Non-noble metal cathode hydrogen evolution catalyst for PEM water electrolysis and use thereof

Abstract

The present application relates to the technical field of catalysts and relates to a non-noble metal cathode hydrogen evolution catalyst for PEM water electrolysis and a use thereof. The present application provides a method for preparing a cathode hydrogen evolution catalyst. A nickel-molybdenum heteropoly acid having a specific structure is generated in situ on the surface of a porous carbon material carrier, and is used as a hydrogen evolution catalyst active component precursor, and an in-situ generated nickel-containing molybdenum sulfide active component is subjected to sulfidation treatment to prepare a non-noble-metal-supported cathode hydrogen evolution catalyst, wherein the in-situ generated nickel-containing molybdenum sulfide active component has a hydrogen adsorption free energy similar to that of Pt and catalytic hydrogen evolution activity, the dispersity is good, and the number of active sites is large, thereby reducing the costs of the catalyst; in addition, during the sulfidation treatment of the nickel-molybdenum heteropoly acid, nitrogen or phosphorus atoms in the carrier can be doped into the lattice of molybdenum disulfide, thereby reducing the hydrogen evolution Gibbs free energy of sulfur atoms on an MoS2 crystal basal surface, and more active sites are formed on a sulfur edge and a molybdenum edge, facilitating a hydrogen evolution reaction.

Description

A non-precious metal cathode hydrogen evolution catalyst for PEM water electrolysis and its application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to a Chinese patent application filed with the Patent Office of China on February 29, 2024, with application number 202410225157.8 and invention name “A non-precious metal cathode hydrogen evolution catalyst for PEM water electrolysis and its application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present application relates to a non-precious metal cathode hydrogen evolution catalyst for PEM water electrolysis and its application, belonging to the technical field of electrochemical catalyst preparation. Background Art

[0004] Hydrogen has a relatively high energy density, and the products after hydrogen combustion are pollution-free to the environment. Therefore, hydrogen is considered to be the most promising clean energy carrier. Green hydrogen refers to electricity generated by renewable energy and then hydrogen obtained by electrolysis of water. Hydrogen production by water electrolysis refers to the decomposition of water molecules into hydrogen and oxygen through an electrochemical process under the action of direct current, which are precipitated at the cathode and anode respectively. There are currently three main technical routes for hydrogen production by water electrolysis, namely alkaline (AWE) water electrolysis hydrogen production, proton exchange membrane (PEM) water electrolysis hydrogen production, and solid oxide (SOEC) water electrolysis hydrogen production. Among them, the proton membrane water electrolysis hydrogen production system is more efficient than the alkaline water electrolysis hydrogen production system, produces purer hydrogen, and is more mature than the solid oxide water electrolysis hydrogen production system technology. It is the current focus of research and development in the field of water electrolysis hydrogen production technology.

[0005] The membrane electrode assembly (MEA) is the core component of a proton exchange membrane (PEM) water electrolysis system. It consists of a proton exchange membrane (PEM), two cation and cathodic catalyst layers on either side of the membrane that are in close contact with the membrane, and a gas diffusion layer (GDL) located outside the catalyst layers. The cation and cathodic catalyst layers are loaded with cathode and anode catalysts, respectively. When the PEM system is operating, water generates and releases oxygen under the catalysis of the anode catalyst, and generates and releases hydrogen under the catalysis of the cathode catalyst. Currently, the most widely used active material for the cathode hydrogen evolution catalyst in PEM water electrolysis systems is platinum nanoparticle catalyst. However, precious metal platinum is expensive and resources are limited. Therefore, the development of non-precious metal cathode hydrogen evolution catalysts is particularly important.

[0006] Summary of the Invention

[0007] To solve the above problems, the present application provides a method for preparing a cathode hydrogen evolution catalyst, the method comprising the following steps:

[0008] Preparation of a carbon material precursor solution: mixing a carbon-based material, a doping compound, and a solvent A, and reacting the mixture to obtain a carbon material precursor solution;

[0009] Preparation of doped porous carbon material: mixing a carbon material precursor solution, a soft template agent and a hard template agent and then performing a carbonization reaction to obtain a carbonized product; acid washing the carbonized product to obtain a doped porous carbon material;

[0010] Preparation of nickel-molybdenum heteropoly acid@doped porous carbon material: nickel salt, molybdenum salt, solvent B, ammonium persulfate, and doped porous carbon material are mixed and reacted to obtain a mixed system containing doped porous carbon material and nickel-molybdenum heteropoly acid cluster precursor; the mixed system is sequentially aged, dried, and calcined to obtain nickel-molybdenum heteropoly acid@doped porous carbon material;

[0011] Preparation of cathode hydrogen evolution catalyst: nickel molybdenum heteropoly acid@ doped porous carbon material is subjected to sulfurization reaction to obtain cathode hydrogen evolution catalyst;

[0012] Alternatively, the method comprises the steps of:

[0013] Preparation of carbon material precursor solution: mixing carbon-based material and solvent A and reacting them to obtain carbon material precursor solution;

[0014] Preparation of porous carbon material: mixing a carbon material precursor solution, a soft template agent and a hard template agent and then performing a carbonization reaction to obtain a carbonized product; acid washing the carbonized product to obtain a porous carbon material;

[0015] Preparation of nickel-molybdenum heteropoly acid@porous carbon material: nickel salt, molybdenum salt, solvent B, ammonium persulfate, and porous carbon material are mixed and reacted to obtain a mixed system containing porous carbon material and nickel-molybdenum heteropoly acid cluster precursor; the mixed system is sequentially aged, dried, and calcined to obtain nickel-molybdenum heteropoly acid@porous carbon material;

[0016] Preparation of cathode hydrogen evolution catalyst: nickel molybdenum heteropoly acid@carbon material is subjected to sulfurization reaction to obtain cathode hydrogen evolution catalyst.

[0017] In one embodiment of the present application, the preparation of the carbon material precursor solution comprises: mixing the carbon-based material, the doping compound and the solvent A, and ultrasonically stirring the mixture at 300-600 r / min and 10-30°C for 0.5-6h to obtain a mixture stock solution A; and heating the mixture stock solution A at 5-20°C·min -1 After heating to 60-180° C. at a rate of 100° C., reacting at 60-180° C. for 6-36 hours to obtain a carbon material precursor solution;

[0018] Alternatively, the preparation of the carbon material precursor solution comprises: mixing the carbon-based material and solvent A, stirring the mixture with ultrasound at 300-600 r / min and 10-30°C for 0.5-6h to obtain a mixture stock solution A; -1 The temperature is raised to 60-180° C. at a rate of 1000 ℃, and the mixture is reacted at 60-180° C. for 6-36 hours to obtain a carbon material precursor solution.

[0019] In one embodiment of the present application, the preparation of the doped porous carbon material or porous carbon material comprises: ultrasonically treating the carbon material precursor solution at 20-50°C for 10-120min, adding a soft template while stirring at 300-600r / min to obtain a mixture stock solution B; stirring the mixture stock solution B at 200-800r / min and 20-50°C for 10-60min to obtain a mixture stock solution C; ultrasonically treating the mixture stock solution C at 20-50°C for 10-120min, adding a hard template while stirring at 300-600r / min to obtain a mixture stock solution D; The raw material solution D is ultrasonically treated at 20-50° C. for 10-120 min, and then dried at 60-100° C. for 6-24 h to obtain a dry product; under the protection of protective gas, the dry product is carbonized at a high temperature of 600-1300° C. for 10-60 min, and then cooled to 10-30° C. to obtain a carbonized product; the carbonized product is mixed with an acidic solution, first stirred at 200-800 r / min and 30-60° C. for 20-120 min, and then filtered and the filtrate is discarded to obtain a reaction product A; the reaction product A is washed and dried at 60-100° C. for 2-12 h to obtain a doped porous carbon material or a porous carbon material.

