A covalent organic framework material for electrocatalytic hydrogen desorption from water, its preparation method and application

Abstract

This invention relates to a covalent organic framework material for electrocatalytic hydrogen evolution from water, its preparation method, and its application. It aims to solve the technical problems of complex preparation and low hydrogen evolution efficiency of existing noble metal-doped covalent organic framework composite materials. The basic structural unit of the covalent organic framework material of this invention is as follows: it is obtained by the condensation reaction of 2-phenyl-1H-phenanthro[9,10-d]imidazolium-5,10-diamine and 2,4,6-tricarboxymethylpyrogallol. When prepared as an electrode for electrocatalytic hydrogen evolution from water, it achieves a hydrogen evolution efficiency of 0.5 mol·L⁻¹. ‑1 In an H2SO4 solution, at 10 mA·cm –2 With an overpotential as low as 167–197 mV, it can be used in the field of hydrogen production by water electrolysis.

Description

Technical Field

[0001] This invention relates to a covalent organic framework material, its preparation method, and its applications. Background Technology

[0002] The burning of fossil fuels and the emission of greenhouse gases have led to problems such as energy depletion and environmental pollution. 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 linked by strong covalent bonds, have many advantages such as diverse and designable structures, high porosity, and good stability, and have been favored by researchers in recent years. In 2021, Santu Ruida's research group reported a new covalent organic framework electrochemical hydrogen evolution material in Volume 14, Issue 22 of the journal *ChemSusChem*, which drove a 10 mA cm⁻¹ hydrogen evolution process in a 0.5 M H₂SO₄ electrolyte. -2 An overpotential of 200 mV is required for the current density. It maintains high catalytic activity after prolonged electrocatalysis, but compared to other electrochemical catalysts, it has a high overpotential and low hydrogen evolution efficiency. In 2021, a series of ruthenium nanoparticle-doped covalent organic framework / graphene (COF / rGO) composites were reported in Volume 60, Issue 30 of the journal *Industrial & Engineering Chemistry Research*. These covalent organic framework composites exhibited high electrochemical hydrogen evolution performance at 10 mA cm⁻¹. -2 It exhibits an overpotential of 42 mV at current density. However, the synthesis process of this material is complex, ruthenium nanoparticles are expensive, and their stability is poor.

[0003] Currently reported covalent organic framework materials for electrocatalytic hydrogen desorption from water mainly suffer from the following drawbacks:

[0004] 1. Most covalent organic framework materials have low efficiency in electrochemical hydrogen desorption from water;

[0005] 2. The preparation steps of covalent organic framework composite materials for hydrogen desorption in electrochemical water treatment are complex;

[0006] 3. Covalent organic framework composite materials used for hydrogen desorption in electrochemical water treatment often use precious metal doping, which is not conducive to environmental protection. Summary of the Invention

[0007] This invention aims to address the technical problems of complex preparation steps and low hydrogen evolution efficiency of existing noble metal-doped covalent organic framework composite materials. Instead, it provides a covalent organic framework material for electrocatalytic hydrogen evolution through water treatment, its preparation method, and its application. This invention achieves highly efficient electrocatalytic hydrogen evolution through water treatment, with a simple synthesis process, overcoming the drawbacks of complex preparation steps in noble metal-doped covalent organic framework composite materials.

[0008] The basic structural unit of the covalent organic framework material for electrocatalytic hydrogen desorption from water in this invention is as follows:

[0009]

[0010] The aforementioned covalent organic framework material for electrocatalytic hydrogen desorption from water was obtained by the condensation reaction of 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine and 2,4,6-tricarboxypyrogallol, and its synthetic formula is as follows:

[0011]

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

[0013] I. Using a molar ratio of 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine to 2,4,6-tricarboxypyrogallol of (1-5):1, add 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine and 2,4,6-tricarboxypyrogallol to a Pyrex tube containing organic solvent I, and mix thoroughly by ultrasonication; then add acid as a catalyst to the Pyrex tube, and mix thoroughly by ultrasonication to obtain the reaction mixture;

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

[0015] 3. Heat the Pyrex tube to 100-180℃ and react for 72-168 h. After the reaction is complete, cool to room temperature to obtain the crude product.

