Covalent organic framework material for electro-catalytic water desorption of hydrogen as well as preparation method and application of covalent organic framework material

Abstract

The invention discloses a covalent organic framework material for hydrogen evolution through electro-catalysis water desorption as well as a preparation method and application of the covalent organic framework material, relates to a covalent organic framework material as well as a preparation method and application of the covalent organic framework material, and aims at solving the technical problems that an existing precious metal doped covalent organic framework composite material is complex in preparation and low in hydrogen evolution efficiency. The basic structural unit of the covalent organic framework material is as follows: # imgabs0 #, the # imgabs0 # is obtained by condensation reaction of 2-phenyl-1H-phenanthro [9, 10-d] imidazole-5, 10-diamine and 2, 4, 6-triformyl phloroglucinol, when the # imgabs0 # is prepared into an electrode, when the # imgabs0 # is used for electro-catalysis water desorption of hydrogen, in a 0.5 mol.L <-1 > H2SO4 solution, the overpotential is as low as 167-197 mV under 10mA. Cm <-2 >, and the potential is as low as 167-197 mV under 10mA. Cm <-2 >. The method can be used in the field of water electrolysis hydrogen production.

Description

Technical Field

[0001] The invention relates to a covalent organic framework material and a preparation method and application thereof. Background Art

[0002] With the combustion of fossil fuels and the emission of greenhouse gases, energy depletion and environmental pollution have caused problems. Hydrogen, as a sustainable energy source and a substitute for traditional fossil fuels, can alleviate the environmental problems caused by greenhouse gases. Electrochemical water splitting is an effective way to produce hydrogen fuel using electrocatalysts. Covalent organic frameworks (COFs), as a class of crystalline porous organic polymers connected by strong covalent bonds, have many advantages such as diverse and designable structures, high porosity and good stability. They have been favored by researchers in recent years. In 2021, SantuRuida's research group reported a new covalent organic framework electrochemical hydrogen evolution material in the 22nd issue of the journal ChemSusChem, Volume 14. In 0.5M H2SO4 electrolyte, it drove 10mAcm -2 The current density requires an overpotential of 200mV. The catalytic activity remains high after a long period of electrocatalysis, but compared with other electrochemical catalysts, the overpotential is high and the hydrogen evolution efficiency is low. In 2021, in the 60th volume and 30th issue of the journal Industrial & Engineering Chemistry Research, a series of ruthenium nanoparticle-doped covalent organic framework / graphene (COF / rGO) composites were reported. The covalent organic framework composites exhibited high electrochemical hydrogen evolution performance at 10mAcm -2 The overpotential is 42 mV at a current density of 400 mV. However, the synthesis steps of the material are complicated, the cost of ruthenium nanoparticles is high, and the stability is poor.

[0003] The covalent organic framework materials for electrocatalytic water splitting and hydrogen splitting reported in the literature currently have the following main defects:

[0004] 1. The electrochemical water separation hydrogen efficiency of most covalent organic framework materials is low;

[0005] 2. The preparation steps of covalent organic framework composite materials for electrochemical water separation and hydrogen separation are complicated;

[0006] 3. Covalent organic framework composite materials used for electrochemical water separation to produce hydrogen are mostly doped with precious metals, which is not conducive to environmental protection. Summary of the invention

[0007] The present invention aims to solve the technical problems of complex preparation steps and low hydrogen evolution efficiency of existing noble metal-doped covalent organic framework composite materials, and provides a covalent organic framework material for electrocatalytic water decomposition of hydrogen and a preparation method and application thereof. The covalent organic framework material for electrocatalytic water decomposition of hydrogen of the present invention realizes efficient electrocatalytic water decomposition of hydrogen, has simple synthesis steps, and solves the defect of complex preparation steps of noble metal-doped covalent organic framework composite materials.