[0020] In one embodiment of the present application, the washing is performed using an acidic solution.

[0021] In one embodiment of the present application, the preparation of the nickel molybdenum heteropoly acid @ doped porous carbon material or the nickel molybdenum heteropoly acid @ porous carbon material comprises: mixing the nickel salt, the molybdenum salt and the solvent B, stirring at 200 to 1200 r / min and 60 to 90 ° C for 30 to 150 min, and adding ammonium persulfate while stirring to obtain a mixture solution E; after adding the doped porous carbon material or the porous carbon material to the mixture solution E, stirring at 200 to 1200 r / min and 60 to 90 ° C for 60 to 240 min, adjusting the pH value to 4 to 5 with an acidic solution, and finally stirring at 200 to 1200 r / min. , stirring at 60-90°C for 20-120 min to obtain a mixed system containing a doped porous carbon material and a nickel-molybdenum heteropoly acid cluster precursor or a mixed system containing a porous carbon material and a nickel-molybdenum heteropoly acid cluster precursor; heating the mixed system at 80-120°C for 0.5-12 h for aging, and then cooling it to 10-30°C to obtain an aging product; filtering the aging product and discarding the filtrate to obtain a reaction product B; drying the reaction product B at 60-80°C for 2-24 h, and then calcining it at 250-400°C for 2-12 h under the protection of a protective gas to obtain nickel-molybdenum heteropoly acid @ doped porous carbon material or nickel-molybdenum heteropoly acid @ porous carbon material.

[0022] In one embodiment of the present application, the preparation of the cathode hydrogen evolution catalyst comprises: purging nickel molybdenum heteropoly acid @ doped porous carbon material or nickel molybdenum heteropoly acid @ porous carbon material with protective gas for 20 to 60 minutes, first heating to 300 to 600° C. at a rate of 2 to 20° C. / min in a sulfiding gas, and then reacting at 300 to 600° C. in a sulfiding gas for 1 to 8 hours to perform sulfidation to obtain a cathode hydrogen evolution catalyst.

[0023] In one embodiment of the present application, the mass ratio of the carbon-based material, the doping compound and the solvent A is 1:0-0.3:0.2-10.

[0024] In one embodiment of the present application, the mass ratio of the carbon material precursor solution, the hard template agent and the soft template agent is 1-2:1-10:0.01-2.

[0025] In one embodiment of the present application, the mass ratio of the acidic solution to the carbonized product is 100:1-20.

[0026] In one embodiment of the present application, the molar ratio of nickel atoms in the nickel salt, molybdenum atoms in the molybdenum salt, solvent B and ammonium persulfate is 1:3-10:10-100:0.5-2.

[0027] In one embodiment of the present application, the mass ratio of the mixture stock solution E to the doped porous carbon material is 1:0.5-10; or, the mass ratio of the mixture stock solution E to the porous carbon material is 1:0.5-10.

[0028] In one embodiment of the present application, the carbon-based material includes one or more of tar pitch, petroleum pitch, sucrose, glycerol, glucose and phenolic resin.

[0029] In one embodiment of the present application, the doping compound includes one or more of a nitrogen source and a phosphorus source.

[0030] In one embodiment of the present application, the nitrogen source includes one or more of dihydrogen amine, polypyrrole, ammonium chloride, urea, hexamethylenetetramine and dimethylformamide; the phosphorus source includes one or more of ammonium phosphate trihydrate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

[0031] In one embodiment of the present application, the nitrogen doping mass fraction is 0-20%; the phosphorus doping mass fraction is 0-10%.

[0032] In one embodiment of the present application, the solvent A includes one or more of deionized water, ethanol, methanol, ether, glycerol, benzene and toluene.

[0033] In one embodiment of the present application, the hard template comprises alkaline oxide nanorods or wire-shaped particles; the alkaline oxide nanorods or wire-shaped particles comprise one or more of basic magnesium sulfate whiskers, zinc oxide nanowires, zinc oxide nanotubes, copper oxide nanowires and iron oxide nanowires.

[0034] In one embodiment of the present application, the hard template has a diameter of 10 to 5000 nm and a length of 100 to 50000 nm.

[0035] In one embodiment of the present application, the soft template includes one or more of ammonium carbonate, ammonium bicarbonate and oxalic acid.

[0036] In one embodiment of the present application, the protective gas includes one or more of argon and nitrogen.

[0037] In one embodiment of the present application, the acidic solution includes one or more of dilute sulfuric acid, dilute nitric acid and hydrochloric acid.

[0038] In one embodiment of the present application, the acidic solution includes one or more of dilute sulfuric acid with a mass fraction of 1 to 30%, dilute nitric acid with a mass fraction of 1 to 30%, and hydrochloric acid with a mass fraction of 1 to 50%.

[0039] In one embodiment of the present application, the nickel salt includes one or more of nickel nitrate, nickel sulfate hexahydrate and nickel carbonate.

[0040] In one embodiment of the present application, the molybdenum salt includes 12-phosphomolybdic acid (H3PO4·12MoO3), (NH4)6Mo7O 24 and molybdenum trioxide.

[0041] In one embodiment of the present application, the solvent B includes one or more of deionized water, ethanol and methanol.

[0042] In one embodiment of the present application, the doped porous carbon material or the porous carbon material is in powder form.

[0043] In one embodiment of the present application, the sulfiding gas includes a mixed gas of H2S and H2.

[0044] In one embodiment of the present application, the volume ratio of H2S to H2 is 1:2-10.

[0045] The present application also provides a cathode hydrogen evolution catalyst, which is prepared using the above method.

[0046] The present application also provides a PEM water electrolysis device, which includes a PEM electrolyzer; the PEM electrolyzer includes the above-mentioned cathode hydrogen evolution catalyst.

[0047] The present application also provides a method for producing hydrogen by electrolysis of water, which comprises: passing deionized water into the above-mentioned PEM water electrolysis device for electrolysis to obtain hydrogen.

[0048] The present application also provides the above-mentioned method for preparing cathode hydrogen evolution catalyst or the above-mentioned cathode hydrogen evolution catalyst or the above-mentioned PEM water electrolysis device or the above-mentioned method for preparing PEM water electrolysis hydrogen production in water electrolysis hydrogen production.

[0049] The technical solution of this application has the following advantages:

[0050] The present application provides a method for preparing a cathode hydrogen evolution catalyst, the method comprising: mixing a carbon-based material, a doping compound and a solvent A and reacting the mixture to obtain a carbon material precursor solution; mixing the carbon material precursor solution, a soft template and a hard template and carbonizing the mixture to obtain a carbonized product; acid-washing the carbonized product to obtain a doped porous carbon material; mixing a nickel salt, a molybdenum salt, a solvent B, ammonium persulfate and a doped porous carbon material and reacting the mixture to obtain a mixed system containing a doped porous carbon material and a nickel-molybdenum heteropoly acid cluster precursor; aging, drying and calcining the mixed system in sequence to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material; and treating the nickel-molybdenum heteropoly acid@doped porous carbon material with the nickel-molybdenum heteropoly acid. The carbon material undergoes a sulfurization reaction to obtain a cathode hydrogen evolution catalyst; or, the method includes: mixing a carbon-based material and a solvent A and reacting them to obtain a carbon material precursor solution; mixing the carbon material precursor solution, a soft template and a hard template and then carbonizing them to obtain a carbonized product; acid-washing the carbonized product to obtain a porous carbon material; mixing a nickel salt, a molybdenum salt, a solvent B, ammonium persulfate and a porous carbon material and reacting them to obtain a mixed system containing a nickel-molybdenum heteropoly acid cluster precursor; aging, drying and calcining the mixed system in sequence to obtain a nickel-molybdenum heteropoly acid @ porous carbon material; and sulfurizing the nickel-molybdenum heteropoly acid @ porous carbon material to obtain a cathode hydrogen evolution catalyst. The method of the present application has the following advantages:

