyridazinedicarboxylic acid, 2, 6-dihydroxy-1, 4-dioxane, 3, 5-pyridazinedicarboxylic acid, 2, 3-dialdehyde pyrrole, 3, 4-dihydroxythiophene, 2, 3-furandicarboxylic acid, 2, 5-pyrroline dicarboxylic acid, 1, 8-naphthalene dicarboxylic acid, 2, 7-quinoline dicarboxylic acid, 1, 4-isoquinoline dicarboxylic acid 2, 5-quinoline dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyrrole-4, 5' -dicarboxylic acid, 2 '-dithiophene-5, 5' -dicarboxylic acid, 2 '-bipfuran-4, 4' -dicarboxylic acid, biphenyl-2, 2 '-dicarboxylic acid, biphenyl-3, 4' -dialdehyde, at least one of biphenyl-3, 4' -dicarboxylic acids.
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 as described in any one of the above to a condensation reaction.
Optionally, the covalent organic framework material has solid fluorescence emission properties from near ultraviolet to near infrared;
the near ultraviolet to near infrared is in a wavelength range of 390nm to 700 nm.
According to another aspect of the present application, there is provided a method of preparing a covalent organic framework material as described in any one of the preceding claims, the method comprising the steps of: and (3) 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 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃.
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 inactive gas is selected from at least one of nitrogen and inert gas.
Optionally, the inert gas is selected from at least one of argon, helium and 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 conditions of the recrystallization are: heating to 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 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 hours, 0.2 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours.
Optionally, the cooling specifically includes: naturally cooling at-20-30 deg.c.
Optionally, the upper cooling temperature limit is selected from 25 ℃, 30 ℃; the lower limit is selected from-20deg.C, -10deg.C, 0deg.C, 10deg.C, and 15deg.C.
Optionally, the preparation method further comprises the following steps: the precursor composition is mixed prior to the reaction.
Alternatively, the method of mixing is not limited, and one skilled in the art may use existing methods for mixing.
Optionally, the mixing method comprises the following steps: the precursor composition is uniformly mixed and then ground.
Alternatively, the condensation reaction in the preparation method of the covalent organic framework material does not require a solvent to participate.
The application has the beneficial effects that:
(1) The precursor composition raw materials of the covalent organic framework material provided by the application are scientific in selection and proportion, and the corresponding covalent organic framework material can be synthesized only through simple steps.
(2) The covalent organic framework material provided by the application has good physical and chemical stability and a good crystal structure, and has great application value in various fields.
(3) According to the preparation method of the covalent organic framework material (COFs), the precursor composition of the covalent organic framework material is subjected to a melt condensation reaction under the protection of inactive gas, and the solvent is not needed to participate. The preparation method can greatly shorten the preparation time of the COFs material, and simultaneously purify the crystal of the product COFs in a recrystallization mode, so that the purity and quality of the crystal of the product COFs can be greatly improved. The preparation method is simple and easy to implement, simple in operation method, low in cost, free of large-scale instruments or processing equipment, and high in application value.
4) The preparation method of the covalent organic framework material provided by the application can realize preparation from hundred gram level to kilogram level and has better industrialization prospect.
Drawings
FIG. 1 shows that the positions of the 1 st substituent I (R1) and the 2 nd substituent I (R2) on the aromatic ring can form 3 or more naphthalene, quinoline, isoquinoline and indole as shown in FIG. 1 (double bond and heteroatom structure are not shown), wherein the position of R2 is any position except the position shown in the R1.
FIG. 2 shows that the positions of the 1 st substituent II (R1) and the 2 nd substituent II (R2) on the aromatic ring can form 3 or more naphthalene, quinoline, isoquinoline and indole as shown in FIG. 2 (double bond and heteroatom structure are not shown), wherein the position of R2 is any position except the position shown in the R1.
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 photoelectron spectrum of COFs obtained in example 6 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.
The analysis method in the embodiment of the application is as follows:
fluorescence spectroscopy was performed using a PerkinElmer LS 55 fluorescence spectrophotometer.
