Method for synthesizing CCOFs photocatalyst through induction of chiral amino acid and application of CCOFs photocatalyst in photocatalytic hydrogen evolution

Abstract

The invention relates to a method for synthesizing CCOFs through induction of chiral amino acid and application of the CCOFs in photocatalytic hydrogen evolution, and belongs to the technical field of functional materials and photocatalysis. The chiral COFs with the helical structure is constructed under the mild condition through the induction effect of chiral amino acid, the obtained material shows remarkably improved hydrogen evolution performance under the driving of visible light, and a novel efficient catalyst is provided for solar energy conversion.

Description

Technical Field

[0001] This invention relates to a method for the chiral amino acid-induced synthesis of CCOFs photocatalysts and their application in photocatalytic hydrogen evolution, belonging to the fields of functional materials and photocatalysis. Background Technology

[0002] Chiral covalent organic frameworks (CCOFs), as an important branch of chiral and porous framework materials, have attracted much attention in recent years due to their potential applications in asymmetric catalysis, chiral separation, and enantioselective sensing. In CCOF synthesis, chiral induction strategies are often used to induce chiral structures in achiral frameworks, i.e., using chiral inducing agents to induce framework chirality. Chiral amines are common chiral inducing agents, but these substances are difficult to recycle and pose significant environmental hazards. Their corrosiveness, ecotoxicity, and threats to human health are all important factors limiting their widespread application. Therefore, developing greener and more environmentally friendly chiral inducing agents is key to solving the current dilemma.

[0003] Chirality can regulate the spin polarization of photogenerated charges in photocatalysts, i.e., chirality-induced spin selectivity (CISS effect). Spin-polarized electrons generated by this effect can reduce electron-hole recombination, improve carrier separation efficiency, and thus enhance photocatalytic hydrogen evolution efficiency.

[0004] Currently, there are no reports on the application of CCOFs in the field of photocatalytic hydrogen evolution and the improvement of their photocatalytic efficiency by means of the CISS effect. Summary of the Invention

[0005] To address the issues of corrosiveness, ecotoxicity, health hazards, and limited availability of chiral amine inducers in existing chiral-induced synthesis methods for CCOFs, this invention leverages the abundant resources and safety advantages of widely distributed chiral amino acids in nature to provide a method for the chiral amino acid-induced synthesis of CCOFs and its application in photocatalytic hydrogen evolution.

[0006] This invention is the first to use chiral amino acids to induce the synthesis of CCOF photocatalysts, avoiding the use of potentially harmful chiral amine inducers, and greatly enhancing the feasibility and safety of this synthesis method in the practical application of CCOF photocatalysts.

[0007] To address the challenge of low photocatalytic hydrogen evolution efficiency due to high photogenerated charge recombination rates in photocatalytic hydrogen evolution research, this invention applies the CCOFs prepared in this paper to photoenergy conversion. Utilizing the unique advantage of chirality in controlling charge spin polarization, its unique chiral structure effectively promotes improved photocatalytic hydrogen evolution performance. By controlling the spin polarization of photogenerated charges through the CISS effect, the problem of photogenerated charge recombination is solved, thereby enhancing the hydrogen production performance from water splitting. This not only expands the application range of CCOFs but also opens up new research directions in the field of photocatalytic hydrogen evolution. The preparation method is green and safe.

[0008] This invention is achieved through the following technical solution: A method for the chiral amino acid-induced synthesis of CCOF photocatalysts includes the following steps: 1) Using chiral amino acids as inducing agents, chiral amino acids are mixed with aldehyde / ketone monomers in a mixed solvent, a catalyst is added, and after the reaction is complete, amine monomers or active methyl / methylene monomers are added. 2) The reaction system of step 1) is heated and reacted under solvothermal conditions through dynamic covalent chemistry. The precipitate obtained from the reaction is washed to remove residual chiral amino acids, then purified and dried to obtain CCOFs.

[0009] According to a preferred embodiment of the present invention, in step 1), the chiral amino acid is D / L-phenylalanine, D / L-tyrosine, D / L-tryptophan, D / L-proline, or D / L-cysteine.