[0051] First, the most commonly used carbon carrier is nanocarbon black, which has a particle diameter of about 30nm and a specific surface area of ​​about 250m 2 / g, the electrical conductivity is 2.77~4S / cm. By increasing the specific surface area and electrical conductivity of the carbon carrier, the active component distribution can be made more uniform, thereby exposing more electrochemical catalytic active sites, and achieving the purpose of improving the electrochemical active area and mass activity of the cathode hydrogen evolution catalyst. Based on this principle, the present application adopts a method combining hard templates and soft templates, using petroleum asphalt or sucrose as carbon-based materials, alkaline oxide nanorod particles as hard templates, ammonium carbonate, ammonium bicarbonate or oxalic acid as soft templates, and doping heteroatoms (nitrogen and phosphorus) to synthesize a porous carbon material carrier with high specific surface area, through-pore structure and high electrical conductivity, which is conducive to exposing more catalytic active sites, significantly improving the transport of reactants and products in the cathode hydrogen evolution process, and enhancing mass transfer. Among them, the hard template alkaline oxide nanorod or wire particles can be prepared using dilute sulfuric acid or dilute sulfuric acid. It can be dissolved and removed by dilute acids such as nitric acid and is easy to remove completely. Compared with other silicon-based templates (such as SBA-15, MCM-48, or KIT-6), there is no need to use highly corrosive HF acid etching to remove the silicon-based template. The soft templates ammonium carbonate, ammonium bicarbonate, or oxalic acid will decompose to produce NH3 or CO2 gas during the carbonization process, which can further expand the pores and increase the specific surface area of ​​the carrier. The negatively charged heteroatoms such as nitrogen and phosphorus doped in the porous carbon material carrier can act as receptors for hydrogen protons, weakening the chemical bond strength between the active components and the hydrogen protons and promoting the hydrogen decomposition reaction.

[0052] Second, the hydrogen adsorption free energy at the edge of molybdenum disulfide is similar to that of Pt (the Gibbs free energy of hydrogen adsorption is only 0.08 eV), and its catalytic hydrogen evolution activity is linearly related to its active number. At the same time, adding the auxiliary metal nickel to molybdenum disulfide can affect the active phase particle size and the number of stacking layers of MoS2 microcrystals, thereby improving the catalytic activity of molybdenum disulfide. Based on this principle, the present application in situ generates a nickel-molybdenum heteropoly acid with a specific structure on the surface of a porous carbon material carrier, and uses it as a precursor of the active component of a hydrogen evolution catalyst. A nickel-containing molybdenum sulfide active component is generated in situ through sulfurization treatment to prepare a non-precious metal-supported cathode hydrogen evolution catalyst. The in situ generated nickel-containing molybdenum sulfide active component has a hydrogen adsorption free energy and catalytic hydrogen evolution activity similar to that of Pt, and has good dispersibility and a large number of active sites, which effectively reduces the cost of the catalyst. At the same time, during the sulfurization treatment of the nickel-molybdenum heteropoly acid, the nitrogen or phosphorus atoms in the carrier will be doped into the lattice of molybdenum disulfide, which can significantly reduce the hydrogen evolution Gibbs free energy of the sulfur atoms on the basal plane of the MoS2 crystal, form more active sites on the sulfur edge and the molybdenum edge, and contribute to the occurrence of the hydrogen evolution reaction.

[0053] Third, the nickel-containing molybdenum sulfide active component prepared by the present application using a nickel-molybdenum heteropolyacid with a specific structure as a precursor has a better catalytic hydrogen evolution activity than the NiMo active component prepared by the conventional impregnation method. This is because the average stacking number of MoS2 in the nickel-containing molybdenum sulfide active component prepared by the present application is smaller than the average stacking number of MoS2 in the NiMo active component prepared by the conventional impregnation method. The smaller the average stacking number of MoS2, the more conducive it is to exposing more catalytic active sites.

[0054] Fourth, the present application adopts nickel-molybdenum heteropoly acid with a specific structure as the precursor of the active component. Since nickel-molybdenum heteropoly acid has a specific spatial configuration, the auxiliary atom Ni is wrapped in the main agent atom Mo, and the distance between the nickel atom and the molybdenum atom is relatively short, which makes the auxiliary effect of the nickel atom obvious, and it is easy to form an active phase by sulfurization. In the active phase, the auxiliary atom Ni is located at the edge of the MoS2 sheet, which reduces the average stacking number of MoS2 microcrystals and increases the hydrogen evolution activity of the catalyst. At the same time, the synergistic effect between the auxiliary atom Ni and MoS2 can also make the catalyst have a low initial overpotential and Tafel slope, high limiting exchange current density and stability. DETAILED DESCRIPTION

[0055] The following examples are provided to further better understand the present application, but are not limited to the best implementation mode described herein, and do not limit the content and protection scope of the present application. Any product identical or similar to the present application obtained by anyone under the inspiration of the present application or by combining the features of the present application with other prior arts shall fall within the scope of protection of the present application.

[0056] If no specific experimental steps or conditions are specified in the following examples, the experiments were carried out according to the conventional experimental steps or conditions described in the literature in the field. If no manufacturer is specified for the reagents or instruments used, they are all commercially available conventional reagents.

[0057] The basic magnesium sulfate whiskers, zinc oxide nanowires and carbon nanofibers (carbon nanofibers with an outer diameter of 200 to 600 nm and a length of 5 to 50 μm) involved in the following examples were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., copper oxide nanowires were purchased from Suzhou Beike Nanotechnology Co., Ltd., and Wells Dawson type phosphomolybdic heteropoly acid H6P2Mo 18 O 62 Sucrose, ammonium carbonate ((NH4)2CO3) and ammonium bicarbonate (NH4HCO3) were purchased from Sinopharm Chemical Reagent Co., Ltd., petroleum asphalt was purchased from China Petrochemical Corporation, Nafion 115 membrane was purchased from DuPont, and iridium black was purchased from Johnson Matthey.

[0058] Example 1: Cathode hydrogen evolution catalyst and its preparation

[0059] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0060] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0061] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium sulfate heptahydrate, magnesium hydroxide and distilled water was 3:1:150.

[0062] 2. Preparation of mesoporous carbon support

[0063] 2.1 Preparation of carbon material precursor solution

[0064] Petroleum asphalt, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1:0.1:4 and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0065] 2.2 Preparation of doped porous carbon materials

[0066] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture stock solution B; the mixture stock solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture stock solution C; the mixture stock solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture stock solution D; the mixture stock solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 800°C. After carbonizing at medium and high temperature for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute nitric acid at a mass ratio of 100:15, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with 3% dilute nitric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of the carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 8:3:0.1.

[0067] 3. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0068] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing doped porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 10 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material.

[0069] 4. Preparation of cathode hydrogen evolution catalyst

[0070] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 30 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 5 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0071] Example 2: Cathode hydrogen evolution catalyst and its preparation

[0072] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0073] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0074] Magnesium oxide, magnesium hydroxide and distilled water were placed in a high-pressure reactor lined with polytetrafluoroethylene and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1:1, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template. The molar ratio of magnesium oxide, magnesium hydroxide and distilled water was 3:1:145.

[0075] 2. Preparation of mesoporous carbon support

[0076] 2.1 Preparation of carbon material precursor solution

[0077] Sucrose, polypyrrole and deionized water were mixed in a mass ratio of 1:0.05:4.5, and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 15°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0078] 2.2 Preparation of doped porous carbon materials

[0079] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture solution B; the mixture solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 750°C. After carbonizing at medium and high temperature for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute sulfuric acid at a mass ratio of 85:20, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain reaction product A; the reaction product A is repeatedly washed three times with 3% dilute sulfuric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 10:3:0.1.