Transmission electron microscopy analysis was performed using JEM-2100.
Infrared spectroscopic analysis was performed using Nicolet iS 50.
The room temperature of the application is 25 ℃.
Example 1:
after 1g of oxalic acid and 1g of o-phenylenediamine were uniformly mixed, the mixture was heated to 160℃under a nitrogen atmosphere and reacted for 60 minutes. The product is dissolved in methanol and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 24 hours at room temperature and filtered to obtain COFs product crystals.
Example 2:
after 10g of tricarballylic acid was uniformly mixed with 0.1g of catechol, the mixture was heated to 120℃under nitrogen protection and reacted for 120 minutes. Dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 12 hours at room temperature, and filtering to obtain COFs product crystals.
Example 3:
after 0.05g of 1, 4-butanedioic acid and 6g of catechol were uniformly mixed, the mixture was heated to 180℃under the protection of argon and reacted for 180 minutes. The product is dissolved in propanol and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 36 hours at room temperature and filtered to obtain COFs product crystals.
Example 4:
after 20g of 1,5 glutaric acid and 60g of resorcinol were homogeneously mixed, the mixture was heated to 280℃under neon protection and reacted for 30 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 10 hours at room temperature, and filtering to obtain COFs product crystals.
Example 5:
160g of 1,6 adipic acid and 460g of p-phenylenediamine were uniformly mixed, heated to 90℃under helium protection, and reacted for 360 minutes. The product is dissolved in ethyl acetate and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 8 hours at room temperature and filtered to obtain COFs product crystals.
Example 6:
after 0.07g of phthalic acid was uniformly mixed with 0.2g of 3, 4-diaminopyridine, the mixture was heated to 260℃under nitrogen protection, and reacted for 160 minutes. Dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 8 hours at room temperature, and filtering to obtain COFs product crystals.
Example 7:
after 0.01g of 4-methoxy-1, 2-phthalic acid was uniformly mixed with 0.05g of 5-ethoxy-1, 4-diaminobenzene, the mixture was heated to 260℃under helium protection and reacted for 240 minutes. The product is dissolved in N, N-dimethylformamide and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 18 hours at room temperature and filtered to obtain COFs product crystals.
Example 8:
after 1g of 4-methyl-1, 3-phthalic acid was uniformly mixed with 0.6g of 5-bromo-1, 4-diaminobenzene, the mixture was heated to 70℃under helium protection and reacted for 150 minutes. Dissolving the product in diethyl ether and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing for 90 hours at room temperature, and filtering to obtain COFs product crystals.
Example 9:
after 0.001 mol (0.194 g) of 5-ethyl-1, 2-phthalic acid was uniformly mixed with 0.0001g of 5-nitro-1, 3-diaminobenzene, the mixture was heated to 170℃under neon-protected conditions and reacted for 390 minutes. The product is dissolved in acetonitrile and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 68 hours at room temperature and filtered to obtain COFs product crystals.
Example 10:
after 1.6g of 2, 5-dibromo-terephthalic acid and 105g of 5-ethoxy-1, 4-diaminobenzene were uniformly mixed, the mixture was heated to 190℃under nitrogen protection and reacted for 480 minutes. The product is dissolved in acetone and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 48 hours at room temperature and filtered to obtain COFs product crystals.
Example 11:
after 0.8g of 5-ethoxy-1, 4-phthalic acid was uniformly mixed with 2.3g of 5-fluoro-1, 3-diaminobenzene, the mixture was heated to 110℃under argon atmosphere and reacted for 720 minutes. The product is dissolved in n-hexane and recrystallized, specifically heated to the boiling point of the solvent, kept for 10 hours, kept stand for 6 hours at room temperature and filtered to obtain COFs product crystals.
Example 12:
360g of 2-nitroso-1, 4-phthalic acid and 2g of 5-sulfo-1, 2-diaminobenzene were homogeneously mixed and heated to 220℃under nitrogen protection and reacted for 600 minutes. The product is dissolved in N-methyl pyrrolidone and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 108 hours at room temperature and filtered to obtain COFs product crystals.
