Synthesis method of covalent organic framework crystal material at normal temperature

Abstract

The invention discloses a synthesis method of a covalent organic framework crystal material at normal temperature, and belongs to the technical field of covalent organic framework synthesis. The synthesis method of the covalent organic framework crystal material at normal temperature comprises the following steps: S1, dissolving an ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolving an aldehyde monomer in a second solvent to obtain an aldehyde monomer solution; the first solvent or the second solvent is one or two of N, N-dimethylacetamide and dichloromethane; s2, mixing and reacting the ammonia monomer solution, the aldehyde monomer solution, a catalyst and a third solvent to obtain the covalent organic framework crystal material. According to the synthesis method provided by the invention, the covalent organic framework crystal material can be synthesized at a relatively low temperature within a short time.

Description

Technical Field

[0001] The invention relates to the technical field of covalent organic framework synthesis, and in particular to a method for synthesizing a covalent organic framework crystal material at room temperature. Background Art

[0002] Covalent organic frameworks (COFs) are porous crystalline organic materials composed of organic building blocks connected by covalent bonds. They have potential applications in catalysis, energy storage, gas separation and storage, optoelectronics, and other fields. Since the first successful synthesis of COF by et al. (DOI:10.1126 / science.1120411), the solvothermal method has been the most commonly used and popular choice for the synthesis of COFs. However, the solvothermal method usually involves harsh experimental conditions and has obvious limitations, mainly manifested in low scalability and yield, and long reaction synthesis time. For example, the preparation method of a two-dimensional covalent organic framework material disclosed in patent CN 117285543 A requires a temperature reaction of more than 24 hours at a temperature above 90°C in a vacuum environment. The methods for the synthesis of COFs have been expanded to mechanochemical method (DOI:10.1021 / jacs.4c06510), sonochemical method (DOI:10.1038 / s44160-021-00005-0), microwave-assisted method (DOI:10.1021 / cm802981m), etc. Ayan Jati et al. (DOI: 10.1021 / jacs.4c06510) successfully synthesized four imine-linked COFs by grinding amino ligands, aldehyde ligands, toluene-4-sulfonic acid monohydrate and a small amount of water thoroughly and then heating them in an oven at 90°C for 16 hours. However, this method still requires a high reaction temperature and a long reaction time. Zamora et al. (DOI: 10.1039 / d0cc02033h) recently successfully synthesized a variety of imine-linked COFs in aqueous solution using acetic acid as a catalyst. However, due to the poor solubility of ammonia or aldehyde monomers in aqueous solution, a large amount of waste liquid was generated in large-scale synthesis, and a high reaction temperature and a long reaction time (5 days) were still required.

[0003] How to quickly prepare covalent organic framework crystalline materials under mild reaction conditions is a technical problem that needs to be solved in the existing technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, provide a method for synthesizing a covalent organic framework crystalline material at room temperature, and solve the technical problem of how to quickly prepare a covalent organic framework crystalline material under mild reaction conditions in the prior art.

[0005] In order to achieve the above technical objectives, the technical solution of the present invention provides a method for synthesizing a covalent organic framework crystal material at room temperature, comprising the following steps:

[0006] S1, dissolving an ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolving an aldehyde monomer in a second solvent to obtain an aldehyde monomer solution; the first solvent or the second solvent is one or both of N,N-dimethylacetamide and dichloromethane;

[0007] S2, mixing the ammonia monomer solution, the aldehyde monomer solution, the catalyst and the third solvent to react to obtain the covalent organic framework crystal material.

[0008] In any embodiment, in step S2, the third solvent is acetonitrile.

[0009] In any embodiment, in step S1, the ammonia monomer is one or more of 2,6-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,3,5,6-tetrakis(amino)-benzoquinone and 2,7-diaminophenanthrenequinone; the aldehyde monomer is one or more of 2,4,6-triformylphloroglucinol, 2-hydroxy-1,3,5-benzenetricarboxaldehyde, 2,4-hydroxy-1,3,5-benzenetricarboxaldehyde and trimesic acid.