[0080] 3. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0081] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing doped porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 12 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material.

[0082] 4. Preparation of cathode hydrogen evolution catalyst

[0083] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 20 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 10°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0084] Example 3: Cathode hydrogen evolution catalyst and its preparation

[0085] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0086] 1. Preparation of mesoporous carbon support

[0087] 1.1 Preparation of carbon material precursor solution

[0088] Petroleum asphalt, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1:0.1:4 and ultrasonically stirred at 550 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0089] 1.2 Preparation of doped porous carbon materials

[0090] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500 r / min to obtain a mixture solution B; the mixture solution B was stirred at 500 r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and zinc oxide nanowires were added while stirring at 500 r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 800°C. After high-temperature carbonization for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 2% dilute sulfuric acid at a mass ratio of 100:10, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain reaction product A; the reaction product A is repeatedly washed 5 times with 2% dilute sulfuric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of carbon material precursor solution, zinc oxide nanowires and NH4HCO3 is 10:3:0.1.

[0091] 2. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0092] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing doped porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 10 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material.

[0093] 3. Preparation of cathode hydrogen evolution catalyst

[0094] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 30 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 5 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0095] Example 4: Cathode hydrogen evolution catalyst and its preparation

[0096] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0097] 1. Preparation of mesoporous carbon support

[0098] 1.1 Preparation of carbon material precursor solution

[0099] Phenolic resin, ammonium phosphate trihydrate and deionized water were mixed in a mass ratio of 1.2:0.1:5, and ultrasonically stirred at 600 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 5°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0100] 1.2 Preparation of doped porous carbon materials

[0101] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture solution B; the mixture solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and copper oxide nanowires were added while stirring at 500r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was high-temperature heated in a horizontal quartz tube reactor at 900°C. After warm carbonization for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute nitric acid at a mass ratio of 100:10, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain reaction product A; the reaction product A is repeatedly washed 5 times with 3% dilute nitric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 10:2.5:0.1.

[0102] 2. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0103] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing doped porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 10 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material.

[0104] 3. Preparation of cathode hydrogen evolution catalyst

[0105] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 30 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 5 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0106] Example 5: Cathode hydrogen evolution catalyst and its preparation

[0107] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0108] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0109] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium oxide, magnesium hydroxide and distilled water was 3:1:150.

[0110] 2. Preparation of mesoporous carbon support

[0111] 2.1 Preparation of carbon material precursor solution

[0112] Glucose, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1.5:0.1:5, and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 5°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0113] 2.2 Preparation of doped porous carbon materials

[0114] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and (NH4)2CO3 was added while stirring at 500r / min to obtain a mixture solution B; the mixture solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 750°C. After carbonizing at medium and high temperature for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 2% dilute sulfuric acid at a mass ratio of 100:10, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain reaction product A; the reaction product A is repeatedly washed 3 times with 2% dilute sulfuric acid (this process removes the hard template), and then dried in an oven at 90°C for 10 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 10:3:0.1.

[0115] 3. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0116] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing doped porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 12 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid@doped porous carbon material.

[0117] 4. Preparation of cathode hydrogen evolution catalyst

[0118] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 20 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 10°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0119] Example 6: Cathode hydrogen evolution catalyst and its preparation

[0120] This embodiment provides a cathode hydrogen evolution catalyst, the preparation method of which includes the following steps:

[0121] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0122] Magnesium oxide, magnesium hydroxide and distilled water were placed in a high-pressure reactor lined with polytetrafluoroethylene and stirred at 500 r / min at a temperature of 10°C / min. -1 The temperature was raised to 160° C. at a rate of 1:10, and the mixture was reacted at 160° C. for 4 hours to obtain basic magnesium sulfate whiskers as a hard template. The molar ratio of magnesium oxide, magnesium hydroxide and distilled water was 3:1:150.

[0123] 2. Preparation of mesoporous carbon support

[0124] 2.1 Preparation of carbon material precursor solution

[0125] After petroleum asphalt and deionized water were mixed in a mass ratio of 1:5, ultrasonic stirring was carried out at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A; the mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0126] 2.2 Preparation of porous carbon materials

[0127] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture solution B; the mixture solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 400r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube at 800°C for 12 hours. After high-temperature carbonization in a reactor for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute sulfuric acid at a mass ratio of 100:15, first stirred at 500r / min and 40°C for 60 minutes, then filtered, and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with 3% dilute sulfuric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a porous carbon material; the porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of the carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 8:3:0.1.

[0128] 3. Preparation of nickel-molybdenum heteropoly acid clusters@porous carbon materials (in situ growth method)

[0129] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80°C for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of powdered doped porous carbon material was added to the mixture solution E, and the mixture was stirred at 500r / min and 80°C for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80°C for 30min to obtain a mixture containing porous carbon material and A mixed system of nickel-molybdenum heteropoly acid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in a 100°C oven and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an 80°C oven for 12 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid @ porous carbon material.

[0130] 4. Preparation of cathode hydrogen evolution catalyst

[0131] Nickel-molybdenum heteropoly acid @ porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 20 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0132] Comparative Example 1: Cathode hydrogen evolution catalyst and its preparation

[0133] This comparative example provides a cathode hydrogen evolution catalyst, the preparation method of which comprises the following steps:

[0134] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0135] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium oxide, magnesium hydroxide and distilled water was 3:1:150.

[0136] 2. Preparation of mesoporous carbon support

[0137] 2.1 Preparation of carbon material precursor solution

[0138] Petroleum asphalt, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1:0.1:4 and ultrasonically stirred at 600 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0139] 2.2 Preparation of doped porous carbon materials

[0140] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and basic magnesium sulfate whiskers were added while stirring at 500 r / min to obtain a mixture solution B; the mixture solution B was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was carbonized at a high temperature of 800°C in a horizontal quartz tube reactor for 30 minutes, and then naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product was mixed with a dilute nitric acid solution having a mass fraction of 3% and a mixture of the ... After the acids are mixed in a mass ratio of 100:20, they are first stirred at 500 r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with dilute nitric acid with a mass fraction of 3% (this process removes the hard template agent), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into a powder (particle diameter of 100μm to 1000μm) for use; wherein, the mass ratio of the carbon material precursor solution and the basic magnesium sulfate whiskers is 8:3.

[0141] 3. Preparation of nickel-molybdenum heteropoly acid clusters@doped porous carbon materials (in situ growth method)

[0142] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After dissolving in 1000mL of deionized water, stirring at 500r / min and 80°C for 60min, and adding 0.005mol of ammonium persulfate while stirring to obtain a mixture solution C; after adding 50g of powdered doped porous carbon material to the mixture solution C, stirring at 500r / min and 80°C for 120min, then adjusting the pH value to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirring at 500r / min and 80°C for 30min to obtain a mixed system containing doped porous carbon material and nickel-molybdenum heteropolyacid cluster precursor; the mixed system was transferred to a high-temperature reactor with a polytetrafluoroethylene lining, sealed, and placed in an oven at 100°C for 6h for aging, then the reactor was taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product was filtered three times, and the filtrate was discarded. The reaction product B was obtained; after the reaction product B was dried in an oven at 80° C. for 12 h, it was placed in a tube furnace and calcined at 400° C. for 6 h in a nitrogen atmosphere to obtain nickel-molybdenum heteropoly acid@doped porous carbon material.

