Synthesis method of covalent organic framework crystal material at room temperature

Abstract

The application 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 amine monomer in a first solvent to obtain an amine 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; S2, mixing and reacting the amine monomer solution, the aldehyde monomer solution, a catalyst and a third solvent to obtain the covalent organic framework crystal material. The synthesis method can synthesize the covalent organic framework crystal material at a low temperature in a short time.

Description

Technical Field

[0001] This invention relates to the field of covalent organic framework synthesis technology, specifically to a method for synthesizing covalent organic framework crystal materials at room temperature. Background Technology

[0002] Covalent organic frameworks (COFs) are porous crystalline organic materials composed of organic building blocks linked by covalent bonds. They have potential applications in catalysis, energy storage, gas separation and storage, and optoelectronics. Since 2005, AP... Since the first successful synthesis of COFs by [Authors' Name] (DOI: 10.1126 / science.1120411), the solvothermal method has become the most commonly used and popular choice for COF synthesis. 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, a method for preparing a two-dimensional covalent organic framework material disclosed in patent CN 117285543 A requires reaction at a temperature above 90°C in a vacuum environment for more than 24 hours. The methods for synthesizing COFs have been expanded to include mechanochemical methods (DOI: 10.1021 / jacs.4c06510), sonochemical methods (DOI: 10.1038 / s44160-021-00005-0), and microwave-assisted methods (DOI: 10.1021 / cm802981m), etc. Ayan Jati et al. (DOI:10.1021 / jacs.4c06510) successfully synthesized four imine-linked COFs by thoroughly grinding an amino ligand, an aldehyde ligand, toluene-4-sulfonic acid monohydrate, and a small amount of water, and then heating the mixture in an oven at 90°C for 16 h. However, this method still requires a high reaction temperature and a long reaction time. Zamora et al. (DOI:10.1039 / d0cc02033h) recently successfully synthesized various 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 during large-scale synthesis, and a high reaction temperature and a long reaction time (5 days) were still required.

[0003] How to rapidly prepare covalent organic framework crystal materials under mild reaction conditions is a technical problem that needs to be solved by existing technologies. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical deficiencies and provide a method for synthesizing covalent organic framework crystal materials at room temperature, thereby solving the technical problem of how to rapidly prepare covalent organic framework crystal materials under mild reaction conditions in the prior art.

[0005] To achieve the above-mentioned technical objectives, the present invention provides a method for synthesizing covalent organic framework crystal materials at room temperature, comprising the following steps:

[0006] S1. Dissolve the ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolve the 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. The ammonia monomer solution, the aldehyde monomer solution, the catalyst, and the third solvent are mixed and reacted 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-tetra(amino)-p-benzoquinone, and 2,7-diaminophenanthrenequinone; the aldehyde monomer is one or more of 2,4,6-tricarboxymethyl phloroglucinol, 2-hydroxy-1,3,5-benzenetrialdehyde, 2,4-hydroxy-1,3,5-benzenetrialdehyde, and pyromellitic tricarboxaldehyde.

[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 catalyst added to the amount of 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, the mixing reaction time in step S2 is 5 min to 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 covalent organic framework crystal materials at room temperature proposed in 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 react and obtain the covalent organic framework crystal material; by adjusting the order of addition of reactants and catalyst, and by dissolving the ammonia monomer and aldehyde monomer separately before adding them to the reactant for reaction, the reaction rate is improved and the generation of reactants is promoted, thereby enabling the synthesis of covalent organic framework crystal materials at a low temperature in a short time, and the target product can be obtained by reacting at room temperature for 5 minutes. Attached Figure Description

[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 an X-ray diffraction pattern of the covalent organic framework crystal material obtained in Example 5 of the present invention.