Example 13:
1000g of 5-sulfonic acid-1, 3-phthalic acid and 1g of 5-chloro-1, 4-diaminobenzene were uniformly mixed, heated to 80℃under nitrogen protection, and reacted for 660 minutes. And dissolving the product in ethylene glycol monomethyl ether, recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 0.5 hour, standing for 168 hours at room temperature, and filtering to obtain COFs product crystals.
Example 14:
after 0.0001 mol (0.0182 g) of 5-hydroxy-1, 2-phthalic acid was homogeneously mixed with 1g of 5-nitro-1, 2-diaminobenzene, the mixture was heated to 80℃under nitrogen protection and reacted for 660 minutes. The product is dissolved in water and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 148 hours at room temperature and filtered to obtain COFs product crystals.
Example 15:
after 9.8g of 2, 6-pyridinedialdehyde was uniformly mixed with 30g of 3, 5-diaminopyridine, the mixture was heated to 210℃under argon atmosphere and reacted for 570 minutes. The product is dissolved in acetonitrile and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 126 hours at room temperature and filtered to obtain COFs product crystals.
Example 16:
40g of 2, 4-dicarboxy-hexahydropyridine and 3g of 2, 5-diamino-hexahydropyridine were homogeneously mixed, heated to 220℃under argon protection and reacted for 510 minutes. Dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 3 hours, standing for 48 hours at room temperature, and filtering to obtain COFs product crystals.
Example 17:
450g of 2, 3-pyran dicarboxylic acid and 330g of 2, 6-diaminopyran were homogeneously mixed, heated to 140℃under argon protection, and reacted for 270 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 4 hours, standing for 120 hours at room temperature, and filtering to obtain COFs product crystals.
Example 18:
700g of 2, 5-dicarboxy-tetrahydropyran and 690g of 3, 4-dimercapto-tetrahydropyran were homogeneously mixed, heated to 140℃under argon protection, and reacted for 270 minutes. Dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 120 hours at room temperature, and filtering to obtain COFs product crystals.
Example 19:
after uniformly mixing 890g of 2, 6-thiopyran dicarboxylic acid with 689g of 3, 5-diaminothiopyran, the mixture was heated to 150℃under neon protection and reacted for 330 minutes. The product is dissolved in N-methyl pyrrolidone and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 120 hours at room temperature and filtered to obtain COFs product crystals.
Example 20:
after 328g of 3, 4-dicarboxy-tetrahydrothiopyran was uniformly mixed with 560 g of 2, 3-diamino-tetrahydrothiopyran, the mixture was heated to 240℃under helium protection and reacted for 390 minutes. The product is dissolved in N, N-dimethyl sulfoxide and recrystallized, specifically heated to the boiling point of the solvent, kept for 2 hours, kept stand for 148 hours at room temperature and filtered to obtain COFs product crystals.
Example 21:
68g of 2, 5-pyrimidine dialdehyde and 239g of 2, 4-diaminopyrimidine were uniformly mixed, heated to 290℃under argon protection, and reacted for 540 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 3 hours, standing for 112 hours at room temperature, and filtering to obtain COFs product crystals.
Example 22:
after 760g of 2, 6-pyrazinedicarboxylic acid and 250g of 2, 6-diaminopyrazine were uniformly mixed, they were heated to 60℃under helium protection and reacted for 720 minutes. Dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 108 hours at room temperature, and filtering to obtain COFs product crystals.
Example 23:
589g of 3, 4-pyridazinedicarboxylic acid were uniformly mixed with 144g of 3, 5-diaminopyridazine, and then heated to 100℃under nitrogen atmosphere, and reacted for 690 minutes. The product is dissolved in acetonitrile and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 72 hours at room temperature and filtered to obtain COFs product crystals.
Example 24:
125g of 2, 6-dihydroxy-1, 4-dioxane and 1.6g of 2, 6-dimercapto-1, 4-dioxane were uniformly mixed, heated to 100℃under neon-protected conditions, and reacted for 690 minutes. Dissolving the product in diethyl ether and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 0.1 hour, standing for 80 hours at room temperature, and filtering to obtain COFs product crystals.