[0143] 4. Preparation of cathode hydrogen evolution catalyst

[0144] Nickel-molybdenum heteropoly acid@doped porous carbon material was placed in a tubular furnace and purged under argon atmosphere for 20 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 10°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0145] Comparative Example 2: Cathode hydrogen evolution catalyst and its preparation

[0146] This comparative example provides a cathode hydrogen evolution catalyst, the preparation method of which comprises the following steps:

[0147] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0148] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium sulfate heptahydrate, magnesium hydroxide and distilled water was 3:1:150.

[0149] 2. Preparation of mesoporous carbon support

[0150] 2.1 Preparation of carbon material precursor solution

[0151] Glucose, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1.5:0.15:5, and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 5°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0152] 2.2 Preparation of porous carbon materials

[0153] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and (NH4)2CO3 was added while stirring at 450r / min to obtain a mixture solution B; the mixture solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture solution C; the mixture solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture solution D; the mixture solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube at 800°C for 12 hours. After high-temperature carbonization in a reactor for 60 minutes (the soft template is removed in this process), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 2% dilute sulfuric acid at a mass ratio of 100:10, first stirred at 500r / min and 40°C for 60 minutes, then filtered, and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with 2% dilute sulfuric acid (the hard template is removed in this process), and then dried in an oven at 80°C for 12 hours to obtain a porous carbon material; the porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of the carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 10:3:0.1.

[0154] 3. Preparation of cathode hydrogen evolution catalyst (impregnation method)

[0155] 3.1 Determination of water absorption of porous carbon material carriers

[0156] Weigh 100 g of the porous carbon material carrier, dry it in an oven at 120°C for 2 hours, weigh it, then put it in a watch glass and slowly add distilled water until the porous carbon material carrier no longer absorbs water. Use filter paper to gently absorb excess water on the surface of the porous carbon material carrier, weigh it again, and calculate the water absorption rate of the porous carbon material carrier (the water absorption rate calculation formula is: η = M / (M+W), where M is the mass of water, W is the mass of the porous carbon material carrier, and the calculated water absorption rate is 45%).

[0157] 3.2. Cathode Hydrogen Evolution Catalyst (NiMo Active Component Prepared by Impregnation Method)

[0158] Molybdenum trioxide, basic nickel carbonate and phosphoric acid were added to deionized water preheated to 80°C while stirring at 600r / min to prepare a nickel-molybdenum-phosphorus impregnation solution, in which the molar ratio of molybdenum trioxide, basic nickel carbonate and phosphoric acid was 9:1:1; according to the water absorption rate of the porous carbon material carrier, 40.91mL of the prepared nickel-molybdenum-phosphorus impregnation solution was taken and mixed evenly with 50g of the porous carbon material carrier while hot, and then allowed to stand for 2h, and then placed in a 100°C oven to dry for 12h, and then calcined at 400°C in a muffle furnace in a nitrogen atmosphere for 6h to obtain a porous carbon material carrier loaded with nickel-molybdenum-phosphorus; the porous carbon material carrier loaded with nickel-molybdenum-phosphorus was placed In a tubular furnace, after purging for 30 minutes under an argon atmosphere (to prevent the catalyst from being oxidized during the heating process), the argon atmosphere was switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9), and the temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the NiMo active component, thereby preparing a cathode hydrogen evolution catalyst (the loading rate of the metal sulfide MoS2 was 10%, and the molar amounts of molybdenum trioxide, basic nickel carbonate and phosphoric acid in the nickel-molybdenum-phosphorus impregnation solution were calculated based on the loading rate of the metal sulfide MoS2).

[0159] Comparative Example 3: Cathode hydrogen evolution catalyst and its preparation

[0160] This comparative example provides a cathode hydrogen evolution catalyst, the preparation method of which comprises the following steps:

[0161] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0162] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium oxide, magnesium hydroxide and distilled water was 3:1:150.

[0163] 2. Preparation of mesoporous carbon support

[0164] 2.1 Preparation of carbon material precursor solution

[0165] Petroleum asphalt, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1:0.1:4 and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0166] 2.2 Preparation of doped porous carbon materials

[0167] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture stock solution B; the mixture stock solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture stock solution C; the mixture stock solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture stock solution D; the mixture stock solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 800°C. After carbonizing at medium and high temperature for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute nitric acid at a mass ratio of 100:15, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with 3% dilute nitric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of the carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 8:3:0.1.

[0168] 3. Preparation of cathode hydrogen evolution catalyst (impregnation method)

[0169] 3.1. Determination of water absorption of doped porous carbon material carriers

[0170] Weigh 100 g of the doped porous carbon material carrier, dry it in an oven at 120°C for 2 hours, weigh it, then put it in a watch glass and slowly add distilled water until the doped porous carbon material carrier no longer absorbs water. Use filter paper to gently absorb excess water on the surface of the doped porous carbon material carrier, weigh it again, and calculate the water absorption rate of the doped porous carbon material carrier (the calculation formula for the water absorption rate is: η = M / (M+W), where M is the mass of water, W is the mass of the porous carbon material carrier, and the calculated water absorption rate is 45%).

[0171] 3.2. Cathode Hydrogen Evolution Catalyst (Preparation of Phosphomolybdenum Heteropolyacid@Doped Porous Carbon Material Catalyst by Impregnation Method)

[0172] In the deionized water preheated to 80℃, Wells Dawson type phosphomolybdic heteropoly acid H6P2Mo was added while stirring at 600r / min. 18 O 62, configured into a phosphorus-molybdenum heteropoly acid impregnation solution; according to the water absorption rate of the doped porous carbon material carrier, 40.91 mL of the configured phosphorus-molybdenum heteropoly acid impregnation solution was taken and mixed evenly with 50 g of the porous carbon material carrier while hot, and then allowed to stand for 2 hours, and then placed in a 100 ° C oven to dry for 12 hours, and then calcined in a muffle furnace at 400 ° C for 6 hours to obtain a porous carbon material carrier loaded with nickel, molybdenum and phosphorus; the porous carbon material carrier loaded with nickel, molybdenum and phosphorus was placed in a tubular furnace and purged under an argon atmosphere for 30 minutes (to avoid catalytic oxidation). The oxidizing agent is oxidized during the heating process), and then the argon atmosphere is switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 is 1:9). The temperature is first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 6 h in the mixed gas of H2S and H2 to complete the sulfurization process of the NiMo active component, thereby preparing a cathode hydrogen evolution catalyst (the loading rate of the metal sulfide MoS2 is 10%, and the Wells Dawson type phosphomolybdic heteropoly acid H6P2Mo in the phosphomolybdic heteropoly acid impregnation solution is 10%). 18 O 62 The molar amount is calculated based on the loading rate of metal sulfide MoS2).

[0173] Comparative Example 4: Cathode Hydrogen Evolution Catalyst and Its Preparation

[0174] This comparative example provides a cathode hydrogen evolution catalyst, the preparation method of which comprises the following steps:

[0175] 1. Preparation of hard template agent basic magnesium sulfate whiskers

[0176] Magnesium sulfate heptahydrate, magnesium hydroxide and distilled water were placed in a polytetrafluoroethylene-lined autoclave and stirred at 500 r / min and heated at 15°C / min. -1 The temperature was raised to 160° C. at a rate of 1000 ℃, and the mixture was reacted at 160° C. for 3 hours to obtain basic magnesium sulfate whiskers as a hard template; wherein the molar ratio of magnesium sulfate heptahydrate, magnesium hydroxide and distilled water was 3:1:150.