[0016] IV. The crude product was filtered, the filter cake was washed with organic solvent II, and then dried under vacuum to obtain a covalent organic framework material for electrocatalytic hydrogen desorption from water.

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

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

[0019] Furthermore, the acid mentioned in step one 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 one, the ratio of the amount of 2,4,6-tricarboxypyrogallol to the volume of acid is 1 mmol: (1-10) mL.

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

[0022] The aforementioned covalent organic framework material for electrocatalytic hydrogen desorption from water is used to prepare electrodes for electrocatalytic hydrogen desorption from water.

[0023] The method for preparing electrodes using the above-mentioned covalent organic framework materials for electrocatalytic hydrogen desorption from water is carried out according to the following steps:

[0024] 1. A 1cm×1cm piece of nickel foam is ultrasonically cleaned sequentially with acetone, water, inorganic acid and water to remove organic matter and oxide film, and then vacuum dried to obtain a clean nickel foam matrix.

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

[0026] 3. The slurry is evenly coated onto the clean nickel foam substrate obtained in step 1, and vacuum dried at a temperature of 50-80℃ for 6-8 hours to obtain a covalent organic framework material electrode for electrocatalytic hydrogen desorption from water.

[0027] Furthermore, the water in step one is distilled water, deionized water, pure water, or ultrapure water.

[0028] Furthermore, the inorganic acid in step one 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] This invention constructs a hydrogen evolution catalyst using a covalent organic framework material rich in nitrogen and oxygen atoms. The introduction of heteroatoms effectively modulates the electronic properties of the covalent organic framework material, improving its conductivity and electrocatalytic activity. Nitrogen and oxygen doping enhances the conductivity of the covalent organic framework material, while the hydroxyl groups on the trialdehyde readily bind to hydrogen protons, increasing the affinity for hydrogen proton adsorption and thus promoting the hydrogen evolution reaction. Compared with other existing covalent organic framework materials, the covalent organic framework material for electrocatalytic hydrogen evolution from water provided by this invention offers more active sites for hydrogen evolution, facilitating electron transfer, exhibiting strong conductivity, and high hydrogen evolution efficiency. Compared with commercial platinum-carbon catalysts, the covalent organic framework material for electrocatalytic hydrogen evolution from water in this invention does not contain precious metals, resulting in lower cost. (The last sentence appears to be incomplete and possibly refers to a specific chemical formula.) -1 In an H2SO4 solution at 10 mA cm – 2 With an overpotential as low as 167–197 mV, it exhibits excellent hydrogen evolution performance and can be used in the field of hydrogen production through water electrolysis. Attached Figure Description

[0030] Figure 1 This is the infrared spectrum of a covalent organic framework material prepared in Example 1 for electrocatalytic hydrogen desorption from water. The horizontal axis represents wavelength, and the vertical axis represents transmittance.

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

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

[0033] Figure 4 This is a Tafel curve of the covalent organic framework material electrode used for electrocatalytic hydrogen desorption from water in Example 1. Detailed Implementation

[0034] The beneficial effects of the present invention will be verified using the following examples.

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

[0036] 1. Add 21 mg of 2,4,6-tricarboxymethylpyrogallol and 32 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine to a Pyrex tube containing 1 mL of o-dichlorobenzene and 1 mL of mesitylene, and mix thoroughly by sonication; then add 0.2 mL of glacial acetic acid to the Pyrex tube and mix thoroughly by sonication to obtain the reaction mixture;

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

[0038] 3. Heat the Pyrex tube to 180°C and react for 72 hours. After the reaction is complete, cool to room temperature to obtain the crude product.

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

[0040] To determine the structure of the covalent organic framework material prepared in Example 1 for electrocatalytic hydrogen desorption from water, infrared spectroscopy was performed on the covalent organic framework material prepared in Example 1 for electrocatalytic hydrogen desorption from water. The obtained infrared spectrum is shown below. Figure 1 As shown, from Figure 1 It can be seen that covalent organic framework materials at 1580 cm⁻¹ -1 The presence of a characteristic peak at this point indicates the stretching vibration of the C=N bond, suggesting a condensation reaction between 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine and 2,4,6-tricarboxypyrogallol. This demonstrates the successful preparation of a covalent organic framework material for electrocatalytic hydrogen desorption from water.

