Hydrogen evolution catalytic self-supporting electrode and preparation method thereof

Abstract

The invention provides a hydrogen evolution catalysis self-supporting electrode and a preparation method thereof, and belongs to the technical field of electrochemical catalysis. The problems that an existing Pt-based electrocatalyst electrode is high in manufacturing cost, insufficient in durability, weak in corrosion resistance and the like are solved. The preparation method comprises the following steps: firstly, placing a carbon cloth subjected to ultrasonic cleaning and plasma treatment in a metal spraying instrument to deposit a Pt seed crystal layer, and then growing a Pt nanosheet on the carbon cloth through electro-deposition in a mixed solution of sulfuric acid, platinum salt and lauryl sodium sulfate; and cleaning the Pt nanosheet coated carbon cloth with deionized water, and carrying out vacuum drying to obtain the low-Pt-load hydrogen evolution catalytic self-supporting electrode applicable to all pH. The Pt nanosheet is directly grown on the carbon cloth to obtain the hydrogen evolution electro-catalysis electrode, so that the coating of a catalyst and the use of a binder in the conventional preparation process of the electrode are avoided; due to the high porosity of the carbon cloth substrate and the vertical distribution of the Pt nanosheets, the electrode has high specific surface area and excellent charge transfer capacity, and the intrinsic activity and density of catalytic active sites are improved.

Description

Technical Field

[0001] The invention provides a hydrogen evolution catalytic self-supporting electrode and a preparation method thereof, belonging to the technical field of electrochemical catalysis. Background Art

[0002] The hydrogen evolution reaction (HER) is a key reaction in the electrolysis of water to produce hydrogen. However, due to the sluggish kinetics of HER, highly active catalysts are required to reduce the reaction barrier and overpotential during the electrolysis of water. Traditional Pt-based HER catalysts have the characteristics of low overpotential and good chemical stability, but they require a large amount of scarce precious metal Pt, which has problems such as high cost, insufficient durability, and weak corrosion resistance, which hinder the large-scale application of electrolysis of water to produce hydrogen. By regulating the morphology and crystal orientation of the precious metal Pt to increase the active sites, improve the catalytic efficiency of Pt, and reduce the amount of Pt used, the integrated preparation of efficient HER catalysts and electrodes is the key to achieving the full popularization of electrolysis of water to produce hydrogen. Therefore, it is necessary to develop low-cost and high-efficiency Pt-based electrocatalyst electrodes to promote the commercial development of electrolysis of water to produce hydrogen.

[0003] The Pt nanosheets grown vertically on the carbon cloth form a three-dimensional stacking configuration, which can increase the density of the atoms at the edge of the nanosheets with high catalytic activity and increase the contact area with the reactants. The gaps between the nanosheets are conducive to rapid mass transfer. The carbon cloth has good conductivity, chemical stability and mechanical properties. The internal fibers form a large number of pores through stacking and interlacing, which greatly increases the specific surface area of ​​the electrode, which is conducive to the charge and mass transfer of the electrolyte and the release of bubbles. Therefore, it can be used as a substrate for excellent water electrolysis hydrogen evolution electrodes. Since electrochemical reactions usually occur on the catalyst surface, the combination of Pt nanosheets with a three-dimensional stacking configuration and a carbon cloth substrate can maximize the number and density of hydrogen evolution active sites on the electrode surface, and increase the mass transfer and charge transfer rate, which is an effective strategy to improve the electrocatalytic performance of hydrogen evolution electrodes. Summary of the invention

[0004] In order to solve the above technical problems, the present invention proposes a hydrogen evolution catalytic self-supporting electrode and a preparation method thereof, which can prepare a simple, efficient, stable, nanosheet self-supporting hydrogen evolution catalytic electrode with low Pt loading and suitable for full pH and high current density, and has broad application prospects in promoting hydrogen energy conversion and application.