[0010] According to a preferred embodiment of the present invention, in step 1), the aldehyde monomer is 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde, pyromellitic tricarboxaldehyde, 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, terephthalaldehyde, or 1,3,6,8-tetra(4-carboxylphenyl)perylene.

[0011] According to a preferred embodiment of the present invention, in step 1), the ketone monomer is 1,3,5-tris(p-formylphenyl)benzene.

[0012] According to a preferred embodiment of the present invention, in step 1), the molar ratio of chiral amino acid to aldehyde / ketone monomer is (0.1~3):1.

[0013] According to a preferred embodiment of the present invention, in step 1), the mixed solvent is a mixture of any two of the following: mesitylene, 1,4-dioxane, o-dichlorobenzene, n-butanol, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0014] According to a preferred embodiment of the present invention, in step 1), the mass-to-volume ratio of the chiral amino acid to the mixed solvent is (10-60):(0.5-5), unit, mg / mL.

[0015] According to a preferred embodiment of the present invention, in step 1), the catalyst is an aqueous solution of acetic acid, cesium carbonate, piperidine, an aqueous solution of sodium hydroxide, or an aqueous solution of potassium hydroxide.

[0016] More preferably, the concentration of the acetic acid aqueous solution is 1-18 mol / L.

[0017] More preferably, the concentration of the sodium hydroxide aqueous solution or potassium hydroxide aqueous solution is 0.1~4 mol / L.

[0018] According to a preferred embodiment of the present invention, in step 1), the amine monomer is p-phenylenediamine, biphenylenediamine, 2,2'-bipyridine-5,5'-diamino, 1,3,5-tris(4-aminophenyl)benzene, tris(4-aminophenyl)amine, or 1,3,6,8-tetra-(p-aminophenyl)-pyrene.

[0019] According to a preferred embodiment of the present invention, in step 1), the active methyl / methylene monomer is terephthalonitrile, benzyldiamine acetonitrile, 2,2'-bipyridine-5,5'-diacetonitrile, 1,3,5-trimethyltriazine, dimethylpyrazine, or tetramethylpyrazine.

[0020] According to a preferred embodiment of the present invention, in step 1), the mass-to-volume ratio of chiral amino acid to catalyst is (10~60):(0.1-1), unit: mg / mL.

[0021] According to a preferred embodiment of the present invention, in step 1), the molar ratio of aldehyde / ketone monomers to amine monomers or active methyl / methylene monomers is (0.5-2):(0.8-3).

[0022] According to a preferred embodiment of the present invention, in step 2), the temperature is heated to 20~200℃ and the reaction time is 12-120h.

[0023] This invention is the first to use dynamic covalent chemical reactions such as imine condensation, Knoevenagel condensation, and aldol condensation induced by chiral amino acids to successfully prepare CCOFs.

[0024] According to a preferred embodiment of the present invention, in step 2), the removal of residual chiral amino acids is achieved by repeatedly washing in N,N-dimethylformamide 10-20 times to remove residual chiral amino acids.

[0025] According to a preferred embodiment of the present invention, in step 2), purification is performed by extraction with methanol and tetrahydrofuran in a Soxhlet extractor for 12-40 hours.

[0026] According to a preferred embodiment of the present invention, in step 2), drying is performed in a vacuum drying oven at 50~100°C for 6-24 hours.

[0027] According to a preferred embodiment of the present invention, the present invention employs CCOF photocatalysts with β-ketoenamine linkages, represented by chiral amino acids such as TpPa-1, TpBd, or TpBpy, and CCOF photocatalysts with vinyl linkages, represented by NKCOF-113.

[0028] A CCOF photocatalyst was prepared using the method described above.

[0029] The above-mentioned CCOF photocatalysts are used as highly efficient photocatalysts in solar-driven hydrogen evolution reaction (HER).

