Metal nitride nanohydrogen evolution catalyst, and preparation method and application thereof

Abstract

The application discloses a metal nitride nano hydrogen evolution catalyst, the catalyst is a brush-shaped metal nitride catalyst, the catalyst contains Ni, Co, Cu, V metal and N element with catalytic activity; wherein, the active component is dispersed in the catalyst; and a preparation method and application of the metal nitride nano hydrogen evolution catalyst. The required overpotential is less than or equal to 220 and 206 mV respectively, which lays a technical foundation for reducing the hydrogen production cost. 2 The required overpotential is less than or equal to 220 and 206 mV respectively, which lays a technical foundation for reducing the hydrogen production cost.

Description

Technical Field

[0001] This invention relates to a hydrogen evolution catalyst, its preparation method and application, specifically to a metal nitride nano-hydrogen evolution catalyst, its preparation method and application. Background Technology

[0002] Since the beginning of the 21st century, the world's population has been growing, leading to an increasing demand for energy. Studies indicate that fossil fuels will be depleted by 2112. Therefore, hydrogen energy, with its advantages of high calorific value, pollution-free combustion products, and abundant reserves, has gradually gained attention. Compared to hydrogen production from fossil fuels and biomass, hydrogen production through water electrolysis is simple, rapid, pollution-free, and can fully utilize primary renewable energy sources such as wind and solar power, making it one of the most promising methods for hydrogen production.

[0003] In industrial hydrogen production via water electrolysis, alkaline solutions are typically used as electrolytes because electrode materials in water electrolysis devices are less susceptible to corrosion in alkaline electrolytes than in acidic electrolytes. Furthermore, natural water is usually neutral or weakly alkaline. Therefore, developing alkaline and neutral electrolytes for water electrolysis to produce hydrogen is of great significance. However, in alkaline or neutral electrolytes, the hydrogen evolution reaction (HER) has a high water dissociation energy barrier, resulting in slow reaction kinetics. Therefore, highly active catalysts are needed to accelerate the HER in alkaline and neutral solutions. Platinum / iridium / ruthenium / rhodium-based catalysts exhibit high catalytic activity in HER, but the scarcity and high cost of these precious metals limit their large-scale application. Meanwhile, the high overpotential and poor stability of inexpensive non-precious metal-based catalysts for HER remain significant challenges. Therefore, developing transition metal water electrolysis catalysts with excellent HER performance in alkaline and neutral solutions is crucial for the industrial-scale production of hydrogen via water electrolysis. Summary of the Invention

[0004] This invention addresses the problems existing in the prior art by proposing a metal nitride nano-catalyst for hydrogen evolution reaction. The aim is to obtain a brush-shaped metal nitride nanoarray hydrogen evolution reaction catalyst that is simple to process, low in cost, and has good catalytic performance in alkaline / neutral electrolytes.

[0005] To achieve the above objectives, the technical solution provided by the present invention is as follows:

[0006] A metal nitride nano-hydrogen evolution catalyst, wherein the catalyst is a brush-shaped metal nitride catalyst, and the catalyst contains catalytically active metals Ni, Co, Cu, V and N elements; wherein the active components are dispersed within the catalyst.

[0007] Furthermore, V in the catalyst is incorporated into Ni4N and CuCoN in the form of dopant. 0.6 Or Ni4N and CuCoN 0.6In the heterojunction formed.

[0008] Furthermore, in the above technical solution, the XRD pattern of the catalyst has diffraction peaks at 2θ of 41.72°, 41.784°, 48.57°, 48.65°, 85.948°, and 86.099°.

[0009] The preparation method of the metal nitride nano-hydrogen evolution catalyst as described above includes the following steps:

[0010] (1) Dissolve the alkali and persulfate in water at a molar ratio of 9-14:1 to prepare solution I. Add the substrate material to solution I, let it stand, take out the substrate material, clean it, and vacuum dry it to obtain sample A.