[0005] The technical solution adopted by the present invention is: a method for preparing a hydrogen evolution catalytic self-supporting electrode, comprising the following steps: Step 1, carbon cloth pretreatment; Step 2, forming a dense Pt seed layer on the surface of the pretreated carbon cloth to provide a large number of sites for the vertical growth of Pt nanosheets; Step 3, using the carbon cloth after Pt deposition as a working electrode and placing it in a solution containing sulfuric acid, platinum salt and sodium dodecyl sulfate, and performing electrodeposition at room temperature, so that Pt crystals grow in a vertical direction under the dual effects of a specific voltage and a surfactant, and obtain three-dimensional stacked nanosheets with uniform distribution and stable structure; Step 4: After the electrodeposition is completed, the working electrode is repeatedly rinsed with deionized water and dried to obtain a low Pt loading hydrogen evolution catalytic self-supporting electrode applicable to all pH values.

[0006] The carbon cloth pretreatment in step 1 specifically includes: ultrasonically cleaning the carbon cloth with acetone, ethanol and deionized water respectively to remove impurities adsorbed on the surface, and then performing plasma activation treatment after drying to improve the hydrophilicity of the carbon cloth.

[0007] Preferably, the size of the carbon cloth is 0.5~5cm 2 The ultrasonic cleaning time is 10~120min, the drying method is vacuum drying, the drying temperature is 40~80℃, and the drying time is 6~24h.

[0008] Preferably, the gas used for plasma activation treatment is selected from at least one of argon and nitrogen, and the cleaning time is 5 to 15 minutes.

[0009] Preferably, in step 2, a gold spraying device is used to deposit Pt nanoparticles on the pretreated carbon cloth, the current of the gold spraying device is 10-30 mA, and the duration is 5-30 seconds.

[0010] Preferably, the platinum salt in step 3 is selected from at least one of chloroplatinic acid, platinum tetrachloride, dinitrosodiammine platinum, potassium chloroplatinate, ammonium chloroplatinate and acetylacetonate platinum.

[0011] Preferably, the concentration of sulfuric acid in step 3 is 0.1-0.5M, the concentration of platinum salt is 0.01-1mM, and the concentration of sodium dodecyl sulfate is 0.1-0.5M.

[0012] Preferably, the electrodeposition in step 3 is constant potential deposition, and the applied potential is -0.5~-0.2V SCE , the electrodeposition time is 10~60 min.

[0013] Preferably, the drying in step 4 is performed by vacuum drying at a temperature of 40 to 80° C. and a drying time of 6 to 24 hours.

[0014] A self-supporting electrode for hydrogen evolution catalysis is prepared by the above method. It is applicable to all pH values ​​and has a low Pt loading. The Pt loading of the electrode is 0.1-0.5wt.%, and the loading per unit area is 0.005-0.02mg / cm 2 ; In 1M KOH alkaline electrolyte, 10mA cm -2The overpotential is as low as 24 mV in 0.5 M H2SO4 acid electrolyte at 500 mA cm -2 The overpotential at 1 is as low as 113 mV.