[0008] The basic structural unit of the covalent organic framework material for electrocatalytic water decomposition of hydrogen of the present invention is as follows:

[0009]

[0010] The above-mentioned covalent organic framework material for electrocatalytic water decomposition of hydrogen is obtained by condensation reaction of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine and 2,4,6-triformylpyrogallol, and its synthesis expression is:

[0011]

[0012] The preparation method of the above-mentioned covalent organic framework material for electrocatalytic water decomposition of hydrogen is specifically carried out according to the following steps:

[0013] 1. According to the molar ratio of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine to 2,4,6-triformylpyrogallol of (1-5):1, 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine and 2,4,6-triformylpyrogallol are added to a Pyrex tube containing an organic solvent I, and ultrasonically mixed; then, an acid is added to the Pyrex tube as a catalyst, and ultrasonically mixed to obtain a reaction mixture;

[0014] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 4 to 5 times, and then seal it;

[0015] 3. Heat the Pyrex tube to 100-180°C and react for 72-168 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0016] Fourth, the crude product is filtered, the filter cake is washed with organic solvent II, and then vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0017] Furthermore, the organic solvent I described in step 1 is any two or three of o-dichlorobenzene, mesitylene, N,N-dimethylformamide, dioxane, chlorobenzene, ethyl acetate and n-butanol.

[0018] Furthermore, in step 1, the ratio of the amount of 2,4,6-triformylpyrogallol to the volume of the organic solvent I is 1 mmol: (10-50) mL.

[0019] Furthermore, the acid described in step 1 is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with a mass percentage concentration of 30% to 37%, or concentrated sulfuric acid with a mass percentage concentration of 95% to 98%.

[0020] Furthermore, in step 1, the ratio of the amount of 2,4,6-triformylpyrogallol to the volume of the acid is 1 mmol: (1 to 10) mL.

[0021] Furthermore, the organic solvent II in step 4 is one or any two of methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform and acetone.

[0022] The application of the above-mentioned covalent organic framework material for electrocatalytic water decomposition of hydrogen is to prepare it into an electrode for electrocatalytic water decomposition of hydrogen.

[0023] The method for preparing an electrode using the above-mentioned covalent organic framework material for electrocatalytic water decomposition of hydrogen is carried out according to the following steps:

[0024] 1. Clean the nickel foam of 1 cm×1 cm size with acetone, water, inorganic acid and water ultrasonic cleaning in turn to remove organic matter and oxide film, and vacuum dry to obtain a clean nickel foam matrix;

[0025] 2. Grinding the covalent organic framework material for electrocatalytic hydrogen evolution in an agate mortar to obtain covalent organic framework material powder; ultrasonically mixing the covalent organic framework material powder, carbon black, a binder naphthol and anhydrous ethanol in a mass ratio of 1:1:0.2:1 to obtain a slurry;

[0026] 3. The slurry is evenly applied on the clean nickel foam substrate obtained in step 1, and vacuum dried at a temperature of 50 to 80° C. for 6 to 8 hours to obtain a covalent organic framework material electrode for electrocatalytic water decomposition of hydrogen.

[0027] Furthermore, the water in step 1 is distilled water, deionized water, pure water or high-purity water.

[0028] Furthermore, the inorganic acid in step 1 is hydrochloric acid with a mass percentage concentration of 10% to 30% or nitric acid with a mass percentage concentration of 10% to 40%.

[0029] The present invention constructs a hydrogen evolution catalyst of a covalent organic framework material containing abundant nitrogen atoms and oxygen atoms. The introduction of heteroatoms can effectively regulate the electronic properties of the covalent organic framework material, and improve the conductivity and electrocatalytic activity of the material. Nitrogen and oxygen doping can enhance the conductivity of the covalent organic framework material. At the same time, the hydroxyl groups on the trialdehyde are more easily combined with hydrogen protons, increasing the affinity for hydrogen proton adsorption, thereby promoting the hydrogen evolution reaction. Compared with other existing covalent organic framework materials, the covalent organic framework material for electrocatalytic water decomposition of hydrogen provided by the present invention provides more active sites for hydrogen evolution, is conducive to electron transfer, has strong conductivity, and has high hydrogen evolution efficiency. Compared with commercial platinum-carbon catalysts, the covalent organic framework material for electrocatalytic water decomposition of hydrogen of the present invention does not contain precious metals and has a lower cost. At 0.5 molL -1 In H2SO4 solution, at 10 mA cm – 2 The overpotential is as low as 167-197 mV, and it has good hydrogen evolution performance and can be used in the field of hydrogen production by water electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is an infrared spectrum of a covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1, with the abscissa being the wavelength and the ordinate being the transmittance.