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

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

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

[0026] Figure 9 This is the X-ray diffraction pattern of the material prepared in Comparative Example 4 of this invention. Detailed Implementation

[0027] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is understood that ranges of 60–110 and 80–120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" means that all real numbers between "0" and "5" have been listed in this article; "0~5" is just a shortened representation of these numerical combinations. In addition, when a parameter is described as an integer ≥2, it is equivalent to disclosing that parameter, such as integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0028] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0029] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: 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 covalent organic framework crystal materials at room temperature, including the following steps:

[0031] S1. Dissolve an ammonia monomer in a first solvent to obtain an ammonia monomer solution; dissolve 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 (DMAC) and dichloromethane (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-tricarboxymethyl phloroglucinol (TP), 2-hydroxy-1,3,5-benzenetriformaldehyde (HT), 2,4-hydroxy-1,3,5-benzenetriformaldehyde (DT), and pyromellitic tricarboxaldehyde (BT);

[0032] S2. The ammonia monomer solution, the aldehyde monomer solution, the catalyst, and the third solvent are mixed and reacted to obtain the covalent organic framework crystal material; the third solvent is acetonitrile; the catalyst is one or both of acetic acid and toluene-4-sulfonic acid monohydrate; in the mixing reaction in 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 catalyst added to the amount of aldehyde monomer added is (2-220):1; the temperature of the mixing reaction is 15-30℃, 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 first mixed, and then the ammonia monomer solution and the aldehyde monomer solution are added.

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0036] In this invention, the terms "some embodiments," "this embodiment," and examples are used to describe a subset of all possible embodiments. However, it is understood that "some embodiments" can be the same subset or different subsets of all possible embodiments and can be combined with each other without conflict.

[0037] If the application documents contain similar descriptions such as "first / second", the following explanation shall be added: In the following description, the terms "first / second / third" are used only to distinguish similar objects and do not represent a specific ordering of objects. It is understood that "first / second / third" may 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 relationship between related objects, indicating that there can be three relationships. For example, object A and / or object B can represent three situations: object A exists alone, object A and object B exist simultaneously, and object B exists alone.

[0039] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

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

[0041] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 0.544 ml of acetic acid (6M) were added sequentially to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution.

[0042] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 300 rpm for 30 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by three washes and filters with acetone to thoroughly remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain COF-TPAQ. Its SEM and XRD patterns are shown below. Figure 1 and Figure 2 As shown, this method can rapidly synthesize highly crystalline two-dimensional covalent organic framework crystal materials at room temperature.

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

[0044] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 1 ml of acetic acid (6M) were added sequentially to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4-hydroxy-1,3,5-benzenetrialdehyde 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 aldehyde monomer solution and ammonia monomer solution.

[0045] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 200 rpm for 30 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by three washes and filters with acetone to completely remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain COF-DTAQ. Its XRD pattern is shown below. Figure 3 As shown, this method can rapidly synthesize highly crystalline two-dimensional covalent organic framework crystal materials at room temperature.

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

[0047] At room temperature (25°C), 10 ml of ultra-dry acetonitrile and 150 mg of toluene-4-sulfonic acid monohydrate (PTSA) were added sequentially to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of trimesin 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 aldehyde monomer solution and ammonia monomer solution.

[0048] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 400 rpm for 20 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by washing and filtering three times with acetone to completely remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain the material COF-BTAQ. Its XRD pattern is shown below. Figure 4 As shown, this method can rapidly synthesize highly crystalline two-dimensional covalent organic framework crystal materials at room temperature.

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

[0050] Referring to Example 1, the system was scaled up 50 times. At room temperature, 500 ml of ultra-dry acetonitrile and 27.2 ml of acetic acid (6M) were sequentially added to a 1000 ml Erlenmeyer flask, and a rotor of appropriate size was added. 4 mmol of 2,4,6-tricarboxymethyl 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 solutions and ammonia monomer solutions. After sequentially filtering the aldehyde monomer solutions and ammonia monomer solutions, they were slowly added to the solutions in the glass flask. The Erlenmeyer flask was placed on a magnetic stirrer and stirred at 300 rpm for 20 min. The solid was collected, washed and filtered three times with tetrahydrofuran and DMAC, and then washed and filtered three times with acetone to completely remove unreacted monomers. The washed solid was dried in a vacuum oven at 80 °C for 12 h to obtain highly crystalline COF-TPAQ.

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

[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-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution.

[0053] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 300 rpm for 5 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by three more washes with acetone to completely remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain COF-TPAQ. Its XRD pattern is shown below. Figure 5 As shown, this method can rapidly synthesize highly crystalline two-dimensional covalent organic framework crystal materials at room temperature.

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

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

[0056] At room temperature, 10 ml of ultra-dry acetonitrile and 0.544 ml of trifluoroacetic acid (6M) were added sequentially to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution.