[0177] 2. Preparation of mesoporous carbon support

[0178] 2.1 Preparation of carbon material precursor solution

[0179] Petroleum asphalt, ammonium dihydrogen phosphate and deionized water were mixed in a mass ratio of 1:0.1:4, and ultrasonically stirred at 500 r / min and room temperature (25°C) for 2 h to completely dissolve them to obtain a mixture solution A. The mixture solution A was transferred to a high-pressure reactor lined with polytetrafluoroethylene and heated at 10°C·min -1 The temperature was raised to 80°C at a rate of 1000 ℃ and the mixture was reacted at 80°C for 12 hours to obtain a carbon material precursor solution.

[0180] 2.2 Preparation of doped porous carbon materials

[0181] The carbon material precursor solution was ultrasonically treated at 30°C for 60 minutes, and NH4HCO3 was added while stirring at 500r / min to obtain a mixture stock solution B; the mixture stock solution B was stirred at 500r / min and room temperature (25°C) for 30 minutes to mix it with the carbon material precursor solution to obtain a mixture stock solution C; the mixture stock solution C was ultrasonically treated at room temperature (25°C) for 20 minutes, and basic magnesium sulfate whiskers were added while stirring at 500r / min to obtain a mixture stock solution D; the mixture stock solution D was ultrasonically treated at room temperature (25°C) for 20 minutes, and then dried in an oven at 80°C for 12 hours to obtain a dry product; argon was introduced as a protective gas, and the dry product was placed in a horizontal quartz tube reactor at 800°C. After carbonizing at medium and high temperature for 60 minutes (this process removes the soft template), it is naturally cooled to room temperature (25°C) to obtain a carbonized product; the carbonized product is mixed with 3% dilute nitric acid at a mass ratio of 100:15, first stirred at 500r / min and 40°C for 60 minutes, then filtered and the filtrate is discarded to obtain a reaction product A; the reaction product A is repeatedly washed three times with 3% dilute nitric acid (this process removes the hard template), and then dried in an oven at 80°C for 12 hours to obtain a doped porous carbon material; the doped porous carbon material is ground into powder (particle diameter is 100μm~1000μm) for use; wherein, the mass ratio of the carbon material precursor solution, basic magnesium sulfate whiskers and NH4HCO3 is 8:3:0.1.

[0182] 3. Preparation of metal Pt@ doped porous carbon materials

[0183] 5 g of doped porous carbon material was added to 500 mL of 5% isopropanol aqueous solution, and ultrasonically dispersed for 3 hours to obtain dispersion A; 6.90 g of 2% H2PtCl6·6H2O solution was added to dispersion A, and ultrasonically dispersed for 2 hours to obtain dispersion B; after adjusting the pH value of dispersion B to 8 with NaOH, 6.25 g of 0.2% NaBH4 aqueous solution was added dropwise at 40°C, and then reacted at 40°C for 2 hours. Finally, the mixture was filtered and the filtrate was discarded to obtain reaction product B; reaction product B was washed three times with distilled water, and then dried in an 80°C oven for 12 hours to obtain a platinum-loaded cathode hydrogen evolution catalyst (platinum metal loading was 1%).

[0184] Comparative Example 5: Cathode Hydrogen Evolution Catalyst and Its Preparation

[0185] This comparative example provides a cathode hydrogen evolution catalyst, the preparation method of which comprises the following steps:

[0186] 1. Preparation of nickel-molybdenum heteropoly acid clusters@carbon nanofibers

[0187] 0.005 mol of nickel nitrate, 0.05 mol of (NH4)6Mo7O 24 After being dissolved in 1000mL of deionized water, the mixture was stirred at 500r / min and 80℃ for 60min, and 0.005mol of ammonium persulfate was added while stirring to obtain a mixture solution E; 50g of carbon nanofibers were added to the mixture solution E, and the mixture was stirred at 500r / min and 80℃ for 120min, and then the pH value was adjusted to 4.4 with 0.1mol / L dilute sulfuric acid, and finally stirred at 500r / min and 80℃ for 30min to obtain a mixture containing carbon nanofibers and nickel-molybdenum hybrids. A mixed system of polyacid cluster precursors; the mixed system is transferred to a high-temperature reactor with a polytetrafluoroethylene liner, and after sealing, the reactor is placed in an oven at 100°C and heated for 6 hours for aging, and then the reactor is taken out and naturally cooled to room temperature (25°C) to obtain an aged product; the reaction product is filtered three times, and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried in an oven at 80°C for 12 hours, placed in a tubular furnace, and calcined at 400°C in a nitrogen atmosphere for 6 hours to obtain a nickel-molybdenum heteropoly acid @ carbon nanofiber material.

[0188] 2. Preparation of cathode hydrogen evolution catalyst

[0189] The nickel-molybdenum heteropoly acid @ carbon nanofiber material was placed in a tubular furnace and purged under argon atmosphere for 30 minutes (to prevent the catalyst from being oxidized during the heating process). The argon atmosphere was then switched to a mixed gas of H2S and H2 (the volume ratio of H2S and H2 was 1:9). The temperature was first raised to 450°C at a rate of 5°C / min in the mixed gas of H2S and H2, and then maintained at 450°C for 5 hours in the mixed gas of H2S and H2 to complete the sulfurization process of the nickel-molybdenum heteropoly acid, thereby obtaining a cathode hydrogen evolution catalyst.

[0190] Experimental Example 1: Texture Performance of Cathode Hydrogen Evolution Catalyst

[0191] The physicochemical properties of the cathode hydrogen evolution catalysts in Examples 1 to 6 and Comparative Examples 1 to 5 were tested, and the test results are shown in Table 1. The textural properties were measured using a Tristar 2020 adsorption instrument purchased from Micromeritics, USA, the specific surface area was measured using the BET method (the BET method is described in "Molecular Sieve and Porous Material Chemistry, edited by Xu Ruren, Science Press, page 151"), the micropores, external specific surface area, and micropore volume were measured using the t-Plot method (the t-Plot method is described in "Molecular Sieve and Porous Material Chemistry, edited by Xu Ruren, Science Press, page 152"), and the mesopore volume was measured using the BJH method (the BJH method is described in "Molecular Sieve and Porous Material Chemistry, edited by Xu Ruren, Science Press, pages 150 and 155").