[0031] Figure 2 This is the XRD spectrum of a covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1.

[0032] Figure 3 This is a linear scanning curve diagram of the covalent organic framework material electrode used for electrocatalytic water decomposition of hydrogen in Example 1.

[0033] Figure 4 This is the Tafel curve of the covalent organic framework material electrode used for electrocatalytic water decomposition of hydrogen in Example 1. DETAILED DESCRIPTION

[0034] The beneficial effects of the present invention are verified by the following examples.

[0035] Example 1: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0036] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 32 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 1 mL of o-dichlorobenzene and 1 mL of mesitylene, and mix them evenly with ultrasound; then add 0.2 mL of glacial acetic acid into the Pyrex tube, and mix them evenly with ultrasound to obtain a reaction mixture;

[0037] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 4 times, and then seal it;

[0038] 3. Heat the Pyrex tube to 180°C for 72 hours, and cool to room temperature after the reaction to obtain a crude product;

[0039] 4. The crude product was filtered, the filter cake was repeatedly washed with ethanol and methanol for 4 times, and vacuum dried at 80°C for 12 hours to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0040] In order to determine the structure of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1, the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1 was subjected to infrared spectroscopy test, and the obtained infrared spectrum is as follows: Figure 1 As shown, from Figure 1 It can be seen that the covalent organic framework material has a wavelength of 1580 cm -1 There is a characteristic peak at , which is the stretching vibration of the C=N bond, indicating that a condensation reaction occurred between 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine and 2,4,6-triformylpyrogallol, proving that the covalent organic framework material for electrocatalytic water decomposition of hydrogen was successfully prepared.

[0041] The XRD spectrum of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1 is as follows: Figure 2 As shown, from Figure 2 It can be seen that from Figure 2 It can be seen that three strong covalent organic framework diffraction peaks are presented at about 2.4°, 4.1° and 23.0°, indicating that the material has a high degree of crystallinity, which also shows that the substance is a covalent organic framework material.

[0042] The electrode was prepared using the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1. The specific method was carried out according to the following steps:

[0043] 1. Take 1.0cm×1.0cm nickel foam, first use acetone ultrasonic cleaning for 15min, then use deionized water ultrasonic cleaning twice, each time for 10min; then use 20% mass percentage concentration of dilute hydrochloric acid ultrasonic cleaning for 2min, and finally use deionized water ultrasonic cleaning 3 times, each time for 10min, to remove organic matter and oxide film, and then dry it in a vacuum drying oven at 60℃ for 6h to obtain a clean nickel foam substrate;

[0044] 2. Grind the covalent organic framework material for electrocatalytic water decomposition for hydrogen in an agate mortar for 0.5 h to obtain a covalent organic framework material powder; then ultrasonically mix 1 mg of the covalent organic framework material powder, 1 mg of carbon black, 0.2 mL of a binder naphthol with a mass percentage concentration of 30%, and 1 mL of anhydrous ethanol to obtain a slurry;

[0045] 3. The slurry is evenly applied on the clean nickel foam substrate prepared in step 1, and vacuum dried at 60° C. for 6 h to obtain a covalent organic framework material electrode for electrocatalytic water decomposition of hydrogen.

[0046] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition and hydrogen prepared in this example was tested on an electrochemical workstation. At room temperature, the covalent organic framework material electrode for electrocatalytic water decomposition and hydrogen was used as the working electrode (geometric area 1 cm 2 ), with graphite rod as counter electrode and Ag / AgCl electrode as reference electrode (electrolyte concentration was 0.5 mol·L -1 H2SO4 solution), linear voltammetry test scan rate of 5mV·s -1 The potential range is -0.80V to -1.4V (relative to the Ag / AgCl reference electrode), and the linear voltammetric scan curve is as follows: Figure 3 As shown. Figure 3 It can be seen that at 10 mA cm – 2 The overpotential under the condition is as low as 167 mV, which indicates that the covalent organic framework material prepared in Example 1 has good hydrogen evolution performance.