[0011] (2) The metal precursor metal salt is dissolved in a solvent to obtain a metal salt solution. The metal salt solution and the sample A are placed in a reaction vessel and stirred for a solvothermal reaction. After the reaction is completed, the mixture is cooled to room temperature. The material obtained from the reaction vessel is taken out, cleaned, and vacuum dried to obtain a preliminary sample. The precursor metal salt is composed of two or three of the following: vanadium salt, cobalt salt, or nickel salt.

[0012] (3) The preliminary sample was placed in a tube furnace and calcined at high temperature with ammonia gas to obtain metal nitride nano hydrogen evolution catalyst.

[0013] Preferably, the persulfate mentioned in step (1) is one of ammonium persulfate, sodium persulfate, or potassium persulfate.

[0014] Preferably, the alkali in step (1) is potassium hydroxide or sodium hydroxide; the substrate material in step (1) is a copper substrate, which is copper wire, copper mesh, copper foil, copper foam or copper sheet.

[0015] Preferably, the solvent in step (2) is obtained by mixing one of the following with deionized water: pyridine, pyrrole, 3-aminopyridine, 4-methylpyridine, 3-chloropyridine, 3-fluoropyridine, 3-bromopyridine, 2,3-diaminopyridine, 2-amino-3-chloropyridine, 2-pyrrolidone, 2-pyrrole carboxylic acid, 3-acetyl-2,4-dimethylpyrrole, hydroxyethylpyrrole, 2-acetylpyrrole, 1-methylpyrrole, tetrahydropyrrole, ethyl pyrrole-2-carboxylate, 2,4-dimethylpyrrole, 4-acetylpyridine, 2-acetylpyrrole, or N-methylpyrrole.

[0016] Preferably, the mass ratio of the metal salt solution in step (2) to solution I in step (1) is 1-5:1-5; and the concentration of the metal salt solution obtained in step (2) is 0.04-0.3 mmol / mL.

[0017] Preferably, the vanadium salt mentioned in step (2) is one of ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium oxide, vanadium tetrachloride, sodium vanadate, vanadium acetylacetonate, vanadium triisopropoxide, vanadium acetylacetonate, vanadium triisopropoxy, or vanadium diacetylacetonate; the cobalt salt is cobalt chloride, cobalt acetate, cobalt phosphate, cobalt phthalocyanine, potassium cobalt cyanocyanate, potassium hexacyanocobaltate, cobalt hexaaminochloride, cobalt perchlorate, cobalt nitrate, cobalt fluoride, etc. The nickel salt is one of cobalt iodide, cobalt bromide, sodium cobalt nitrite, cobalt oxalate, cobalt sulfate, cobalt sulfite, cobalt ammonium sulfate, cobalt naphthenate, or cobalt acetylacetonate; the nickel salt is one of nickel chloride, nickel acetylacetonate, nickel acetylacetonate, nickel acetate, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel ammonium sulfate, nickel hypophosphite, nickel ammonium nitrate, nickel aminosulfonate, basic nickel carbonate, nickel formate, nickel dicene, nickel bis(triphenylphosphine)bromide, or nickel bis(triphenylphosphine)chloride.

[0018] Preferably, the stirring in step (2) is carried out at a speed of 60-70 rpm for 15 minutes; the solvothermal reaction is carried out at a temperature of 100-200℃ for 2-48 hours.

[0019] Preferably, the high-temperature calcination in step (3) is performed with a heating rate of 1-20℃ / minute, a calcination temperature of 300-1000℃, and a holding time of 1-6 hours.

[0020] The application of metal nitride nano-catalysts in hydrogen evolution reactions, as described above.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] This invention uses a copper substrate as a carrier and vanadium salts, cobalt salts, and nickel salts as metal sources. The mixture is first solvothermally synthesized and then calcined at high temperature to obtain a metal nitride nanoarray water electrolysis catalyst. The preparation process is simple and low-cost. The resulting metal nitride nano-hydrogen evolution catalyst is brush-shaped and exhibits good electrochemical catalytic activity in both alkaline and neutral solutions, reaching -10 mA / cm² in both solutions. 2 The required overpotentials are less than or equal to 220 mV and 206 mV, respectively, which lays the technical foundation for reducing the cost of hydrogen production. Attached Figure Description

[0023] Figure 1 (a) is a field emission scanning electron microscope (SEM) image of the metal nitride nano-hydrogen evolution catalyst prepared in Example 3 of the present invention. Figure 1 (b) is a transmission electron microscope (TEM) image.