[0030] According to a preferred embodiment of the present invention, the specific application method is as follows: CCOF photocatalysts were dispersed in a sacrificial aqueous solution, and Pt cocatalysts were loaded using photodeposition. After purging with an inert atmosphere and sealing, the mixture was placed under visible light for photocatalytic hydrogen evolution.

[0031] According to a preferred embodiment of the present invention, the sacrificial agent is ascorbic acid, sodium ascorbate, citric acid, sodium citrate, lactic acid, triethylamine, or triethanolamine.

[0032] According to a preferred embodiment of the present invention, the concentration of the sacrificial agent aqueous solution is 0.1-10M.

[0033] According to a preferred embodiment of the present invention, the mass-to-volume ratio of the CCOFs photocatalyst to the sacrificial agent aqueous solution is (1-50):100, unit: mg / mL.

[0034] According to a preferred embodiment of the present invention, the precursor of the Pt co-catalyst is an aqueous solution of chloroplatinic acid, with a loading of 0.01 wt% to 20 wt% based on the atomic mass of Pt.

[0035] According to a preferred embodiment of the present invention, the mass ratio of the CCOFs photocatalyst to the Pt cocatalyst precursor is 10:(0.1~2), and the photodeposition time is 0.1-1.5 h.

[0036] According to a preferred embodiment of the present invention, the inert atmosphere is Ar, and the inert atmosphere treatment time is 10 min to 2 h.

[0037] According to a preferred embodiment of the present invention, the photocatalytic hydrogen evolution pressure is 1 atm, the reaction temperature is 0-50℃, and the time is 0.1-20h.

[0038] According to a preferred embodiment of the present invention, the visible light wavelength λ > 400 nm.

[0039] The CCOF photocatalyst obtained in this invention exhibits excellent photocatalytic performance. During the photocatalytic process, the spin polarization effect of the chiral structure on the photogenerated charge enhances the photocatalytic hydrogen evolution reaction performance, achieving long-term stable photocatalytic hydrogen evolution. Therefore, chiral amino acids, as a greener and safer chiral inducer, not only realize the synthesis of CCOFs but also enhance their photocatalytic hydrogen evolution activity.

[0040] Technical features and advantages of the present invention: 1. This invention addresses the corrosiveness, ecotoxicity, and health hazards of chiral amine inducers in existing chiral-induced synthesis methods for CCOFs. It utilizes the abundance and safety advantages of chiral amino acids widely distributed in nature to provide a green and safe method for the chiral amino acid-induced synthesis of CCOFs.

[0041] 2. This invention successfully applies CCOFs to photocatalytic hydrogen evolution research, expanding the application of CCOFs in the field of photocatalytic hydrogen evolution. Photocatalytic activity tests show that the CCOF photocatalyst of this invention has a long-term stable hydrogen generation rate. Compared with the photocatalytic hydrogen evolution performance of isomeric achiral COFs, its photocatalytic hydrogen evolution activity is significantly improved, and the apparent quantum yield (AQY) of photocatalytic hydrogen evolution is increased to over 50%.

[0042] 3. The CCOFs of the present invention have high crystallinity, large specific surface area, and obvious chiral structure characteristics. The chiral structure promotes the spin polarization and rapid migration of photogenerated charges, thereby enhancing the photocatalytic hydrogen evolution performance. Attached Figure Description

[0043] Figure 1 Synthetic pathway of tryptophan-induced chiral TpPa-1 (a), PXRD, N2 adsorption-desorption isotherms and their corresponding pore size distribution (d).

[0044] Figure 2 Infrared spectrum of chiral TpPa-1; Figure 3 Spin polarization, CD, CPL, and photocurrent diagrams: a) Spin polarization of D-Try-TpPa-1 and L-Try-TpPa-1 on photogenerated charges; b) CD of D-Try-TpPa-1 and L-Try-TpPa-1; c) CPL of D-Try-TpPa-1, L-Try-TpPa-1, and TpPa-1; d) Photocurrent of TpPa-1 under different magnetic field directions; e) Photocurrent of D-Try-TpPa-1 under different magnetic field directions; f) Photocurrent of L-Try-TpPa-1 under different magnetic field directions.