[0047] Figure 4 The Tafel slope curve of the covalent organic framework material electrode for electrocatalytic water decomposition of hydrogen prepared in Example 1 is shown in FIG. Figure 4 It can be calculated that the Tafel slope is 107.4mV·dec – 1 , further proving that the covalent organic framework material for electrocatalytic water decomposition of hydrogen has good hydrogen evolution performance. The hydrogen evolution catalytic performance of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1 is compared with the hydrogen evolution catalytic performance of existing materials as shown in Table 1.

[0048] Table 1 Performance comparison of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 1 and other existing hydrogen evolution catalysts

[0049]

[0050] Example 2: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0051] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 32 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 1 mL of N,N-dimethylformamide and 1 mL of dioxane, and mix them evenly with ultrasound; then add 0.4 mL of trifluoroacetic acid into the Pyrex tube, and mix them evenly with ultrasound to obtain a reaction mixture;

[0052] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 5 times, and then seal it;

[0053] 3. Heat the Pyrex tube to 160°C and react for 96 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0054] Fourth, the crude product is filtered, the filter cake is repeatedly washed with methanol and acetonitrile, and vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0055] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 2 was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA cm – 2 The overpotential is as low as 184 mV, which indicates that the covalent organic framework material prepared in Example 2 has good hydrogen evolution performance.

[0056] Example 3: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0057] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 97 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 1 mL of chlorobenzene and 4 mL of ethyl acetate, and mix them evenly with ultrasound; then add 0.6 mL of benzenesulfonic acid into the Pyrex tube, and mix them evenly with ultrasound to obtain a reaction mixture;

[0058] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 4 times, and then seal it;

[0059] 3. Heat the Pyrex tube to 140°C and react for 128 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0060] Fourth, the crude product is filtered, the filter cake is repeatedly washed with acetonitrile and tetrahydrofuran, and vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0061] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 3 was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA·cm – 2 The overpotential under the condition is as low as 195 mV, which indicates that the covalent organic framework material prepared in Example 3 has good hydrogen evolution performance.

[0062] Example 4: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0063] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 129 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 2 mL of dioxane and 3 mL of n-butanol, and mix them evenly by ultrasonication; then add 0.6 mL of p-toluenesulfonic acid into the Pyrex tube, and mix them evenly by ultrasonication to obtain a reaction mixture;

[0064] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 5 times, and then seal it;

[0065] 3. Heat the Pyrex tube to 120°C and react for 144 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0066] 4. The crude product is filtered, the filter cake is repeatedly washed with tetrahydrofuran and dichloromethane, and vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0067] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition of hydrogen prepared in Example 4 was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA cm – 2 The overpotential under the condition is as low as 193 mV, which indicates that the covalent organic framework material prepared in Example 4 has good hydrogen evolution performance.

[0068] Example 5: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0069] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 162 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 3 mL of mesitylene and 2 mL of ethyl acetate, and mix them evenly by ultrasonication; then add 0.8 mL of 30% concentrated hydrochloric acid into the Pyrex tube, and mix them evenly by ultrasonication to obtain a reaction mixture;

[0070] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 5 times, and then seal it;

[0071] 3. Heat the Pyrex tube to 170°C and react for 168 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0072] 4. The crude product is filtered, the filter cake is repeatedly washed with dichloromethane and chloroform, and vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0073] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition and hydrogen prepared in Example 5 was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA·cm – 2 The overpotential is as low as 187 mV, which indicates that the covalent organic framework material prepared in Example 5 has good hydrogen evolution performance.

[0074] Example 6: The preparation method of the covalent organic framework material for electrocatalytic water decomposition of hydrogen in this example is carried out according to the following steps:

[0075] 1. Add 21 mg of 2,4,6-triformylpyrogallol and 65 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine into a Pyrex tube containing 1 mL of N,N-dimethylformamide and 2 mL of mesitylene, and mix them evenly by ultrasonication; then add 1 mL of 95% concentrated sulfuric acid into the Pyrex tube, and mix them evenly by ultrasonication to obtain a reaction mixture;

[0076] 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 5 times, and then seal it;

[0077] 3. Heat the Pyrex tube to 180°C and react for 72 hours. After the reaction is completed, cool to room temperature to obtain a crude product.