[0192] As shown in Table 1, and in Examples 1, 3, and 4, the catalyst prepared using basic magnesium sulfate whiskers as the hard template has a specific surface area of ​​654 m 2 / g, the catalyst prepared by using zinc oxide nanowires as hard template has a specific surface area of ​​563m 2 / g, the catalyst prepared by using copper oxide nanowires as hard template has a specific surface area of ​​515m 2 / g, indicating that the cathode hydrogen evolution catalyst prepared by using basic magnesium sulfate whiskers as a hard template has a larger specific surface area and pore volume. This is because the three-dimensional structure of the hard template is closely related to the texture properties of the cathode hydrogen evolution catalyst support. From Examples 1, 2 and 6, it can be seen that the specific surface area of ​​the catalyst prepared by doping P atoms is 654 m 2 / g, and the specific surface area of ​​the catalyst prepared by doping with nitrogen is 637m 2 / g, the specific surface area of ​​the catalyst prepared without doping is 621m 2 / g, doping heteroatoms in the carrier has little effect on the texture properties of the catalyst; from Example 1, Example 5 and Comparative Example 1, it can be seen that the specific surface area of ​​the catalyst prepared by adding the soft template NH4HCO3 is 654m 2 / g, the specific surface area of ​​the catalyst prepared by adding soft template (NH4)2CO3 is 628m 2 / g, the specific surface area of ​​the catalyst prepared without adding soft template is 575m 2 / g, indicating that a cathode hydrogen evolution catalyst with a large specific surface area and large pore volume can be obtained by adding a soft template in the preparation process of the cathode hydrogen evolution catalyst support, and the pore expansion effect of adding NH4HCO3 is better than that of adding (NH4)2CO3. This is because during the preparation process of the support, the soft template will decompose during the high-temperature carbonization process to produce gases such as NH3, CO2 or H2O, which play a role in pore expansion or volume expansion. It can be seen from Example 1 and Comparative Example 2 that the specific surface area of ​​the catalyst prepared by in-situ sulfurization of heteropolyacid is 654m 2 / g, the specific surface area of ​​the catalyst prepared by impregnation method is 596m 2 / g, indicating that the specific surface area of ​​the catalyst prepared by in-situ sulfurization of heteropolyacid is higher than that of the catalyst prepared by impregnation method; from Example 1 and Comparative Example 3, it can be seen that the specific surface area of ​​the NiMo-based non-precious metal catalyst prepared by in-situ sulfurization of heteropolyacid is 654 m 2 / g, the Mo-based non-precious metal catalyst prepared by impregnation method has a specific surface area of ​​582m 2 / g, the specific surface area of ​​the noble metal Pt catalyst prepared by in-situ reduction method is 621m 2 / g, indicating that the specific surface area of ​​the catalyst prepared by the in-situ synthesis method is higher than that of the catalyst prepared by the impregnation method; from Examples 1 to 6 and Comparative Example 4, it can be seen that the specific surface area of ​​the NiMo-based non-precious metal catalyst prepared by in-situ sulfurization of heteropolyacid is 575 to 654 m 2 The specific surface area of ​​the noble metal Pt catalyst prepared by in-situ reduction method is 621m / g. 2 / g, and the textural properties of the two are comparable, indicating that the method of preparing NiMo-based non-precious metal catalysts by in-situ sulfurization of heteropolyacids in Examples 1 to 6 can produce catalysts with good specific surface area without using precious metal Pt at all; it can be seen from Example 1 and Comparative Example 5 that the catalyst prepared by using basic magnesium sulfate whiskers as hard template and NH4HCO3 as soft template to prepare the doped porous carbon material carrier has a higher specific surface area than the catalyst prepared by using carbon nanofibers as carrier, which indicates that the carrier has a greater influence on the textural properties of the catalyst.

[0193] Table 1 Textural properties of different cathode hydrogen evolution catalysts

[0194] Experimental Example 2: Electrochemical Performance of Cathode Hydrogen Evolution Catalyst

[0195] The electrochemical performance test of the cathode hydrogen evolution catalyst was carried out on a homemade PEM electrolyzer. The PEM electrolyzer consists of anode and cathode plates and a membrane electrode assembly. The cathode and cathode plates are titanium plates. Deionized water is used as the electrolyte. The electrolyte is introduced into the electrolytic cell from the anode at a flow rate of 60 mL / min. The operating temperature of the electrolytic cell is 60°C. The preparation process of the membrane electrode assembly is as follows:

[0196] 1. Prepare proton exchange membrane materials

[0197] The treated Nafion 115 membrane (purchased from DuPont, USA) was cut into 6×6 cm 2 Size, actual spraying area is 25cm 2 .

[0198] 2. Prepare cathode hydrogen evolution catalyst layer slurry

[0199] 30 mg of a cathode hydrogen evolution catalyst was weighed, 1000 mg of isopropanol and 1000 mg of ethanol were added, and the mixture was ultrasonicated for 30 minutes to obtain a mixture; 200 mg of a 6% (w / w) Nafion solution (purchased from DuPont, USA) was added to the mixture, and the mixture was ultrasonicated for 90 minutes to obtain a cathode hydrogen evolution catalyst layer slurry.

[0200] 3. Prepare anode oxygen evolution catalyst slurry

[0201] 15 mg of iridium black (purchased from Johnson Matthey) was weighed, 500 mg of isopropanol and 500 μg of ethanol were added, and the mixture was ultrasonicated for 30 min to obtain a mixture; 60 mg of 6% (w / w) Nafion solution (purchased from DuPont, USA) was added to the mixture, and the mixture was ultrasonicated for 90 min to obtain an anode hydrogen evolution catalyst layer slurry.

[0202] 4. Spraying electrode

[0203] Spraying was carried out on a negative pressure hot plate at 70°C. The cathode catalyst layer slurry was first sprayed on one side of the proton exchange membrane. After spraying, it was dried on the spray plate for 15 minutes. Then, the anode catalyst layer slurry was sprayed on the other side of the proton exchange membrane. After spraying, it was dried on the spray plate for 15 minutes to obtain a membrane electrode assembly.

[0204] The electrochemical performance of the membrane electrodes with different cathode hydrogen evolution catalytic layers in Examples 1 to 6 and Comparative Examples 1 to 5 were tested. The test results are shown in Tables 2 and 3.

[0205] As shown in Tables 2 and 3, by comparing Example 1, Example 3 and Example 4, it is found that the electrolysis voltage (1.788V) and DC power consumption (4.237kW·h / m 3 ) is smaller than that of the catalyst prepared by zinc oxide nanowires and copper oxide nanowires, indicating that the use of different hard templates to prepare doped porous carbon material carriers will affect the electrochemical activity of the catalyst; it can be seen from Examples 1, 2 and 6 that adding phosphorus atoms to the doped porous carbon material carrier is beneficial to improving the electrochemical activity of the catalyst. This is because the phosphorus atoms are negatively charged and can act as proton acceptors to weaken the chemical bond strength between the catalytically active components and the protons, thereby promoting the occurrence of hydrogen evolution reaction; it can be seen from Examples 1, 5 and Comparative Example 1 that the electrolysis voltage of the catalyst prepared by adding the soft template NH4HCO3 is 1.788V and the DC power consumption is 4.273kW·h / m 3 The electrolysis voltage of the catalyst prepared by adding the soft template (NH4)2CO3 was 1.803V and the DC power consumption was 4.309kW·h / m 3 The electrolysis voltage of the catalyst prepared without adding soft template is 1.862V and the DC power consumption is 4.450kW·h / m 3Among them, the electrolysis voltage and DC power consumption of the catalyst prepared by using NH4HCO3 as a soft template are the lowest. This is because the soft template will decompose during the carbonization process of the carrier, which will expand the pores of the carrier and increase the specific surface area, thereby making the active components of the catalyst more evenly dispersed, exposing more catalytic active sites, and achieving the purpose of improving the electrochemical activity of the catalyst; From Example 1 and Comparative Example 2, it can be seen that the electrolysis voltage and DC power consumption of the catalyst prepared by the in-situ synthesis of heteropolyacid method are lower than those of the catalyst prepared by the impregnation NiMo solution method, which is because the active components of the catalyst prepared by the in-situ synthesis of heteropolyacid method are more evenly distributed ... 1 and Comparative Example 3, the electrolysis voltage and DC power consumption of the catalyst prepared by the in situ synthesis of nickel-molybdenum heteropoly acid method are lower than those of the catalyst prepared by impregnation of molybdenum heteropoly acid. On the one hand, this is because the catalyst prepared by the in situ synthesis of heteropoly acid method is more conducive to the dispersion of active components. On the other hand, nickel atoms can affect the particle size of the active phase MoS2 and the number of stacking layers of MoS2 crystallites, thereby improving the catalytic activity. It can be seen from Examples 1 to 6 and Comparative Example 4 that the electrolysis voltage of the catalyst prepared by the in situ synthesis of nickel-molybdenum heteropoly acid method is 1.788~1.853V, and the DC power consumption is 4.273~4.429kW·h / m 3 The electrolysis voltage of the noble metal Pt catalyst prepared by in-situ reduction method is 1.797V, and the DC power consumption is 4.295kW·h / m 3 The electrochemical activities of the two are comparable, indicating that the methods of preparing the catalysts by in-situ synthesis of nickel-molybdenum heteropolyacids in Examples 1 to 6 can produce catalysts with good electrochemical activity without using precious metal Pt. It can be seen from Example 1 and Comparative Example 5 that the electrolysis voltage (1.788 V) and DC power consumption (4.273 kW·h / m 3 ) is lower than the electrolysis voltage (1.837V) and DC power consumption (4.390kW·h / m 3 ), which shows that the support has a great influence on the electrochemical activity of the catalyst.