[0041] The XRD pattern of the covalent organic framework material prepared in Example 1 for electrocatalytic hydrogen desorption from water is shown below. 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 observed at approximately 2.4°, 4.1°, and 23.0°, indicating that the material has high crystallinity, which also confirms that the substance is a covalent organic framework material.

[0042] An electrode was prepared using the covalent organic framework material for electrocatalytic hydrogen desorption from water prepared in Example 1. The specific method is as follows:

[0043] 1. Take a 1.0cm×1.0cm piece of nickel foam. First, ultrasonically clean the nickel foam with acetone for 15 minutes, then ultrasonically clean it twice with deionized water for 10 minutes each time. Next, ultrasonically clean it with 20% hydrochloric acid for 2 minutes, and finally ultrasonically clean it three times with deionized water for 10 minutes each time to remove organic matter and oxide film. Then, dry it in a vacuum drying oven at 60℃ for 6 hours to obtain a clean nickel foam matrix.

[0044] 2. The covalent organic framework material used for electrocatalytic hydrogen desorption from water is ground in an agate mortar for 0.5 hours to obtain covalent organic framework material powder; then 1 mg of covalent organic framework material powder, 1 mg of carbon black, 0.2 mL of 30% (w / w) binder naphthol and 1 mL of anhydrous ethanol are ultrasonically mixed evenly to obtain a slurry.

[0045] 3. The slurry is evenly coated onto the clean nickel foam substrate prepared in step 1, and then vacuum dried at 60°C for 6 hours to obtain a covalent organic framework material electrode for electrocatalytic hydrogen desorption from water.

[0046] The catalytic performance of a covalent organic framework material prepared in this embodiment for electrocatalytic hydrogen desorption from water was tested on an electrochemical workstation. At room temperature, the working electrode was a covalent organic framework material electrode (geometric area 1 cm²). 2 A graphite rod was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode (electrolyte concentration was 0.5 mol·L⁻¹). -1 (H2SO4 solution), linear voltammetry scan rate was 5 mV·s -1 The potential range was -0.80V to -1.4V (relative to the Ag / AgCl reference electrode), and the obtained linear voltammetric scan curve is shown below. Figure 3 As shown. From Figure 3 It can be seen that at 10mA·cm – 2 The overpotential is as low as 167mV, which indicates that the covalent organic framework material prepared in Example 1 has good hydrogen evolution performance.

[0047] Figure 4 This is a Tafel slope curve of the covalent organic framework material electrode for electrocatalytic hydrogen desorption from water prepared in Example 1. Figure 4 The slope of Tafel can be calculated to be 107.4 mV·dec. – 1 This further demonstrates that the covalent organic framework material used for electrocatalytic hydrogen evolution from water exhibits excellent hydrogen evolution performance. Table 1 compares the hydrogen evolution catalytic performance of the covalent organic framework material prepared in Example 1 with that of existing materials.

[0048] Table 1. Performance comparison of the covalent organic framework material prepared in Example 1 for electrocatalytic hydrogen evolution reaction with other existing hydrogen evolution catalysts.

[0049]

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

[0051] 1. Add 21 mg of 2,4,6-tricarboxypyrogallol and 32 mg of 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine to a Pyrex tube containing 1 mL of N,N-dimethylformamide and 1 mL of dioxane, and mix thoroughly by sonication; then add 0.4 mL of trifluoroacetic acid to the Pyrex tube and mix thoroughly by sonication to obtain the reaction mixture;

[0052] 2. Perform liquid nitrogen freezing, vacuuming, and thawing cycles on the Pyrex tube, repeating 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 complete, cool to room temperature to obtain the crude product.

[0054] IV. The crude product was filtered, and the filter cake was repeatedly washed with methanol and acetonitrile and dried under vacuum to obtain a covalent organic framework material for electrocatalytic hydrogen desorption from water.

[0055] The catalytic performance of the covalent organic framework material prepared in Example 2 for electrocatalytic hydrogen desorption from water was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA / cm², the catalytic performance was good. – 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 hydrogen desorption from water in this example is carried out according to the following steps:

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

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

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

[0060] 4. The crude product was filtered, and the filter cake was repeatedly washed with acetonitrile and tetrahydrofuran and dried under vacuum to obtain a covalent organic framework material for electrocatalytic hydrogen desorption from water.