[0024] Figure 2The X-ray diffraction (XRD) pattern of the metal nitride nano-catalyst for hydrogen evolution prepared in Example 3 of this invention; wherein V-CuCoN 0.6 / Ni4N represents the XRD data of the metal nitride nano-hydrogen evolution catalyst prepared in Example 3 of this invention. Cu and CuCoN are also relevant data. 0.6 Ni4N is the standard card.

[0025] Figure 3 The energy dispersive X-ray spectroscopy (EDS) spectrum of the metal nitride nano-hydrogen evolution catalyst prepared in Example 3 of this invention is obtained by X-ray energy dispersive spectroscopy.

[0026] Figure 4 Hydrogen evolution polarization curves (LSV) of the catalysts of this invention in a series of metal nitride nano-catalysts in 1.0 mol / L potassium hydroxide solution;

[0027] Figure 5 Tafel slope diagrams of hydrogen evolution of the catalysts of this invention in a series of metal nitride nano-catalysts in 1.0 mol / L potassium hydroxide solution;

[0028] Figure 6 The hydrogen evolution polarization curves (LSV) of the catalysts of this invention in 1.0 mol / L phosphate buffered saline (PBS) solution are shown for a series of metal nitride nano-catalysts for hydrogen evolution.

[0029] Figure 7 The Tafel slope diagram of the hydrogen evolution of the catalyst of the present invention in a series of metal nitride nano-catalysts in 1.0 mol / L phosphate buffered saline (PBS) solution is shown.

[0030] in, Figure 4 , Figure 5 , Figure 6 , Figure 7 V-CuCoN 0.6 The / Ni4N line represents the catalyst data obtained in Example 3, CuCoN. 0.6 The / Ni4N line represents the catalyst data prepared in Example 2, and the V-Ni4N line represents the catalyst data prepared in Comparative Example 1, V-CuCoN. 0.6 The lines represent the catalyst data prepared in Comparative Example 4. Detailed Implementation

[0031] The following detailed description, in conjunction with the accompanying drawings, outlines specific embodiments. However, it should be understood that the scope of protection of this invention is not limited to these specific embodiments. Unless otherwise specified, all raw materials and reagents used in the examples are commercially available.

[0032] In this invention, the XRD testing method involves using a Minflex 600 X-ray diffractometer (Rigaku, Japan) to test the catalyst and determine its material composition. The conditions are as follows: the X-ray tube operates at 40 kV and 40 mA, with a scanning speed of 10° / min. -1 The 2θ scan range is 5-90°.

[0033] Example 1

[0034] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0035] (1) Dissolve 3g sodium hydroxide, 3g potassium hydroxide and 2.58g ammonium persulfate in 100mL of deionized water to prepare solution I. Add copper foam to solution I, let stand for 2 minutes, take out the copper foam substrate material, clean it and vacuum dry it to obtain sample A;

[0036] (2) Dissolve 450 mg of nickel nitrate and 200 mg of cobalt oxalate in a solvent consisting of 0.5 mL of 3-bromopyridine and 30 mL of deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 100 °C for 30 hours (the mass ratio of the metal salt solution to solution I in step (1) is 3:1). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0037] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 23 mL / min, maintain the heating rate at 3℃ / min, heat to 400℃ and hold for 2 hours for high-temperature calcination, and obtain the metal nitride nano hydrogen evolution catalyst, which is a heterostructure water electrolysis catalyst of nickel nitride and copper cobalt nitride.