[0206] Table 2 Electrolysis voltage of different cathode hydrogen evolution catalyst layer membrane electrodes (unit: V)

[0207] Table 3 DC unit energy consumption of different cathode hydrogen evolution catalyst layer membrane electrodes (unit: kW·h / m 3 )

[0208] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing a cathode hydrogen evolution catalyst, characterized in that: The method comprises the following steps: Preparation of a carbon material precursor solution: mixing a carbon-based material, a doping compound, and a solvent A and reacting the mixture to obtain a carbon material precursor solution; Preparation of doped porous carbon material: mixing a carbon material precursor solution, a soft template agent and a hard template agent and then performing a carbonization reaction to obtain a carbonized product; acid-washing the carbonized product to obtain a doped porous carbon material; Preparation of nickel-molybdenum heteropoly acid@doped porous carbon material: nickel salt, molybdenum salt, solvent B, ammonium persulfate, and doped porous carbon material are mixed and reacted to obtain a mixed system containing doped porous carbon material and nickel-molybdenum heteropoly acid cluster precursor; the mixed system is sequentially aged, dried, and calcined to obtain nickel-molybdenum heteropoly acid@doped porous carbon material; Preparation of cathode hydrogen evolution catalyst: nickel molybdenum heteropoly acid@ doped porous carbon material is subjected to sulfurization reaction to obtain cathode hydrogen evolution catalyst; Alternatively, the method comprises the steps of: Preparation of carbon material precursor solution: mixing carbon-based material and solvent A and reacting them to obtain carbon material precursor solution; Preparation of porous carbon materials: mixing a carbon material precursor solution, a soft template agent and a hard template agent and then performing a carbonization reaction to obtain a carbonized product; acid-washing the carbonized product to obtain a porous carbon material; Preparation of nickel-molybdenum heteropoly acid@porous carbon material: nickel salt, molybdenum salt, solvent B, ammonium persulfate, and porous carbon material are mixed and reacted to obtain a mixed system containing porous carbon material and nickel-molybdenum heteropoly acid cluster precursor; the mixed system is sequentially aged, dried, and calcined to obtain nickel-molybdenum heteropoly acid@porous carbon material; Preparation of cathode hydrogen evolution catalyst: nickel molybdenum heteropoly acid@carbon material is subjected to sulfurization reaction to obtain cathode hydrogen evolution catalyst.

2. The method according to claim 1, wherein The preparation of the carbon material precursor solution comprises: mixing the carbon-based material, the doping compound and the solvent A, and ultrasonically stirring the mixture at 300-600 r / min and 10-30° C. for 0.5-6 h to obtain a mixture stock solution A; and heating the mixture stock solution A at 5-20° C. min -1 After heating to 60-180° C. at a rate of 100° C., reacting at 60-180° C. for 6-36 hours to obtain a carbon material precursor solution; Alternatively, the preparation of the carbon material precursor solution comprises: mixing the carbon-based material and solvent A, stirring the mixture with ultrasound at 300-600 r / min and 10-30°C for 0.5-6h to obtain a mixture stock solution A; -1 The temperature is raised to 60-180° C. at a rate of 1000 ℃, and the mixture is reacted at 60-180° C. for 6-36 hours to obtain a carbon material precursor solution.

3. The method according to claim 1, wherein The preparation of the doped porous carbon material or porous carbon material comprises: subjecting a carbon material precursor solution to ultrasonic treatment at 20-50° C. for 10-120 min, adding a soft template while stirring at 300-600 r / min to obtain a mixture stock solution B; stirring the mixture stock solution B at 200-800 r / min and 20-50° C. for 10-60 min to obtain a mixture stock solution C; subjecting the mixture stock solution C to ultrasonic treatment at 20-50° C. for 10-120 min, adding a hard template while stirring at 300-600 r / min to obtain a mixture stock solution D; and subjecting the mixture stock solution D to ultrasonic treatment at 20-50° C. for 10-120 min. ~50℃ for 10~120min, and then drying at 60~100℃ for 6~24h to obtain a dry product; under the protection of protective gas, carbonizing the dry product at a high temperature of 600~1300℃ for 10~60min, and then cooling to 10~30℃ to obtain a carbonized product; mixing the carbonized product with an acidic solution, stirring at 200~800r / min and 30~60℃ for 20~120min, and then filtering and discarding the filtrate to obtain a reaction product A; washing the reaction product A, and drying it at 60~100℃ for 2~12h to obtain a doped porous carbon material or a porous carbon material.

4. The method according to claim 1, wherein The preparation of the nickel-molybdenum heteropoly acid@doped porous carbon material or nickel-molybdenum heteropoly acid@porous carbon material comprises: mixing nickel salt, molybdenum salt and solvent B, stirring at 200-1200 r / min and 60-90° C. for 30-150 min, and adding ammonium persulfate while stirring to obtain a mixture solution E; adding the doped porous carbon material or the porous carbon material to the mixture solution E, The mixture is first stirred at 200-1200 r / min and 60-90° C. for 60-240 min, then the pH value is adjusted to 4-5 with an acidic solution, and finally stirred at 200-1200 r / min and 60-90° C. for 20-120 min to obtain a mixed system containing a doped porous carbon material and a nickel-molybdenum heteropoly acid cluster precursor or a mixed system containing a porous carbon material and a nickel-molybdenum heteropoly acid cluster precursor; the mixed system is heated at 80-120° C. for 0.5-12 h for aging, and then cooled to 10-30° C. to obtain an aging product; the aging product is filtered and the filtrate is discarded to obtain a reaction product B; the reaction product B is dried at 60-80° C. for 2-24 h, and then calcined at 250-400° C. for 2-12 h under the protection of a protective gas to obtain nickel-molybdenum heteropoly acid@doped porous carbon material or nickel-molybdenum heteropoly acid@porous carbon material.

5. The method according to claim 1, wherein The preparation of the cathode hydrogen evolution catalyst comprises: purging nickel-molybdenum heteropoly acid@doped porous carbon material or nickel-molybdenum heteropoly acid@porous carbon material with protective gas for 20 to 60 minutes, heating the material to 300 to 600° C. at a rate of 2 to 20° C. / min in a sulfiding gas, and then reacting the material at 300 to 600° C. for 1 to 8 hours in the sulfiding gas to obtain the cathode hydrogen evolution catalyst.

6. The method according to any one of claims 1 to 5, wherein: The mass ratio of the carbon-based material, the doping compound and the solvent A is 1:0-0.3:0.2-10; the mass ratio of the carbon material precursor solution, the hard template agent and the soft template agent is 1-2:1-10:0.01-2.

7. A cathode hydrogen evolution catalyst, characterized in that The cathode hydrogen evolution catalyst is prepared by the method according to any one of claims 1 to 6.

8. A PEM water electrolysis device, characterized in that: The PEM water electrolysis device includes a PEM electrolyzer; the PEM electrolyzer includes the cathode hydrogen evolution catalyst according to claim 7.

9. A method for producing hydrogen by electrolysis of water, characterized in that: The method comprises: passing deionized water into the PEM water electrolysis device according to claim 8 for electrolysis to obtain hydrogen.

10. Use of the method for preparing a cathode hydrogen evolution catalyst according to any one of claims 1 to 6, the cathode hydrogen evolution catalyst according to claim 7, the PEM water electrolysis device according to claim 8, or the method for preparing hydrogen production by PEM water electrolysis according to claim 9 in hydrogen production by water electrolysis.

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