[0045] Figure 4(a) Photocatalytic hydrogen production at specific time intervals after loading Pt onto D-Try-TpPa-1, L-Try-TpPa-1, and TpPa-1; (b) Stability test of photocatalytic hydrogen evolution performance; (c) Apparent quantum yield (AQY) at different wavelengths.

[0046] Figure 5 (a) PXRD and (b) CD spectra of chiral TpPa-1 induced by phenylalanine; (c) PXRD of chiral TpPa-1 induced by tyrosine; (d) PXRD of chiral TpPa-1 induced by cysteine; (e) PXRD of chiral TpBpy induced by tryptophan; and (f) PXRD of chiral NKCOF-113. Detailed Implementation

[0047] Unless otherwise stated in the context of this application, the technical terms and abbreviations used herein have the conventional meanings known to those skilled in the art; unless otherwise stated, the raw material compounds used in the following examples are all commercially available.

[0048] The specific implementation methods for material preparation and characterization testing of various properties as described in this invention are as follows. Conversely, the following examples are only for further explanation and illustration of this invention and should not be considered as limiting the scope of the invention, which will be limited only by the claims.

[0049] Example 1 The method for inducing the synthesis of chiral TpPa-1 using chiral amino acids comprises the following steps: 1) Add 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde (Tp, 32 mg) and 1 equivalent of D-tryptophan (Try, 31.1 mg) to a Shrek tube containing a mixture of 1.5 mL of mesitylene, 1.5 mL of 1,4-dioxane and 0.6 mL of acetic acid aqueous solution (concentration 6 M). After the mixture is completely transparent and turns bright yellow, add p-phenylenediamine (Pa, 24.3 mg).

[0050] 2) The Shrek tube was frozen and evacuated at 77 K to remove air, then sealed and transferred to an oil bath. It was heated at 120 °C for 3 days to produce a red solid. The solid was separated by filtration and repeatedly washed with DMF 10 times. The obtained solid was washed with tetrahydrofuran and methanol for 24 hours each in a Soxhlet extractor. Then, the chiral TpPa-1 was activated by vacuum drying at 80 °C for 12 hours (yield 90%), and denoted as D-Try-TpPa-1.

[0051] Example 2 The preparation method is the same as that described in Example 1, except that: L-tryptophan was used instead of D-tryptophan, and the rest was carried out as in Example 1. The resulting product was denoted as L-Try-TpPa-1.

[0052] Experimental Example 1: 1. The synthetic pathway of tryptophan-induced chiral TpPa-1 is shown below. Figure 1 Figure 1(a) shows the X-ray powder diffraction (PXRD) of the synthesized D-Try-TpPa-1, L-Try-TpPa-1, and TpPa-1. The obvious diffraction peaks appear at the same positions as those of TpPa-1, indicating the successful synthesis of highly crystalline COFs. The chiral induction process does not affect the crystal structure of the COFs. The N2 adsorption-desorption isotherms and corresponding pore size distributions of D / L-Try-TpPa-1 and TpPa-1 are shown in Figure 1(b). Figure 1 (c) Figure 1 The high specific surface area and identical pore size distribution in the middle (d) further demonstrate that the present invention yields a highly crystalline COF structure.

[0053] 2. The Fourier Transmission Spectra (FT-IR) of D-Try-TpPa-1, L-Try-TpPa-1, TpPa-1 and D-Try, L-Try are shown below. Figure 2 The obvious C=O and NH signals in COFs indicate that the COF structure is linked by β-ketoenamine, and no characteristic peaks of amino acids were found in the COF spectrum, indicating that the residual amino acid components were removed during the post-processing.