[0015] The beneficial effects of the present invention compared with the prior art are as follows: (1) In the self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values ​​of the present invention, Pt nanosheets are vertically distributed on a carbon cloth substrate. Compared with the granular Pt loaded in the traditional Pt / C catalyst, the Pt nanosheets provide high-density edge active sites, increasing the number of active sites; (2) The unique structure of the carbon cloth substrate combined with the three-dimensional stacked Pt nanosheets gives the electrode a larger specific surface area, providing more channels for charge transfer and material transport, and exhibiting higher catalytic activity and efficiency in hydrogen evolution in water electrolysis; (3) The self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values ​​of the present invention can be directly used as a HER working electrode. Compared with the existing commercial Pt / C catalyst electrode, the steps of coating the catalyst to prepare the electrode are reduced, which is convenient for industrial application; (4) The Pt loading of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading is 0.1-0.5 wt.%, and the hydrogen evolution overpotential is comparable to that of 20 wt.% Pt / C, with a working current density of 500 mA cm-1. -2 ; (5) The low Pt loading hydrogen evolution catalytic self-supporting electrode applicable to all pH values ​​of the present invention can adapt to acidic, alkaline and neutral electrolytes, has good long-term stability in different electrolytes, and is a HER catalyst electrode applicable to all pH values. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present invention will be further described below in conjunction with the accompanying drawings: Figure 1 This is a Pt nanosheet stacking morphology image of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading suitable for all pH values ​​prepared in Example 1 of the present invention observed under a scanning electron microscope (SEM); Figure 2 The preparation method and application of the hydrogen evolution catalytic self-supporting electrode prepared in Example 1 of the present invention are the Pt mass ratio and the Pt loading per unit area obtained by weighing with a high-precision balance; Figure 3 The LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading suitable for all pH values ​​prepared in Example 1 of the present invention in 1M KOH electrolyte solution; Figure 4This is the LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading suitable for all pH values ​​prepared in Example 1 of the present invention in 1 M PBS buffer; Figure 5 The LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading suitable for all pH values ​​prepared in Example 1 of the present invention in 0.5M H2SO4 electrolyte solution; Figure 6 This is a morphology picture of the hydrogen evolution catalytic self-supporting electrode prepared in Example 5 of the present invention observed under SEM. DETAILED DESCRIPTION

[0017] like Figures 1 to 6 As shown, the present invention provides a method for preparing a hydrogen evolution catalytic self-supporting electrode, which specifically comprises the following steps: Step 1, pretreatment of carbon cloth: The carbon cloth is ultrasonically cleaned with acetone, ethanol and deionized water respectively to remove impurities adsorbed on the surface, and then plasma activated after drying to improve the hydrophilicity of the carbon cloth.

[0018] The size of the carbon cloth can be selected from 0.5 to 5 cm 2 The ultrasonic cleaning time is 10~120min, the drying method is vacuum drying, the drying temperature is 40~80℃, and the drying time is 6~24h.

[0019] The gas used for plasma activation treatment is selected from at least one of argon and nitrogen, and the cleaning time is 5 to 15 minutes.

[0020] Step 2: Place the pretreated carbon cloth in a gold spraying apparatus to deposit Pt nanoparticles, forming a dense Pt seed layer on the surface of the carbon cloth, providing a large number of sites for the vertical growth of Pt nanosheets.

[0021] The current of the gold spraying instrument is 10~30mA and the duration is 5~30s.

[0022] Step 3, using the carbon cloth after Pt deposition as a working electrode and placing it in a solution containing sulfuric acid, platinum salt and sodium dodecyl sulfate, and performing electrodeposition at room temperature, so that the Pt crystals grow in the vertical direction under the dual action of a specific voltage and a surfactant, and obtain uniformly distributed and structurally stable three-dimensional stacked nanosheets, which promote the activity, charge-mass transfer and efficiency of the hydrogen evolution reaction.

[0023] The platinum salt is selected from at least one of chloroplatinic acid, platinum tetrachloride, dinitrosodiammine platinum, potassium chloroplatinate, ammonium chloroplatinate and platinum acetylacetonate.

[0024] The concentration of sulfuric acid is 0.1~0.5M, the concentration of platinum salt is 0.01~1mM, and the concentration of sodium dodecyl sulfate is 0.1~0.5M.

[0025] Electrodeposition is constant potential deposition, the applied potential is -0.5~-0.2V SCE , the electrodeposition time is 10~60 min.

[0026] Step 4: After the electrodeposition is completed, the working electrode is repeatedly rinsed with deionized water and dried to obtain a low Pt loading hydrogen evolution catalytic self-supporting electrode applicable to all pH values.

[0027] The drying is carried out by vacuum drying, the temperature is 40~80℃, and the drying time is 6~24h.