[0010] In any embodiment, in step S2, the catalyst is one or both of acetic acid and toluene-4-sulfonic acid monohydrate.

[0011] In any embodiment, the catalyst is a mixed catalyst of acetic acid and toluene-4-sulfonic acid monohydrate.

[0012] In any embodiment, the material ratio of toluene-4-sulfonic acid monohydrate to acetic acid is 50 mg:(1-5) mL, and the molar concentration of acetic acid is 3-17.5 mol / L.

[0013] In any embodiment, in the mixing reaction of step S2, the molar ratio of the amount of aldehyde monomer added to the amount of ammonia monomer added is 1:(1.5-2); and / or, the molar ratio of the amount of the catalyst added to the aldehyde monomer is (2-220):1.

[0014] In any embodiment, in step S2, the temperature of the mixing reaction is 15-30°C.

[0015] In any embodiment, in step S2, the mixing reaction time is 5 min-30 min.

[0016] In any embodiment, in step S2, the catalyst and the third solvent are first mixed, and then the ammonia monomer solution and the aldehyde monomer solution are added.

[0017] Compared with the prior art, the beneficial effects of the present invention include: the method for synthesizing a covalent organic framework crystal material at room temperature proposed by the present invention includes the following steps: S1, dissolving an ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolving an aldehyde monomer in a second solvent to obtain an aldehyde monomer solution; S2, mixing the ammonia monomer solution, the aldehyde monomer solution, a catalyst and a third solvent to obtain the covalent organic framework crystal material; by adjusting the order of adding reactants and catalysts, and dissolving the ammonia monomer and the aldehyde monomer separately and then adding them to the reactant for reaction, the reaction rate is increased and the generation of reactants is promoted, so that the covalent organic framework crystal material can be synthesized at a lower temperature in a short time, and the target product can be obtained by reacting for 5 minutes at room temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is an electron microscope image of the covalent organic framework crystal material prepared in Example 1 of the present invention.

[0019] Figure 2 This is an X-ray diffraction pattern of the covalent organic framework crystal material prepared in Example 1 of the present invention.

[0020] Figure 3 This is an X-ray diffraction pattern of the covalent organic framework crystal material prepared in Example 2 of the present invention.

[0021] Figure 4 This is an X-ray diffraction pattern of the covalent organic framework crystal material prepared in Example 3 of the present invention.

[0022] Figure 5 This is the X-ray diffraction pattern of the covalent organic framework crystal material prepared in Example 5 of the present invention.

[0023] Figure 6 This is the X-ray diffraction pattern of the material prepared in Comparative Example 1 of the present invention.

[0024] Figure 7 This is the X-ray diffraction pattern of the material prepared in Comparative Example 2 of the present invention.

[0025] Figure 8 This is the X-ray diffraction pattern of the material prepared in Comparative Example 3 of the present invention.

[0026] Fig. 9 This is the X-ray diffraction pattern of the material prepared in Comparative Example 4 of the present invention. DETAILED DESCRIPTION

[0027] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing the parameter, such as the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0028] If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0029] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0030] This specific embodiment provides a method for synthesizing a covalent organic framework crystal material at room temperature, comprising the following steps:

[0031] S1. Dissolving an ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolving an aldehyde monomer in a second solvent to obtain an aldehyde monomer solution; the first solvent or the second solvent is one or both of N,N-dimethylacetamide (i.e., DMAC) and dichloromethane (i.e., CH2Cl2); the ammonia monomer is one or more of 2,6-diaminoanthraquinone (AQ), 1,5-diaminoanthraquinone (TQ), tetraaminobenzoquinone and 2,7-diaminophenanthrenequinone (PQ); the aldehyde monomer is one or more of 2,4,6-triformylphloroglucinol (TP), 2-hydroxy-1,3,5-benzenetricarboxaldehyde (HT), 2,4-hydroxy-1,3,5-benzenetricarboxaldehyde (DT) and trimesic acid (BT);

[0032] S2. Mixing the ammonia monomer solution, the aldehyde monomer solution, the catalyst and the third solvent to obtain the covalent organic framework crystal material; the third solvent is acetonitrile; the catalyst is one or two of acetic acid and toluene-4-sulfonic acid monohydrate; in the mixing reaction of step S2, the molar ratio of the amount of aldehyde monomer added to the amount of ammonia monomer added is 1:(1.5-2); the molar ratio of the amount of the catalyst added to the aldehyde monomer is (2-220):1; the temperature of the mixing reaction is 15-30°C, the time of the mixing reaction is 5min-30min; the stirring speed of the mixing reaction is 200r / min-400r / min.