[0038] Example 2

[0039] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0040] (1) Dissolve 6g of sodium hydroxide and 2.58g of ammonium persulfate in 100mL of deionized water to prepare solution I. Add copper foam to solution I, let stand for 2 minutes, take out the copper foam, wash and vacuum dry to obtain sample A;

[0041] (2) Dissolve 600 mg of nickel sulfate and 400 mg of cobalt fluoride in a solvent consisting of 0.5 mL of 2,3-diaminopyridine and 30 mL of deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 170 °C for 10 hours (the mass ratio of the metal salt solution to solution I in step (1) is 1:3). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0042] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 27 mL / min, maintain a heating rate of 5 °C / min, heat to 400 °C and hold for 3 hours for high-temperature calcination to obtain the metal nitride nano hydrogen evolution catalyst, which is a heterostructure water electrolysis catalyst of nickel nitride and copper cobalt nitride (CuCoN). 0.6 / Ni4N).

[0043] Example 3

[0044] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0045] (1) Dissolve 6g of sodium hydroxide and 2.58g of sodium persulfate in 100mL of deionized water to prepare solution I. Add copper foil to solution I, let stand for 2 minutes, take out the copper foil, wash it, and vacuum dry it to obtain sample A.

[0046] (2) Dissolve 414 mg of nickel nitrate, 250 mg of sodium cobalt nitrite and 80 mg of vanadium oxide in a solvent consisting of 0.5 mL of pyridine and 30 mL of deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 140 °C for 10 hours (the mass ratio of the metal salt solution to solution I in step (1) is 1:1). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it and vacuum dry it to obtain a preliminary sample.

[0047] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at a rate of 20 mL / min, maintain a heating rate of 5 °C / min, heat to 500 °C and hold for 3 hours for high-temperature calcination to obtain the metal nitride nano-hydrogen evolution catalyst, which is vanadium-doped Ni4N and CuCoN. 0.6 Heterogeneous water electrolysis catalyst (V-CuCoN) 0.6 / Ni4N).

[0048] Comparative Example 1

[0049] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0050] (1) Dissolve 6g of sodium hydroxide and 2.58g of sodium persulfate in 100mL of deionized water to prepare solution I. Add copper foam to solution I, let stand for 2 minutes, take out the copper foam, wash and vacuum dry to obtain sample A;

[0051] (2) Dissolve 414 mg of nickel nitrate and 30 mg of vanadium chloride in a solvent consisting of 0.5 mL of pyridine and 30 mL of deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 160 °C for 10 hours (the mass ratio of the metal salt solution to solution I in step (1) is 1:1). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0052] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 20 mL / min, maintain the heating rate at 5 °C / min, heat to 500 °C and hold for 3 hours for high-temperature calcination, and obtain the metal nitride nano hydrogen evolution catalyst, which is a vanadium-doped nickel nitride electrolysis catalyst (V-Ni4N).

[0053] Comparative Example 2

[0054] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0055] (1) Dissolve 6g of sodium hydroxide and 2.58g of ammonium persulfate in 100mL of deionized water to prepare solution I. Add copper sheet to solution I, let stand for 2 minutes, then take out the copper sheet, clean it, and vacuum dry it to obtain sample A.

[0056] (2) Dissolve 500 mg of nickel nitrate and 50 mg of ammonium metavanadate in a solvent consisting of 0.5 mL of pyrrole dissolved in 30 mL of deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 180 °C for 8 hours (the mass ratio of the metal salt solution to solution I in step (1) is 1:2). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0057] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 25 mL / min, maintain the heating rate at 5℃ / min, heat to 450℃ and hold for 3 hours for high-temperature calcination, and obtain the metal nitride nano hydrogen evolution catalyst, which is a vanadium-doped nickel nitride electrolysis catalyst.

[0058] Comparative Example 3

[0059] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0060] (1) Dissolve 6g of sodium hydroxide and 2.58g of sodium persulfate in 100mL of deionized water to prepare solution I. Add copper wire to solution I, let stand for 2 minutes, take out the copper wire, clean it, and vacuum dry it to obtain sample A.