Example 25:
after 920g of 3, 5-pyridazinedicarboxylic acid was uniformly mixed with 6.9g of 3, 4-diaminopyrazine, the mixture was heated to 100℃under nitrogen atmosphere and reacted for 690 minutes. And dissolving the product in ethylene glycol monomethyl ether, recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 0.5 hour, standing for 96 hours at room temperature, and filtering to obtain COFs product crystals.
Example 26:
after 0.56g of 3, 5-pyridazinedial was uniformly mixed with 0.06g of 3, 5-dihydroxypyridazine, the mixture was heated to 230℃under nitrogen protection and reacted for 480 minutes. Dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing for 12 hours at room temperature, and filtering to obtain COFs product crystals.
Example 27:
after 8g of 2, 3-dialdehyde pyrrole and 0.9g of 2, 5-diaminopyrrole were uniformly mixed, the mixture was heated to 130℃under argon protection and reacted for 90 minutes. The product is dissolved in acetonitrile and recrystallized, specifically heated to the boiling point of a solvent, kept for 1 hour, kept stand for 8 hours at room temperature and filtered to obtain COFs product crystals.
Example 28:
56g of 3, 4-dihydroxythiophene and 69g of 3, 4-dihydroxythiophene were uniformly mixed, heated to 140℃under nitrogen protection, and reacted for 690 minutes. Dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 20 hours at room temperature, and filtering to obtain COFs product crystals.
Example 29:
891g of 2, 3-furandicarboxylic acid was homogeneously mixed with 578g of 2, 3-diaminofuran, heated to 190℃under helium protection, and reacted for 720 minutes. The product is dissolved in acetone and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 120 hours at room temperature and filtered to obtain COFs product crystals.
Example 30:
after being uniformly mixed with 612 g of 2, 5-pyrroline dicarboxylic acid and 751 g of 3, 4-diaminopyrroline, heating to 70 ℃ under the protection of nitrogen, and reacting for 660 minutes. The product is dissolved in normal hexane and recrystallized, specifically heated to the boiling point of the solvent, kept for 3 hours, kept stand for 98 hours at room temperature and filtered to obtain COFs product crystals.
Example 31:
after 8g of 1, 8-naphthalene dicarboxylic acid and 13g of 2, 7-diaminonaphthalene were uniformly mixed, the mixture was heated to 110℃under argon atmosphere and reacted for 210 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 4 hours, standing for 64 hours at room temperature, and filtering to obtain COFs product crystals.
Example 32:
1000g of 2, 7-quinolinedicarboxylic acid and 800g of 2, 5-diaminoquinoline were uniformly mixed, heated to 170℃under nitrogen protection, and reacted for 390 minutes. The product is dissolved in propanol and recrystallized, specifically heated to the boiling point of the solvent, kept for 6 hours, kept stand for 20 hours at room temperature and filtered to obtain COFs product crystals.
Example 33:
69g 1, 4-isoquinoline dicarboxylic acid and 68g 1, 5-two amino isoquinoline after homogeneous mixing, under argon protection of heating to 300 ℃, and reaction for 90 minutes. The product is dissolved in methanol and recrystallized, specifically heated to the boiling point of the solvent, kept for 10 hours, kept stand for 88 hours at room temperature and filtered to obtain COFs product crystals.
Example 34:
93g of 2, 5-quinolinedicarboxylic acid and 106g of 2, 5-diaminoquinoline were heated to 280℃under nitrogen protection and reacted for 450 minutes. The product is dissolved in ethyl acetate and recrystallized, specifically heated to the boiling point of the solvent, kept for 0.1 hour, kept standing for 80 hours at room temperature and filtered to obtain COFs product crystals.