[0078] 4. The crude product is filtered, the filter cake is repeatedly washed with chloroform and acetone, and vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

[0079] The catalytic performance of the covalent organic framework material for electrocatalytic water decomposition hydrogen prepared in Example 6 was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA·cm – 2 The overpotential under the condition is as low as 197 mV, which indicates that the covalent organic framework material prepared in Example 6 has good hydrogen evolution performance.

Claims

1. A covalent organic framework material for electrocatalytic water decomposition of hydrogen, characterized in that The basic structural unit of the covalent organic framework material is as follows:

2. A method for preparing a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 1, characterized in that The method proceeds as follows:

1. According to the molar ratio of 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine to 2,4,6-triformylpyrogallol of (1-5):1, 2-phenyl-1H-phenanthro[9,10-d]imidazole-5,10-diamine and 2,4,6-triformylpyrogallol are added to a Pyrex tube containing an organic solvent I, and ultrasonically mixed; then, an acid is added to the Pyrex tube as a catalyst, and ultrasonically mixed to obtain a reaction mixture; 2. Perform liquid nitrogen freezing, vacuuming and thawing cycles on the Pyrex tube, repeat the operation 4 to 5 times, and then seal it; 3. Heat the Pyrex tube to 100-180°C and react for 72-168 hours. After the reaction is completed, cool to room temperature to obtain a crude product. Fourth, the crude product is filtered, the filter cake is washed with organic solvent II, and then vacuum dried to obtain a covalent organic framework material for electrocatalytic water decomposition of hydrogen.

3. The method for preparing a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 2, characterized in that: The organic solvent I described in step 1 is any two or three of o-dichlorobenzene, mesitylene, N,N-dimethylformamide, dioxane, chlorobenzene, ethyl acetate and n-butanol.

4. A method for preparing a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 2 or 3, characterized in that: The acid described in step 1 is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with a mass percentage concentration of 30% to 37%, or concentrated sulfuric acid with a mass percentage concentration of 95% to 98%.

5. The method for preparing a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 2 or 3, characterized in that: In step 1, the ratio of the amount of 2,4,6-triformylpyrogallol to the volume of the acid is 1 mmol: (1-10) mL.

6. A method for preparing a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 2 or 3, characterized in that: The organic solvent II described in step 4 is one or any two of methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform and acetone.

7. The use of a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 1, characterized in that: This application is to prepare a covalent organic framework material for electrocatalytic water decomposition of hydrogen into an electrode for use in electrocatalytic water decomposition of hydrogen.

8. The use of a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 7, characterized in that: The method for preparing an electrode using a covalent organic framework material for electrocatalytic water decomposition of hydrogen is carried out in the following steps:

1. Clean the nickel foam of 1 cm×1 cm size with acetone, water, inorganic acid and water ultrasonic cleaning in turn to remove organic matter and oxide film, and vacuum dry to obtain a clean nickel foam matrix; 2. Grinding the covalent organic framework material for electrocatalytic hydrogen evolution in an agate mortar to obtain covalent organic framework material powder; ultrasonically mixing the covalent organic framework material powder, carbon black, a binder naphthol and anhydrous ethanol in a mass ratio of 1:1:0.2:1 to obtain a slurry; 3. The slurry is evenly applied on the clean nickel foam substrate obtained in step 1, and vacuum dried at a temperature of 50 to 80° C. for 6 to 8 hours to obtain a covalent organic framework material electrode for electrocatalytic water decomposition of hydrogen.

9. The use of a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 8, characterized in that: The water in step 1 is distilled water, deionized water, pure water or high-purity water.

10. The use of a covalent organic framework material for electrocatalytic water decomposition of hydrogen according to claim 8 or 9, characterized in that: The inorganic acid in step 1 is hydrochloric acid with a mass percentage concentration of 10% to 30% or nitric acid with a mass percentage concentration of 10% to 40%.

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