[0061] (2) Dissolve 550 mg cobalt acetate and 40 mg sodium vanadate in a solvent consisting of 0.5 mL pyrrole and 30 mL deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 140 °C for 12 hours (the mass ratio of the metal salt solution to solution I in step (1) is 2:1). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0062] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 30 mL / min, maintain the heating rate at 5 °C / min, heat to 400 °C and hold for 3 hours for high-temperature calcination, and obtain the metal nitride nano hydrogen evolution catalyst, which is a vanadium-doped copper cobalt nitride water electrolysis catalyst.

[0063] Comparative Example 4

[0064] A method for preparing a metal nitride nano-catalyst for hydrogen evolution includes the following steps:

[0065] (1) Dissolve 6g of potassium hydroxide and 2.58g of potassium persulfate in 100mL of deionized water to prepare solution I. Add copper foam to solution I, let stand for 2 minutes, take out the copper foam, wash and vacuum dry to obtain sample A;

[0066] (2) Dissolve 450 mg cobalt nitrate and 30 mg vanadium tetrachloride in a solvent consisting of 0.5 mL 3-aminopyridine and 30 mL deionized water to obtain a metal salt solution. Put the metal salt solution and sample A obtained in step (1) into a reaction vessel and stir for 15 min. Then, carry out a solvothermal reaction at 200 °C for 6 hours (the mass ratio of the metal salt solution to solution I in step (1) is 2:13). After the reaction is completed, cool to room temperature, take out the material obtained in the reaction vessel, clean it, and vacuum dry it to obtain a preliminary sample.

[0067] (3) Place the preliminary sample obtained in step (2) in a tube furnace, introduce ammonia gas at 18 mL / min, maintain a heating rate of 3 °C / min, heat to 500 °C and hold for 2 hours for high-temperature calcination to obtain the metal nitride nano hydrogen evolution catalyst, which is a vanadium-doped copper cobalt nitride water electrolysis catalyst (V-CuCoN). 0.6 ).

[0068] Table 1. Electrochemical hydrogen evolution performance in potassium hydroxide solution

[0069]

[0070] Table 2. Electrochemical hydrogen evolution performance in PBS solution

[0071]

[0072]

[0073] Table 1 shows the catalysts prepared in Comparative Examples 1, 4, 2, and 3 (catalyst dosage 0.2 cm). 2 The results were obtained by linear sweep voltammetry (LSV) tests in a 1.0 mol / L potassium hydroxide solution. The different current densities required for the catalyst to reach different voltages in the 1.0 mol / L potassium hydroxide solution were obtained and listed in the table. The Tafel slope was calculated based on the LSV and listed in the table. The results are as follows: Figure 4 and Figure 5 As shown in Table 2. Table 2 shows the catalysts prepared in Comparative Examples 1, 4, 2, and 3 (catalyst dosage 0.2 cm). 2 The results were obtained by linear sweep voltammetry (LSV) tests in 1.0 mol / L PBS solution. The different current densities required for the catalyst to reach different voltages in 1.0 mol / L PBS solution were obtained, and the Tafel slope was calculated and listed in the table based on the LSV. The results are as follows: Figure 6 , Figure 7 As shown in Tables 1 and 2, the metal nitride nanoarray catalysts exhibit good hydrogen evolution reaction performance in both alkaline and neutral electrolytes.

[0074] from Figure 1 and Figure 2 as well as Figure 3 It can be seen that the metal nitride nano-catalyst for hydrogen evolution of this invention has been successfully prepared. From Figure 4 , Figure 5 , Figure 6 and Figure 7 As can be seen, the metal nitride nano-hydrogen evolution catalyst of the present invention has good hydrogen evolution reaction performance in both alkaline and neutral electrolytes.