[0061] The catalytic performance of the covalent organic framework material prepared in Example 3 for electrocatalytic hydrogen desorption from water was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA·cm⁻¹, the catalytic performance was good. – 2 The overpotential is as low as 195mV, 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 hydrogen desorption from water in this example is carried out according to the following steps:

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

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

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

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

[0067] The catalytic performance of the covalent organic framework material prepared in Example 4 for electrocatalytic hydrogen desorption from water was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA / cm², the catalytic performance was good. – 2 The overpotential is as low as 193mV, 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 hydrogen desorption from water in this example is carried out according to the following steps:

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

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

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

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

[0073] The catalytic performance of the covalent organic framework material prepared in Example 5 for electrocatalytic hydrogen desorption from water was tested on an electrochemical workstation using the same method as in Example 1. The results showed that at 10 mA·cm⁻¹, the catalytic performance was good. – 2 The overpotential is as low as 187mV, 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 hydrogen desorption from water in this example is carried out according to the following steps:

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

[0076] 2. Perform liquid nitrogen freezing, vacuuming, and thawing cycles on the Pyrex tube, repeating 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 complete, cool to room temperature to obtain the crude product.

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

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

Claims

1. A method for preparing a covalent organic framework material for electrocatalytic hydrogen desorption from water, characterized in that, This method is performed in the following steps: I. Using a molar ratio of 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine to 2,4,6-tricarboxypyrogallol of (1~5):1, add 2-phenyl-1H-phenanthro[9,10-d]imidazol-5,10-diamine and 2,4,6-tricarboxypyrogallol to a Pyrex tube containing organic solvent I, and mix thoroughly by ultrasonication; then add acid as a catalyst to the Pyrex tube, and mix thoroughly by ultrasonication to obtain the reaction mixture; 2. Perform liquid nitrogen freezing, vacuuming, and thawing cycles on the Pyrex tube, repeating the operation 4-5 times, and then seal it.

3. Heat the Pyrex tube to 100~180℃ and react for 72~168 h. After the reaction is completed, cool to room temperature to obtain the crude product. IV. The crude product was filtered, the filter cake was washed with organic solvent II, and then dried under vacuum to obtain a covalent organic framework material for electrocatalytic hydrogen desorption from water.

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

3. A method for preparing a covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 1 or 2, characterized in that, The acid mentioned in step one 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%.

4. A method for preparing a covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 1 or 2, characterized in that, In step one, the ratio of the amount of 2,4,6-tricarboxypyrogallol to the volume of acid is 1 mmol: (1~10) mL.

5. A method for preparing a covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 1 or 2, characterized in that, The organic solvent II mentioned in step four is one or any two of methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, trichloromethane and acetone.

6. The application of a covalent organic framework material prepared by the method of claim 1 for electrocatalytic hydrogen desorption from water, characterized in that, This application involves fabricating an electrode from a covalent organic framework material used for electrocatalytic hydrogen desorption from water.

7. The application of the covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 6, characterized in that, The method for preparing electrodes using covalent organic framework materials for electrocatalytic hydrogen desorption from water comprises the following steps:

1. A 1 cm × 1 cm piece of nickel foam is ultrasonically cleaned sequentially with acetone, water, inorganic acid and water to remove organic matter and oxide film, and then vacuum dried to obtain a clean nickel foam matrix.

2. The covalent organic framework material used for electrocatalytic hydrogen evolution is ground in an agate mortar to obtain covalent organic framework material powder; the covalent organic framework material powder, carbon black, binder naphthol and anhydrous ethanol are ultrasonically mixed evenly in a mass ratio of 1:1:0.2:1 to obtain a slurry; 3. The slurry is evenly coated onto the clean nickel foam substrate obtained in step 1, and vacuum dried at a temperature of 50~80 ℃ for 6~8 h to obtain a covalent organic framework material electrode for electrocatalytic hydrogen desorption from water.

8. The application of the covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 7, characterized in that, The water used in step one is distilled water, deionized water, pure water, or high-purity water.

9. The application of a covalent organic framework material for electrocatalytic hydrogen desorption from water according to claim 7 or 8, characterized in that, The inorganic acid in step one 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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