[0028] The hydrogen evolution catalytic self-supporting electrode obtained based on the above preparation method is a hydrogen evolution catalytic self-supporting electrode with low Pt loading applicable to all pH values, and its Pt loading is 0.1-0.5wt.%, and the loading per unit area is 0.005-0.02mg / cm 2 ; In 1M KOH alkaline electrolyte, 10 mA cm -2 The overpotential at 500 mA cm-2 is as low as 24 mV in 0.5 M H2SO4 acidic electrolyte. -2 The overpotential at is as low as 113 mV.

[0029] The present invention will be further described below based on specific embodiments and drawings.

[0030] Example 1 Step 1, size 1×2cm 2 The carbon cloth was ultrasonically cleaned with acetone, ethanol and deionized water for 30 min respectively, dried at 60 °C in a vacuum drying oven for 12 h and then subjected to plasma activation treatment.

[0031] Step 2: Place the pretreated carbon in a gold spraying instrument to deposit Pt nanoparticles. The current of the gold spraying instrument is set to 20 mA and the duration is 15 seconds.

[0032] Step 3: prepare a mixed solution of 0.5 M sulfuric acid, 0.02 mM chloroplatinic acid and 0.5 M sodium dodecyl sulfate, and then transfer the solution to the electrolytic cell as the electrolyte, use the carbon cloth as the working electrode, and SCE The constant voltage electrodeposition was carried out at a potential of , and the deposition time was 30 min.

[0033] Step 4, after the electrodeposition is completed, the working electrode is taken out, repeatedly rinsed with deionized water, and then placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain a self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values.

[0034] Figure 1This is a morphology image of the self-supporting electrode for hydrogen evolution catalysis with a low Pt loading applicable to all pH values ​​prepared in Example 1 observed under SEM. It can be seen from the image that the surface of the self-supporting electrode for hydrogen evolution catalysis with a low Pt loading applicable to all pH values ​​has an ultra-thin three-dimensional stacked layer structure. The vertical distribution of Pt nanosheets enables the electrode to have not only a large number of high-efficiency electrocatalytic active sites, but also a large specific surface area and excellent charge-mass transfer capacity, thereby making the prepared self-supporting electrode for hydrogen evolution catalysis with a low Pt loading applicable to all pH values ​​have excellent electrocatalytic hydrogen evolution performance.

[0035] Figure 2 The Pt mass ratio and unit area loading of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading suitable for all pH prepared in Example 1 were obtained by weighing with a high-precision balance, showing that its Pt mass ratio was 0.32wt.%, and the unit area loading was 0.011mg / cm 2 .

[0036] Figure 3 The LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​prepared in Example 1 in 1M KOH electrolyte solution is shown in the figure. As can be seen from the figure, the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​is 10 mA cm -2 The overpotential at 500 mA cm -2 The overpotential is 327 mV.

[0037] Figure 4 The LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​prepared in Example 1 in 1M PBS buffer solution is shown in the figure. As can be seen from the figure, the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​is 10 mA cm -2 The overpotential at 500 mA cm -2 The overpotential is 589 mV.

[0038] Figure 5 The LSV curve of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​prepared in Example 1 in 0.5M H2SO4 electrolyte solution is shown in the figure. As can be seen from the figure, the self-supporting electrode for hydrogen evolution catalysis with low Pt loading in all pH values ​​has a good stability at 10 mA cm -2 The overpotential at 500 mA cm -2 The overpotential is 113mV.

[0039] The LSV curves of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values ​​tested in different electrolyte solutions show that the self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values ​​prepared by the present invention has excellent electrocatalytic hydrogen evolution performance in all pH values ​​and can be suitable for HER applications with high current density.

[0040] Example 2 Step 1, size 1×2cm 2 The carbon cloth was ultrasonically treated with acetone, ethanol and deionized water for 30 min respectively, dried at 60 °C in a vacuum drying oven for 12 h, and then plasma activated.