[0075] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A metal nitride nano-catalyst for hydrogen evolution, characterized in that: The catalyst is a brush-shaped metal nitride catalyst, which contains catalytically active metals such as Ni, Co, Cu, and V, as well as the element N; wherein the active components are dispersed within the catalyst. The preparation method of the metal nitride nano-hydrogen evolution catalyst includes the following steps: (1) Dissolve the alkali and persulfate in water at a molar ratio of 9-14:1 to prepare solution I. Add the substrate material to solution I, let it stand, take out the substrate material, clean it and dry it to obtain sample A; (2) The metal precursor metal salt is dissolved in a solvent to obtain a metal salt solution. The metal salt solution and the sample A are placed in a reaction vessel and stirred for a solvothermal reaction. After the reaction is completed, the mixture is cooled to room temperature. The material obtained from the reaction vessel is taken out, washed, and dried to obtain a preliminary sample. The precursor metal salt is composed of two or three of the following: vanadium salt, cobalt salt, or nickel salt. (3) The preliminary sample was placed in a tube furnace and calcined at high temperature with ammonia gas to obtain metal nitride nano hydrogen evolution catalyst.

2. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: In the catalyst, V is incorporated into Ni4N and CuCoN in the form of dopant. 0.6 Or Ni4N and CuCoN 0.6 In the heterojunction formed.

3. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: The persulfate mentioned in step (1) is one of ammonium persulfate, sodium persulfate or potassium persulfate; the alkali mentioned in step (1) is potassium hydroxide or sodium hydroxide; the substrate material mentioned in step (1) is a copper substrate, which is copper wire, copper mesh, copper foil, copper foam or copper sheet.

4. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: The solvent mentioned in step (2) is obtained by mixing one of the following with water: pyridine, pyrrole, 3-aminopyridine, 4-methylpyridine, 3-chloropyridine, 3-fluoropyridine, 3-bromopyridine, 2,3-diaminopyridine, 2-amino-3-chloropyridine, 2-pyrrolidone, 2-pyrrolic acid, 3-acetyl-2,4-dimethylpyrrole, hydroxyethylpyrrolidone, 2-acetylpyrrole, 1-methylpyrrole, tetrahydropyrrole, ethyl pyrrole-2-carboxylate, 2,4-dimethylpyrrole, 4-acetylpyridine, 2-acetylpyrrole, or N-methylpyrrole; the vanadium salt mentioned in step (2) is ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, vanadium chloride, vanadium oxide, vanadium tetrachloride, sodium vanadate, vanadium acetylacetonate, triisopropyltrimonium chloride, vanadium trivanadate, etc. The cobalt salt is one of the following: vanadium oxyethanol, vanadium acetylacetonate, vanadium triisopropoxy, or vanadium diacetylacetonate; the cobalt salt is one of the following: cobalt chloride, cobalt acetate, cobalt phosphate, cobalt phthalocyanine, potassium cobalt cyanocobalt, potassium hexacyanocobalt, cobalt hexaaminochloride, cobalt perchlorate, cobalt nitrate, cobalt fluoride, cobalt iodide, cobalt bromide, sodium cobalt nitrite, cobalt oxalate, cobalt sulfate, cobalt sulfite, ammonium cobalt sulfate, cobalt naphthenate, or cobalt acetylacetonate; the nickel salt is one of the following: nickel chloride, nickel acetylacetonate, nickel acetylacetonate, nickel acetate, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, ammonium nickel sulfate, nickel hypophosphite, ammonium nickel nitrate, nickel aminosulfonate, basic nickel carbonate, nickel formate, nickel dicene, nickel bis(triphenylphosphine)bromide, or nickel bis(triphenylphosphine)chloride.

5. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: In step (2), the mass ratio of the metal salt solution to solution I in step (1) is 1-5:1-5; the concentration of the metal salt solution obtained in step (2) is 0.04-0.3 mmol / mL.

6. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: The stirring in step (2) is carried out at a speed of 60-70 rpm for 15 minutes; the solvothermal reaction is carried out at a temperature of 100-200℃ for 2-48 hours.

7. The metal nitride nano-hydrogen evolution catalyst according to claim 1, characterized in that: The high-temperature calcination in step (3) is characterized by a heating rate of 1-20℃ / minute, a calcination temperature of 300-1000℃, and a holding time of 1-6 hours.

8. The application of the metal nitride nano-hydrogen evolution catalyst as described in any one of claims 1-7 in the hydrogen evolution reaction.

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