[0033] In some embodiments, the catalyst is a mixed catalyst of acetic acid and toluene-4-sulfonic acid monohydrate; the material ratio of toluene-4-sulfonic acid monohydrate to acetic acid is 50 mg:(1-5) mL, and the molar concentration of acetic acid is 3-17.5 mol / L.

[0034] In some embodiments, the catalyst and the third solvent are mixed first, and then the ammonia monomer solution and the aldehyde monomer solution are added.

[0035] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0036] In the present invention, reference is made to “some embodiments”, “this embodiment”, examples, etc., which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

[0037] If similar descriptions of "first / second" appear in the application documents, the following instructions are added. In the following description, the terms "first\second\third" involved are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It can be understood that "first\second\third" can be interchanged in a specific order or sequence where permitted, so that the embodiments described herein can be implemented in an order other than that illustrated or described herein.

[0038] In this embodiment, the term "and / or" is merely a description of the association relationship between associated objects, indicating that three relationships may exist. For example, object A and / or object B may represent three situations: object A exists alone, object A and object B exist at the same time, and object B exists alone.

[0039] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0040] Example 1 Synthesis of covalent organic framework crystal material COF-TPAQ crystal:

[0041] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 0.544 ml of acetic acid (6 M) were added to a 20 ml glass bottle in sequence, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of CH2Cl2 and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0042] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 300r / min for 30 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC three times respectively, and then wash and filter with acetone three times to completely remove the unreacted monomers, and place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain COF-TPAQ. Its SEM and XRD patterns are shown as follows: Figure 1 and Figure 2 As shown, it can be seen that this method can quickly synthesize high-crystallinity two-dimensional covalent organic framework crystal materials at room temperature.

[0043] Example 2 Synthesis of covalent organic framework crystal material COF-DTAQ crystal

[0044] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 1 ml of acetic acid (6 M) were added to a 20 ml glass bottle in sequence, and a rotor of a suitable size was added. 0.08 mmol of 2,4-hydroxy-1,3,5-benzenetricarboxaldehyde and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of DMAC and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0045] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 200r / min for 30 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC three times respectively, and then wash and filter with acetone three times to completely remove the unreacted monomers, place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain COF-DTAQ. Its XRD is as follows Figure 3 As shown, it can be seen that this method can quickly synthesize high-crystallinity two-dimensional covalent organic framework crystal materials at room temperature.

[0046] Example 3 Synthesis of covalent organic framework crystal material COF-BTAQ crystal

[0047] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 150 mg of toluene-4-sulfonic acid monohydrate (PTSA) were added to a 20 ml glass bottle in sequence, and a rotor of a suitable size was added. 0.08 mmol of trimesaldehyde and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of DMAC and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0048] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 400r / min for 20 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC three times respectively, and then wash and filter with acetone three times to completely remove the unreacted monomers, place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain the material COF-BTAQ. Its XRD is as follows Figure 4 As shown, it can be seen that this method can quickly synthesize high-crystallinity two-dimensional covalent organic framework crystal materials at room temperature.

[0049] Example 4 Synthesis of covalent organic framework crystal material COF-TPAQ crystal

[0050] Referring to Example 1, the system was expanded 50 times. At room temperature, 500 ml of ultra-dry acetonitrile and 27.2 ml of acetic acid (6M) were added to a 1000 ml conical flask in sequence, and a rotor of suitable size was added. 4 mmol of 2,4,6-triformyl phloroglucinol and 6 mmol of 2,6-diaminoanthraquinone were dissolved in 75 ml of dichloromethane and 50 ml of DMAC solution, respectively, to prepare aldehyde monomer solution and ammonia monomer solution. After the aldehyde monomer solution and ammonia monomer solution were filtered in sequence and slowly added to the above glass bottle solution, the conical flask was placed on a magnetic stirrer and mixed and stirred at a stirring speed of 300 r / min for 20 min, and then the solid was collected, washed and filtered 3 times with tetrahydrofuran and DMAC, and then washed and filtered 3 times with acetone to completely remove the unreacted monomers. The washed solid was placed in a vacuum oven at 80°C for 12 hours to obtain COF-TPAQ with high crystallinity.