[0041] Step 2: Place the pretreated carbon in a gold spraying instrument to deposit Pt nanoparticles. The current of the gold spraying instrument is set to 20 mA and the duration is 15 seconds.

[0042] Step 3: prepare a mixed solution of 0.5 M sulfuric acid, 0.02 mM chloroplatinic acid and 0.5 M sodium dodecyl sulfate, and then transfer the solution to the electrolytic cell as the electrolyte, use the carbon cloth as the working electrode, and SCE The constant voltage electrodeposition was carried out at a potential of , and the deposition time was 30 min.

[0043] Step 4, after the electrodeposition is completed, the carbon cloth used as the working electrode is taken out, repeatedly rinsed with deionized water, and then placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain a self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values.

[0044] Example 3 Step 1, size 1×2cm 2 The carbon cloth was ultrasonically treated with acetone, ethanol and deionized water for 30 min respectively, dried at 60 °C in a vacuum drying oven for 12 h, and then plasma activated.

[0045] Step 2: Place the pretreated carbon in a gold spraying instrument to deposit Pt nanoparticles. The current of the gold spraying instrument is set to 20 mA and the duration is 15 seconds.

[0046] Step 3: prepare a mixed solution of 0.5 M sulfuric acid, 0.02 mM chloroplatinic acid and 0.5 M sodium dodecyl sulfate, and then transfer the solution to the electrolytic cell as the electrolyte, use the carbon cloth as the working electrode, and SCE The constant voltage electrodeposition was carried out at a potential of , and the deposition time was 30 min.

[0047] Step 4, after the electrodeposition is completed, the carbon cloth used as the working electrode is taken out, repeatedly rinsed with deionized water, and then placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain a self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values.

[0048] Example 4 Step 1, size 1×2cm 2 The carbon cloth was ultrasonically treated with acetone, ethanol and deionized water for 30 min respectively, dried at 60 °C in a vacuum drying oven for 12 h, and then plasma activated.

[0049] Step 2: Place the pretreated carbon in a gold spraying instrument to deposit Pt nanoparticles. The current of the gold spraying instrument is set to 20 mA and the duration is 15 seconds.

[0050] Step 3: prepare a mixed solution of 0.5 M sulfuric acid, 0.02 mM chloroplatinic acid and 0.5 M sodium dodecyl sulfate, and then transfer the solution to the electrolytic cell as the electrolyte, use the carbon cloth as the working electrode, and SCE The constant voltage electrodeposition was carried out at a potential of , and the deposition time was 60 min.

[0051] Step 4, after the electrodeposition is completed, the carbon cloth used as the working electrode is taken out, repeatedly rinsed with deionized water, and then placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain a self-supporting electrode for hydrogen evolution catalysis with low Pt loading applicable to all pH values.

[0052] Example 5 Step 1, size 1×2cm 2 The carbon cloth was ultrasonically treated with acetone, ethanol and deionized water for 30 min respectively and then dried. Then, the carbon cloth was cleaned by Ar plasma.

[0053] Step 2: prepare a mixed solution of 0.5 M sulfuric acid, 0.02 mM chloroplatinic acid and 0.5 M sodium dodecyl sulfate, and then transfer the solution to the electrolytic cell as the electrolyte, use the carbon cloth as the working electrode, and SCE The constant voltage electrodeposition was carried out at a potential of , and the deposition time was 30 min.

[0054] Step 3: After the electrodeposition is completed, the carbon cloth used as the working electrode is taken out, repeatedly rinsed with deionized water, and then vacuum dried at 60° C. for 12 h.

[0055] Figure 6 This is a morphology of the hydrogen evolution catalytic self-supporting electrode prepared in Example 5 observed under SEM. It can be seen from the figure that in the absence of a Pt seed layer as a nucleation site, there are insufficient nucleation sites for Pt to attach to during growth, resulting in uneven distribution of the deposited Pt nanosheets.