[0054] 3. The spin polarization effect of the chiral structure (D-Try-TpPa-1) on the photogenerated charge of COFs is shown in the schematic diagram. Figure 3 The circular dichroism (CD) spectra of D-Try-TpPa-1 and L-Try-TpPa-1 are shown in (a). Figure 3 In (b), the obvious absorption peak at 550 nm under polarized light confirms the chiral structure of the COFs. Its circularly polarized fluorescence (CPL) spectrum is shown in [reference needed]. Figure 3 In (c), the obvious circularly polarized fluorescence generated by its excitation verifies its chiral structure and simultaneously verifies... Figure 3 Spin polarization in (a). Photocurrent measurements of TpPa-1 with D-Try-TpPa-1 and L-Try-TpPa-1 are shown in [reference needed]. Figure 3 In the middle (df), all three showed enhanced photocurrent under the action of a magnetic field. This is due to the Lorentz force on the photogenerated charge. D-Try-TpPa-1 and L-Try-TpPa-1 showed different enhanced photocurrent signals under different magnetic field directions, which proved the spin polarization of photoelectrons and the CISS effect.

[0055] Experimental Example 2: Photocatalytic hydrogen evolution reaction: 10 mg of D-Try-TpPa-1, L-Try-TpPa-1, and TpPa-1 samples were dispersed in 0.1 mol / L ascorbic acid aqueous solution, and 1 mg of chloroplatinic acid aqueous solution was added as a precursor for Pt co-catalyst. The system was purged with argon gas, sealed, and placed under visible light for in-situ photodeposition photocatalytic hydrogen evolution reaction (λ>420 nm). The gas above the system was collected and quantitatively analyzed by gas chromatography.

[0056] The photocatalytic hydrogen evolution tests were performed using the methods described above, and the test results are as follows: Figure 4 As shown in (a), the chiral structure enhances the photocatalytic hydrogen evolution performance by nearly 3.5 times and exhibits good cycling stability, showing no performance degradation after four cycles. Figure 4 (b) Under optimal conditions, its apparent quantum yield (AQY) exceeds 50% at both 475 nm and 500 nm, demonstrating its excellent solar energy conversion capability.

[0057] Example 3 The preparation method is the same as that described in Example 1, except that: The product obtained by replacing D-tryptophan with D-phenylalanine (Phe, 25.2 mg) is denoted as D-Phe-TpPa-1.

[0058] Example 4 The preparation method is the same as that described in Example 1, except that: The product obtained by replacing D-tryptophan with L-phenylalanine (Phe, 25.2 mg) is designated L-Phe-TpPa-1. The PXRD patterns of D-Phe-TpPa-1 and L-Phe-TpPa-1 are shown below. Figure 5 (a) The obvious diffraction peaks indicate the successful synthesis of highly crystalline COFs, and their CD spectrum is shown in Figure 1. Figure 5 In (b), the obvious absorption peak at a wavelength of 550 nm under polarized light proves its chiral structure.

[0059] To investigate the universality of this chiral COF synthesis method, chiral TpPa-1 was also synthesized using D / L-tyrosine and D / L-cysteine ​​induction. Its PXRD values ​​are shown below. Figure 5 (c) and Figure 5 In the middle (d), the obvious diffraction peaks demonstrate the universality of chiral amino acid-induced synthesis of crystalline chiral COFs. Furthermore, β-ketoenamine COFs with larger pore sizes, represented by TpBpy, and vinyl-bridged COFs, represented by NKCOF-113, were synthesized using D / L-tryptophan induction, respectively. PXRD results are shown in [Figure 1]. Figure 5 (e) and Figure 5In (f), chiral COFs with good crystallinity were obtained, demonstrating that chiral amino acids can induce the synthesis of various types of chiral COF structures, further illustrating the universality of this method.

[0060] Example 5 Using the preparation method described in Example 1, the difference is that: D-tyrosine (Tyr, 27.6 mg) was used instead of D-tryptophan, and the obtained product was denoted as D-Tyr-TpPa-1.

[0061] Example 6 Using the preparation method described in Example 1, the difference is that: L-tyrosine (Tyr, 27.6 mg) was used instead of D-tryptophan, and the obtained product was denoted as L-Tyr-TpPa-1.

[0062] The PXRD of D-Tyr-TpPa-1 and L-Tyr-TpPa-1 is shown in Figure 5 (c) in.