Example 35:
668g of 2,2 '-bipyridine-4, 4' -dicarboxylic acid and 635g of 4,4 '-diamino-2, 2' -bipyridine were uniformly mixed, heated to 250℃under helium protection and reacted for 420 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing for 95 hours at room temperature, and filtering to obtain COFs product crystals.
Example 36:
235g of 2,2 '-bipyridine-4, 4' -dicarboxylic acid and 180g of p-phenylenediamine were uniformly mixed, heated to 130℃under neon-protected conditions, and reacted for 330 minutes. The product is dissolved in N, N' -dimethylformamide and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 60 hours at room temperature and filtered to obtain COFs product crystals.
Example 37:
118g of 2,2 '-bipyridine-3, 3' -dicarboxylic acid and 260g of 3,3 '-dihydroxy-2, 2' -bipyridine were uniformly mixed, heated to 160℃under argon protection, and reacted for 480 minutes. Dissolving the product in ethanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 1 hour, standing for 70 hours at room temperature, 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 were uniformly mixed, heated to 120℃under nitrogen protection and reacted for 540 minutes. The product is dissolved in ethyl acetate and recrystallized, specifically heated to the boiling point of the solvent, kept for 1 hour, kept stand for 20 hours at room temperature and filtered to obtain COFs product crystals.
Example 39:
864g of 2,2 '-dithiophene-5, 5' -dicarboxylic acid was uniformly mixed with 325 g of 3,3 '-diamino-2, 2' -dithiophene, heated to 140℃under neon protection, and reacted for 240 minutes. Dissolving the product in water and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 0.5 hour, standing for 144 hours at room temperature, and filtering to obtain COFs product crystals.
Example 40:
978g of 2,2 '-bisfuran-4, 4' -dicarboxylic acid and 942g of 4,4 '-diamino-2, 2' -bisfuran were uniformly mixed, heated to 280℃under argon protection, and reacted for 60 minutes. Dissolving the product in dimethyl sulfoxide and recrystallizing, specifically heating to the boiling point of the solvent, preserving the heat for 2 hours, standing for 120 hours at room temperature, and filtering to obtain COFs product crystals.
Example 41:
356g of biphenyl-2, 2 '-dicarboxylic acid was homogeneously mixed with 428g of 4,4' -diaminobiphenyl, and then heated to 150℃under argon protection, and reacted for 90 minutes. The product is dissolved in N-methyl pyrrolidone and recrystallized, specifically heated to the boiling point of the solvent, kept for 7 hours, kept stand for 20 hours at room temperature and filtered to obtain COFs product crystals.
Example 42:
856g of biphenyl-3, 4 '-dialdehyde were homogeneously mixed with 835g of 3,3' -diaminobiphenyl, and then heated to 80℃under neon-protected conditions, and reacted for 630 minutes. The product is dissolved in N, N-dimethylformamide and recrystallized, specifically heated to the boiling point of the solvent, kept for 6 hours, kept stand for 36 hours at room temperature and filtered to obtain COFs product crystals.
Example 43:
after 10g of biphenyl-3, 4 '-dicarboxylic acid and 12g of 2,2' -dihydroxybiphenyl were uniformly mixed, the mixture was heated to 230℃under nitrogen protection and reacted for 150 minutes. Dissolving the product in butanol and recrystallizing, specifically heating to the boiling point of the solvent, preserving the temperature for 10 hours, standing for 168 hours at room temperature, and filtering to obtain COFs product crystals.
Example 44:
110g of biphenyl-2, 2 '-dicarboxylic acid and 148g of 3,3' -dimercaptobiphenyl were homogeneously mixed, heated to 260℃under argon protection, and reacted for 90 minutes. The product is dissolved in acetonitrile and recrystallized, specifically heated to the boiling point of a solvent, kept for 5 hours, kept stand for 12 hours at room temperature and filtered to obtain COFs product crystals.
Example 45: characterization of
The COFs obtained in examples 1 to 44 were subjected to an X-ray diffraction spectrum test. A typical X-ray diffraction spectrum is shown in FIG. 3, corresponding to COFs in example 6. FIG. 3 shows that example 6 synthesizes the corresponding COFs with a better crystal structure. Other examples similar to example 6, the corresponding COFs were synthesized and the crystal structure was good.