[0056] The present invention obtains a hydrogen evolution electrocatalytic electrode by directly growing Pt nanosheets on carbon cloth, avoiding the coating of catalysts and the use of binders in the conventional preparation process of electrodes; the high porosity of the carbon cloth substrate and the vertical distribution of Pt nanosheets give the electrode a high specific surface area and excellent charge-mass transfer capacity, thereby improving the intrinsic activity and density of catalytic active sites. The Pt loading of the self-supporting electrode for hydrogen evolution catalysis with low Pt loading is <0.5wt.%, which is much lower than the 20wt.% of the commercial Pt / C catalyst, and can achieve stable hydrogen evolution under full pH conditions, with a hydrogen evolution overpotential of 10m Acm -2 The current density is comparable to that of Pt / C at 500 mA cm -2 The electrode preparation method of the present invention is simple, has high hydrogen evolution electrocatalytic activity, good stability, is easy to use, has low Pt content, reduces the cost of the catalyst, and can meet the requirements of high current density hydrogen evolution reaction in industrial electrocatalytic scenarios.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a hydrogen evolution catalytic self-supporting electrode, characterized in that: The following steps are involved: Step 1, carbon cloth pretreatment; Step 2, forming a dense Pt seed layer on the surface of the pretreated carbon cloth to provide a large number of sites for the vertical growth of Pt nanosheets; Step 3, using the carbon cloth after Pt deposition as a working electrode and placing it in a solution containing sulfuric acid, platinum salt and sodium dodecyl sulfate, and performing electrodeposition at room temperature, so that Pt crystals grow in a vertical direction under the dual effects of a specific voltage and a surfactant, and obtain three-dimensional stacked nanosheets with uniform distribution and stable structure; Step 4: After the electrodeposition is completed, the working electrode is repeatedly rinsed with deionized water and dried to obtain a low Pt loading hydrogen evolution catalytic self-supporting electrode applicable to all pH values.

2. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 1, characterized in that: The carbon cloth pretreatment in step 1 specifically includes: ultrasonically cleaning the carbon cloth with acetone, ethanol and deionized water respectively to remove impurities adsorbed on the surface, and then performing plasma activation treatment after drying to improve the hydrophilicity of the carbon cloth.

3. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 2, characterized in that: The size of the carbon cloth is 0.5~5cm 2 The ultrasonic cleaning time is 10~120min, the drying method is vacuum drying, the drying temperature is 40~80℃, and the drying time is 6~24h.

4. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 2, characterized in that: The gas used for plasma activation treatment is selected from at least one of argon and nitrogen, and the cleaning time is 5 to 15 minutes.

5. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 1, characterized in that: In step 2, a gold spraying device is used to deposit Pt nanoparticles on the pretreated carbon cloth. The current of the gold spraying device is 10-30 mA and the duration is 5-30 seconds.

6. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 1, characterized in that: The platinum salt in step 3 is selected from at least one of chloroplatinic acid, platinum tetrachloride, dinitrosodiammine platinum, potassium chloroplatinate, ammonium chloroplatinate and acetylacetonate platinum.

7. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 6, characterized in that: The concentration of sulfuric acid in step 3 is 0.1~0.5M, the concentration of platinum salt is 0.01~1mM, and the concentration of sodium dodecyl sulfate is 0.1~0.5M.

8. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 1, characterized in that: The electrodeposition in step 3 is constant potential deposition, and the applied potential is -0.5~-0.2V SCE , the electrodeposition time is 10~60 min.

9. The method for preparing a hydrogen evolution catalytic self-supporting electrode according to claim 1, characterized in that: The drying in step 4 is performed by vacuum drying at a temperature of 40 to 80° C. and a drying time of 6 to 24 hours.

10. A self-supporting electrode for hydrogen evolution catalysis, characterized in that: The method is prepared by any one of claims 1 to 9.

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