[0051] Example 5 Synthesis of covalent organic framework crystal material COF-TPAQ crystal:

[0052] At room temperature (25°C), 10 ml of ultra-dry acetonitrile, 50 mg of toluene-4-sulfonic acid monohydrate (PTSA) and 1 ml of acetic acid (3M) were added to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of CH2Cl2 and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0053] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 300r / min for 5 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC for 3 times, and then wash and filter with acetone for 3 times to completely remove the unreacted monomers, and place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain COF-TPAQ. Its XRD is as follows Figure 5 As shown, it can be seen that this method can quickly synthesize high-crystallinity two-dimensional covalent organic framework crystal materials at room temperature.

[0054] Comparative Example 1 Synthesis of covalent organic framework crystal material COF-TPAQ crystal

[0055] The difference between this comparative example and Example 1 is that the acetic acid in Example 1 is replaced by trifluoroacetic acid as a catalyst, as follows:

[0056] At room temperature, 10 ml of ultra-dry acetonitrile and 0.544 ml of trifluoroacetic acid (6 M) were added to a 20 ml glass bottle in sequence, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of CH2Cl2 and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0057] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 300r / min for 30 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC three times respectively, and then wash and filter with acetone three times to completely remove the unreacted monomers, place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain a solid powder. Its XRD pattern is as follows Figure 6 As shown, it can be seen that the material synthesized by this method at room temperature is not a two-dimensional covalent organic crystal material.

[0058] Comparative Example 2 Synthesis of covalent organic framework crystal material COF-TPAQ crystal:

[0059] Compared with Example 1, the first solvent and the second solvent of this comparative example are benzonitrile, respectively, as follows:

[0060] At room temperature, 10 ml of ultra-dry acetonitrile and 0.544 ml of acetic acid (6 M) were added to a 20 ml glass bottle in sequence, and a rotor of suitable size was added to dissolve 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone in 1.5 ml of benzonitrile and 0.7 ml of benzonitrile, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0061] After filtering the ammonia monomer solution and the aldehyde monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 300r / min for 30 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC three times respectively, and then wash and filter with acetone three times to completely remove the unreacted monomers, place the washed solid in a vacuum oven at 80℃ for 12 hours to dry, and obtain a solid powder. Its XRD pattern is as follows Figure 7 As shown, it can be seen that the material synthesized by this method at room temperature is not a two-dimensional covalent organic crystal material.

[0062] Comparative Example 3 Synthesis of COF-TPAQ Crystals

[0063] The difference between this comparative example and Example 1 is that the mixing and stirring reaction time is only 5 minutes, and the other reaction steps and conditions are the same as those in Example 1. Figure 8 As shown, it can be seen that the crystallinity of the material synthesized by this method at room temperature is poor and the desired material is not obtained.

[0064] Comparative Example 4

[0065] The difference between this comparative example and Example 5 is that the catalyst is replaced by trifluoroacetic acid instead of acetic acid, as follows:

[0066] At room temperature (25°C), 10 ml of ultra-dry acetonitrile, 50 mg of toluene-4-sulfonic acid monohydrate (PTSA) and 1 ml of trifluoroacetic acid (3M) were added to a 20 ml glass bottle, and a rotor of a suitable size was added, 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of DMAC and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0067] After filtering the aldehyde monomer solution and the ammonia monomer solution in sequence, slowly add them to the above glass bottle solution, place the glass bottle on a magnetic stirrer and stir at a stirring speed of 300 r / min for 5 minutes, collect the solid, wash and filter with tetrahydrofuran and DMAC for 3 times, and then wash and filter with acetone for 3 times to completely remove the unreacted monomers, and place the washed solid in a vacuum oven at 80°C for 12 hours to dry. Fig. 9 As shown, the synthesized material is not a two-dimensional covalent organic crystal material.