[0063] Example 7 Using the preparation method described in Example 1, the difference is that: D-cysteine (Cys, 18.4 mg) was used instead of D-tryptophan, and the obtained product was denoted as D-Cys-TpPa-1.

[0064] Example 8 Using the preparation method described in Example 1, the difference is that: L-cysteine (Cys, 18.4 mg) was used instead of D-tryptophan, and the obtained product was denoted as L-Cys-TpPa-1.

[0065] The PXRD of D-Cys-TpPa-1 and L-Cys-TpPa-1 is shown in Figure 5 (d) in.

[0066] Example 9 The method for inducing the synthesis of chiral TpBpy with D-tryptophan is as follows: 2,4,6-Trihydroxybenzene-1,3,5-tricarboxaldehyde (Tp, 32 mg) and 1 equivalent of D-tryptophan (Try, 31.1 mg) were added to a Shrek tube containing a mixture of 3 mL N,N-dimethylacetamide, 1 mL o-dichlorobenzene, and 0.4 mL acetic acid aqueous solution (6 M concentration). After the mixture became completely clear and turned bright yellow, 2,2'-bipyridine-5,5'-diamino (Bpy, 42.5 mg) was added. The tube was frozen at 77 K to remove air, then sealed and transferred to an oil bath. Heating at 120 °C for 3 days produced a red solid, which was separated by filtration and repeatedly washed 10 times with DMF. The resulting solid was washed in a Soxhlet extractor with tetrahydrofuran and methanol for 24 hours each. Chiral TpBpy was then activated by vacuum drying at 80 °C for 12 hours (75% yield), and the resulting product was designated D-Try-TpBpy.

[0067] Example 10 The method described in the same way as in Example 9 differs in that: L-Try (31.1 mg) was used instead of D-Tryptophan, and the rest was carried out as in Example 9. The resulting product was named L-Try-TpBpy.

[0068] The PXRD values ​​for D-Try-TpBpy and L-Try-TpBpy are shown below. Figure 5 Middle (e).

[0069] Example 11 The method for D-tryptophan-induced synthesis of chiral NKCOF-113 comprises the following steps: 2,4,6-Tris(4-aldehydephenyl)-1,3,5-triazine (TFP, 25.2 mg) and 1 equivalent of D-tryptophan (Try, 13.1 mg) were added to a Shrek tube containing a mixture of 0.8 mL n-butanol, 0.2 mL o-dichlorobenzene, and 64 mg cesium carbonate. After the mixture became completely clear, 2,2'-bipyridine-5,5'-diacetonitrile (Bpy-CN, 22.6 mg) was added. The tube was frozen at 77 K to remove air, then sealed and transferred to an oil bath. It was heated at 120 °C for 3 days, producing a yellow solid. This solid was separated by filtration and repeatedly washed 10 times with DMF. The resulting solid was washed in a Soxhlet extractor with tetrahydrofuran and methanol for 24 hours each. The chiral NKCOF-113 was then activated by vacuum drying at 80°C for 12 hours (95% yield), and was designated as D-Try-NKCOF-113.

[0070] Example 12 The method described in the same way as in Example 11, except that: L-tryptophan (Try, 31.1 mg) was used instead of D-tryptophan, and the rest was carried out as in Example 11. The resulting product was designated as L-Try-NKCOF-113.

[0071] The PXRD values ​​for D-Try-NKCOF-113 and L-Try-NKCOF-113 are shown below. Figure 5 (f)

Claims

1. A method for the chiral amino acid-induced synthesis of CCOF photocatalysts, comprising the following steps: 1) Using chiral amino acids as inducing agents, chiral amino acids are mixed with aldehyde / ketone monomers in a mixed solvent, a catalyst is added, and after the reaction is complete, amine monomers or active methyl / methylene monomers are added. 2) The reaction system of step 1) is heated and reacted under solvothermal conditions through dynamic covalent chemistry. The precipitate obtained from the reaction is washed to remove residual chiral amino acids, then purified and dried to obtain CCOFs photocatalyst.