The COFs obtained in examples 1 to 44 were subjected to infrared spectroscopic testing. A typical IR spectrum is shown in FIG. 4, corresponding to COFs in example 6. FIG. 4 shows that example 6 synthesizes the corresponding COFs. Other examples also synthesize the corresponding COFs.
Photoelectron spectroscopy tests were performed on COFs obtained in examples 1 to 44. 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 synthesize the corresponding COFs.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (9)

1. A method of preparing a covalent organic framework material, the method comprising the steps of:
the component A and the component B are subjected to condensation reaction;
the conditions of the condensation reaction are as follows: under the condition of inactive gas, the reaction temperature is 60-300 ℃ and the reaction time is 1-720 minutes; no solvent participates in the condensation reaction;
wherein, the A is selected from the group consisting of 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-piperidine, 2, 6-diaminopyran, 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-dioxan, 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 at least one of 3,3 '-dihydroxy-2, 2' -bipyridine, 5 '-diamino-2, 2' -bipyrrole, 3 '-diamino-2, 2' -bithiophene, 4 '-diamino-2, 2' -bisfuran, 4 '-diaminobiphenyl, 3' -diaminobiphenyl, 2 '-dihydroxybiphenyl, 3' -dimercaptobiphenyl;
the B is selected from oxalic acid, tricarballylic 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-sulfonic acid-1, 3-phthalic acid, 5-hydroxy-1, 2-phthalic acid, 2, 6-pyridinedialdehyde, 2, 4-dicarboxyl-hexahydropyridine, 2, 3-pyrandicarboxylic acid, 2, 5-dicarboxyl-tetrahydropyran, 2, 6-thiopyrandicarboxylic acid, 3, 4-dicarboxyl-tetrahydrothiopyran, 2, 5-pyrimidinedialdehyde, 2, 6-pyrazinedicarboxylic acid 3, 4-pyridazinedicarboxylic acid, 2, 6-dihydroxy-1, 4-dioxane, 3, 5-pyridazinedicarboxylic acid, 2, 3-dialdehyde pyrrole, 3, 4-dihydroxythiophene, 2, 3-furandicarboxylic acid, 2, 5-pyrroline dicarboxylic acid, 1, 8-naphthalene dicarboxylic acid, 2, 7-quinoline dicarboxylic acid, 1, 4-isoquinoline dicarboxylic acid 2, 5-quinoline dicarboxylic acid, 2 '-bipyridine-4, 4' -dicarboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 2 '-bipyrrole-4, 5' -dicarboxylic acid, 2 '-dithiophene-5, 5' -dicarboxylic acid, 2 '-bipfuran-4, 4' -dicarboxylic acid, biphenyl-2, 2 '-dicarboxylic acid, biphenyl-3, 4' -dialdehyde, at least one of biphenyl-3, 4' -dicarboxylic acids.
2. The method for preparing a covalent organic framework material according to claim 1, wherein the reaction time is 60-180 minutes.
3. The method for preparing a covalent organic framework material according to claim 1, wherein the inert gas is at least one selected from nitrogen and inert gases.
4. The method for preparing a covalent organic framework material according to claim 1, further comprising a separation and purification step of: after the condensation reaction is finished, a recrystallization step is also included.
5. The method for preparing a covalent organic framework material according to claim 4, wherein 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.
6. The method of claim 4, wherein the recrystallization conditions are: heating to reach the boiling point of the solvent, and cooling for 1-168 hours.
7. The method of claim 6, wherein the heating to a boiling point of the solvent is specifically: heating to reach the boiling point of the solvent, and preserving heat for 0.1-10 hours.
8. The method of preparing a covalent organic framework material according to claim 6, characterized in that the cooling is specifically: naturally cooling in an environment of-20-30 ℃.
9. The method for preparing a covalent organic framework material according to claim 1, wherein the mass ratio of the component A to the component B is 0.0005-120:1.
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