[0057] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 300 rpm for 30 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by three more washes with acetone to thoroughly remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain a solid powder. Its XRD pattern is shown below. Figure 6 As shown, the material synthesized by this method at room temperature is not a two-dimensional covalent organic crystal material.

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

[0059] Compared with Example 1, the first solvent and the second solvent in this comparative example are benzonitrile, as detailed below:

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

[0061] After filtering the ammonia monomer solution and the aldehyde monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at 300 rpm for 30 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by three more washes with acetone to completely remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours to obtain a solid powder. Its XRD pattern is shown below. Figure 7 As shown, the material synthesized by this method at room temperature is not a two-dimensional covalent organic crystal material.

[0062] Synthesis of 3COF-TPAQ crystal (comparative example)

[0063] The difference between this comparative example and Example 1 is that the mixing and stirring reaction time was only 5 minutes; all other reaction steps and conditions were the same as in Example 1. Its XRD pattern is shown below. Figure 8 As shown, the material synthesized by this method at room temperature has poor crystallinity, and the desired material was not obtained.

[0064] Comparative Example 4

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

[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 appropriate size was added. 0.08 mmol of 2,4,6-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution.

[0067] After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was placed on a magnetic stirrer and stirred at 300 rpm for 5 minutes. The solid was collected and washed three times with tetrahydrofuran and DMAC, followed by washing and filtering three times with acetone to completely remove unreacted monomers. The washed solid was then dried in a vacuum oven at 80°C for 12 hours. Figure 9 As shown, the synthesized material is not a two-dimensional covalent organic crystal material.

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

[0069] At room temperature (25°C), 10 ml of ultra-dry acetonitrile was added to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution.

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

[0071] Following the method of Comparative Example 5, the mixing and stirring time was extended to 2 hours, and the synthesized material was a highly crystalline two-dimensional covalent organic crystal material.

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

Claims

1. A method for synthesizing a covalent organic framework crystal material at room temperature, characterized in that, Includes the following steps: S1. Dissolve the ammonia monomer in the first solvent to obtain an ammonia monomer solution; An aldehyde monomer is dissolved in a second solvent to obtain an aldehyde monomer solution; the first solvent and the second solvent are one or both of N,N-dimethylacetamide and dichloromethane; 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-tricarboxymethyl phloroglucinol, 2-hydroxy-1,3,5-benzenetrialdehyde, 2,4-hydroxy-1,3,5-benzenetrialdehyde, and pyromellitic tricarboxaldehyde. S2. The ammonia monomer solution, the aldehyde monomer solution, the catalyst, and the third solvent are mixed and reacted to obtain the covalent organic framework crystal material; the third solvent is acetonitrile; the catalyst is one or both of acetic acid and toluene-4-sulfonic acid monohydrate; the temperature of the mixing reaction is 15-30℃, and the time of the mixing reaction is 20min-30min.

2. The method for synthesizing covalent organic framework crystal materials at room temperature according to claim 1, characterized in that, The catalyst is a mixed catalyst of acetic acid and toluene-4-sulfonic acid monohydrate.

3. The method for synthesizing covalent organic framework crystal materials at room temperature according to claim 2, 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.

4. The method for synthesizing covalent organic framework crystal materials at room temperature according to claim 1, characterized in that, 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 catalyst added to the amount of aldehyde monomer is (2-220):

1.

5. The method for synthesizing covalent organic framework crystal materials 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.

6. A method for synthesizing a covalent organic framework crystal material at room temperature, characterized in that, Includes the following steps: At 25°C, 10 ml of ultra-dry acetonitrile, 50 mg of toluene-4-sulfonic acid monohydrate, and 1 ml of 3M acetic acid were added to a 20 ml glass bottle, and a rotor of appropriate size was added. 0.08 mmol of 2,4,6-tricarboxymethyl phloroglucinol 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 aldehyde monomer solution and ammonia monomer solution. After filtering the aldehyde monomer solution and the ammonia monomer solution sequentially, the mixture was slowly added to the solution in the glass bottle. The glass bottle was then placed on a magnetic stirrer and stirred at a speed of 300 r / min for 5 min. The solid was collected and washed and filtered three times with tetrahydrofuran and DMAC, and then washed and filtered three times with acetone to completely remove unreacted monomers. The washed solid was then placed in a vacuum oven at 80℃ for 12 h to dry, thus obtaining the covalent organic framework crystal material.

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