2. The method according to claim 1, characterized in that, In step 1), the chiral amino acid is D / L-phenylalanine, D / L-tyrosine, D / L-tryptophan, D / L-proline, or D / L-cysteine; the aldehyde monomer is 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde, pyromellitic tricarboxaldehyde, 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, terephthalaldehyde, or 1,3,6,8-tetra(4-formaldehydephenyl)perylene; and the ketone monomer is 1,3,5-tris(p-formylphenyl)benzene.

3. The method according to claim 1, characterized in that, In step 1), the molar ratio of chiral amino acid to aldehyde / ketone monomer is (0.1~3):

1. The mixed solvent is a mixture of any two of the following: mesitylene, 1,4-dioxane, o-dichlorobenzene, n-butanol, N,N-dimethylacetamide, and N,N-dimethylformamide. The mass-volume ratio of chiral amino acid to mixed solvent is (10-60):(0.5-5), unit: mg / mL.

4. The method according to claim 1, characterized in that, In step 1), the catalyst is an aqueous solution of acetic acid, cesium carbonate, piperidine, an aqueous solution of sodium hydroxide, or an aqueous solution of potassium hydroxide. The concentration of the aqueous solution of acetic acid is 1-18 mol / L, and the concentration of the aqueous solution of sodium hydroxide or potassium hydroxide is 0.1-4 mol / L.

5. The method according to claim 1, characterized in that, The amine monomers are p-phenylenediamine, biphenylenediamine, 2,2'-bipyridine-5,5'-diamino, 1,3,5-tris(4-aminophenyl)benzene, tris(4-aminophenyl)amine, or 1,3,6,8-tetra-(p-aminophenyl)-pyrene; the active methyl / methylene monomers are terephthalic acid acetonitrile, biphenylenediamine acetonitrile, 2,2'-bipyridine-5,5'-diacetonitrile, 1,3,5-trimethyltriazine, dimethylpyrazine, or tetramethylpyrazine; the mass-to-volume ratio of chiral amino acids to catalyst is (10~60):(0.1-1), unit, mg / mL; the molar ratio of aldehyde / ketone monomers to amine monomers or active methyl / methylene monomers is (0.5-2):(.8-3).

6. The method according to claim 1, characterized in that, In step 2), the reaction temperature is heated to 20-200℃ and the reaction time is 12-120 h. The residual chiral amino acids are removed by washing repeatedly in N,N-dimethylformamide 10-20 times. The purification is carried out by extraction with methanol and tetrahydrofuran in a Soxhlet extractor for 12-40 h. The drying is carried out in a vacuum drying oven at 50-100℃ for 6-24 h.

7. A CCOFs photocatalyst, prepared by the method described in any one of claims 1-6.

8. The application of the CCOFs photocatalyst as a highly efficient photocatalyst in solar-driven hydrogen evolution reaction (HER), specifically the following application method: CCOF photocatalysts were dispersed in a sacrificial aqueous solution, and Pt cocatalysts were loaded using photodeposition. After purging with an inert atmosphere and sealing, the mixture was placed under visible light for photocatalytic hydrogen evolution.

9. The application according to claim 8, characterized in that, The sacrificial agent is ascorbic acid, sodium ascorbate, citric acid, sodium citrate, lactic acid, triethylamine or triethanolamine, and the concentration of the sacrificial agent aqueous solution is 0.1-10M. The mass-volume ratio of CCOFs photocatalyst to sacrificial agent aqueous solution is (1-50):100, unit, mg / mL.

10. The application according to claim 8, characterized in that, The precursor for the Pt co-catalyst is an aqueous solution of chloroplatinic acid, with a loading of 0.01 wt% to 20 wt%. The mass ratio of the CCOFs photocatalyst to the Pt co-catalyst precursor is 10:(0.1~2) based on the atomic mass of Pt. The photodeposition time is 0.1-1.5 h, the inert atmosphere is Ar, the inert atmosphere treatment time is 10 min-2 h, the photocatalytic hydrogen evolution pressure is 1 atm, the reaction temperature is 0-50℃, the time is 0.1-20 h, and the visible light λ>400 nm.

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