[0068] Comparative Example 5 Synthesis of covalent organic framework crystal material COF-TPAQ crystal:

[0069] At room temperature (25°C), 10 ml of ultra-dry acetonitrile was added to a 20 ml glass bottle, and a rotor of suitable size was added. 0.08 mmol of 2,4,6-triformylphloroglucinol and 0.12 mmol of 2,6-diaminoanthraquinone were dissolved in 1.5 ml of DMAC and 0.7 ml of DMAC solution, respectively, to prepare an aldehyde monomer solution and an ammonia monomer solution.

[0070] The aldehyde monomer solution and the ammonia monomer solution were filtered in sequence and then slowly added to the above glass bottle solution. Finally, 0.544 ml of acetic acid (6M) was added to the above mixed solution. The glass bottle was placed on a magnetic stirrer and mixed and stirred at a stirring speed of 300 r / min for 30 minutes, and then the solid was collected. It was washed and filtered 3 times with tetrahydrofuran and DMAC respectively, and then washed and filtered 3 times with acetone to completely remove the unreacted monomers. The washed solid was placed in a vacuum oven at 80°C for 12 hours to dry to obtain COF-DATQ. The synthesized material has poor crystallinity.

[0071] According to the method of Comparative Example 5, the mixing and stirring time is extended to 2 hours, and the synthesized material is a two-dimensional covalent organic crystal material with high crystallinity.

[0072] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for synthesizing a covalent organic framework crystalline material at room temperature, characterized in that: The following steps are involved: S1, dissolving ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolving an aldehyde monomer in a second solvent to obtain an aldehyde monomer solution; wherein the first solvent or the second solvent is one or both of N,N-dimethylacetamide and dichloromethane; S2, mixing the ammonia monomer solution, the aldehyde monomer solution, the catalyst and the third solvent to react to obtain the covalent organic framework crystal material.

2. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 1, characterized in that: In step S2, the third solvent is acetonitrile.

3. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 1 or 2, characterized in that: In step S1, the ammonia monomer is one or more of 2,6-diaminoanthraquinone, 1,5-diaminoanthraquinone, tetraaminobenzoquinone and 2,7-diaminophenanthrenequinone; the aldehyde monomer is one or more of 2,4,6-triformylphloroglucinol, 2-hydroxy-1,3,5-benzenetricarboxaldehyde, 2,4-hydroxy-1,3,5-benzenetricarboxaldehyde and trimesic acid.

4. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 1, characterized in that: In step S2, the catalyst is one or both of acetic acid and toluene-4-sulfonic acid monohydrate.

5. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 4, characterized in that: The catalyst is a mixed catalyst of acetic acid and toluene-4-sulfonic acid monohydrate.

6. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 5, characterized in that: The material ratio of toluene-4-sulfonic acid monohydrate to acetic acid is 50 mg:(1-5) mL, and the molar concentration of acetic acid is 3-17.5 mol / L.

7. The method for synthesizing a covalent organic framework crystal material at room temperature according to claim 1, characterized in that: In the mixing reaction of step S2, the molar ratio of the amount of the aldehyde monomer added to the amount of the ammonia monomer added is 1:(1.5-2); and / or, the molar ratio of the amount of the catalyst added to the aldehyde monomer is (2-220):

1.

8. The method for synthesizing a covalent organic framework crystalline material at room temperature according to claim 1, characterized in that: In step S2, the temperature of the mixed reaction is 15-30°C.

9. The method for synthesizing a covalent organic framework crystal material at room temperature according to claim 8, characterized in that: In step S2, the mixing reaction time is 5 min-30 min.

10. The method for synthesizing a covalent organic framework crystal material at room temperature according to claim 1, characterized in that: In step S2, the catalyst and the third solvent are first mixed, and then the ammonia monomer solution and the aldehyde monomer solution are added.

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