Nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper and preparation method and application thereof

Abstract

The invention discloses a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper, and a preparation method and application thereof. The preparation method first prepares nickel-doped molybdenum disulfide (Ni-MoS2) and NaHSe solutions respectively. A nickel source, a molybdenum source and a sulfur source are stirred evenly in deionized water and then placed in a polytetrafluoroethylene-lined autoclave containing clean carbon paper for hydrothermal reaction to obtain a Ni-MoS2 catalyst; in an inert atmosphere, selenium powder and sodium borohydride are completely reacted in anhydrous ethanol, and then deionized water is added to obtain a NaHSe solution. The NaHSe solution is transferred to a polytetrafluoroethylene-lined autoclave containing Ni-MoS2 for solvothermal reaction to obtain a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper, and applied to an electrocatalytic hydrogen evolution reaction. This method has the characteristics of simple preparation, low cost and environmental friendliness.

Description

Technical Field

[0001] The invention belongs to the technical field of electrocatalysis, and in particular relates to a nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper, and a preparation method and application thereof. Background Art

[0002] Since the Industrial Revolution, a large amount of fossil energy has been mined and utilized, resulting in the emission of toxic gases and a huge energy gap. People need to develop other green energy sources to achieve sustainable social development. Hydrogen, as a highly potential green energy carrier, has an energy density of up to 1.2×10 5 kJ / kg, producing hydrogen through the cathode reduction reaction of water electrolysis - hydrogen evolution reaction (HER) is an efficient and green method. The catalyst reaches 10mA / cm 2 The overpotential (η) required for the current density 10 ) is an important indicator for measuring HER catalysts, η 10 The smaller it is, the better the HER performance of the material. At present, the mainstream HER electrocatalyst is Pt-based catalyst (such as 20% Pt / C). However, limited earth reserves and high industrial costs limit the large-scale application of Pt-based catalysts in industry. Therefore, preparing cheap HER electrocatalysts with high catalytic performance to replace Pt is one of the current research hotspots.

[0003] As a transition metal sulfide, molybdenum disulfide (MoS2) has a two-dimensional layered structure similar to graphene. Ever since researchers calculated that unsaturated molybdenum at the edge of MoS2 has extremely small hydrogen adsorption free energy, this material has received widespread attention and research. However, factors such as MoS2's extremely poor electrical conductivity, small interlayer spacing, and few catalytic sites seriously hinder its HER performance. In recent years, studies have found that transition metal doping, such as cobalt and iron, can effectively create more catalytic active sites on the MoS2 basal plane. A Chinese patent application for a cobalt-doped molybdenum disulfide electrocatalytic material, its preparation method and application discloses the preparation of cobalt-doped MoS2 using a one-step hydrothermal method. The material is simple to prepare, but the material η 10 Still large; on the other hand, non-metallic doping, such as selenium, can effectively increase the defects of MoS2 and improve its conductivity. The Chinese patent application "Preparation and application of in-situ loaded selenium-doped molybdenum disulfide / transition metal boride nanomaterials" discloses a composite material of selenium-doped MoS2 and transition metal boride. Although the material has good electrocatalytic performance, the preparation process is cumbersome, and the tail gas generated by the high-temperature gas-solid phase selenization process will cause certain environmental pollution. At present, it is still a huge challenge to use a simple method to prepare a MoS2-based catalyst with high catalytic activity and low cost for electrocatalytic hydrogen evolution. Summary of the invention

[0004] In order to solve the problem that molybdenum disulfide has few catalytic active sites, poor conductivity, and poor electrocatalytic hydrogen evolution performance, the purpose of the present invention is to provide a nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper and its preparation method and application. The nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper prepared by the present invention has good HER performance, low preparation method cost, simple operation, and has reference significance for the preparation of other MoS2-based catalysts.

[0005] In the present invention, nickel-selenium co-doped molybdenum disulfide supported on carbon paper is prepared through a two-step reaction, the operation is simple, the experimental cost is low, and the prepared catalyst has excellent HER performance in an alkaline environment, which has reference value for the industrial production of hydrogen production by water electrolysis.

[0006] The present invention is achieved through the following technical solutions:

[0007] The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper comprises the following steps:

[0008] (1) Carbon paper pretreatment: The purchased carbon paper was cut into rectangular shapes and ultrasonicated in acetone, anhydrous ethanol and deionized water in turn to remove impurities and organic matter on the surface of the carbon paper to obtain clean carbon paper.

[0009] (2) Preparation of nickel-doped molybdenum disulfide (Ni-MoS2): Molybdenum source, sulfur source and nickel source are added to deionized water in sequence. After stirring evenly, the solution and the washed carbon paper are transferred to a polytetrafluoroethylene-lined high-pressure reactor and placed in an oven for hydrothermal reaction. After the reaction is completed, the carbon paper is washed and dried to obtain Ni-MoS2 loaded on the carbon paper.

[0010] (3) Preparation of NaHSe solution: In an inert atmosphere, add selenium powder and sodium borohydride to anhydrous ethanol. After sufficient reaction, add deionized water to dilute and continue stirring until the solution turns wine red. This solution is the NaHSe solution.

[0011] (4) Solvothermal selenization: The Ni-MoS2 loaded on the carbon paper in step (2) is placed in a polytetrafluoroethylene-lined autoclave, and the NaHSe solution obtained in step (3) is transferred to the polytetrafluoroethylene-lined autoclave and placed in an oven for solvent thermal reaction. After the reaction is completed, the carbon paper is taken out, washed and dried. A nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper is obtained.

[0012] Furthermore, the size of the rectangle in step (1) is 1 cm×3 cm.

[0013] Furthermore, in step (1), the carbon paper is ultrasonicated in acetone, anhydrous ethanol and deionized water for 10-20 minutes respectively.

[0014] Furthermore, the molybdenum source in step (2) is one or more of sodium molybdate, ammonium molybdate, and potassium molybdate; the sulfur source in step (2) is thiourea; and the nickel source in step (2) is one or more of nickel chloride hexahydrate, nickel nitrate hexahydrate, and nickel acetylacetonate.

[0015] Furthermore, in step (2), the ratio of the amount of the molybdenum source to the volume of the added water is 0.03125-0.04000 mol / L.

[0016] Furthermore, the molar ratio of the molybdenum source, sulfur source and nickel source in step (2) is 1:(4-6):(0.1-0.2), and the amount of the molybdenum source added in step (2) is 0.8-2.0 mmol.

[0017] Furthermore, the time of the hydrothermal reaction in step (2) is 18-24 hours, and the temperature of the hydrothermal reaction in step (2) is 190-210°C.

[0018] Furthermore, the carbon paper is washed with deionized water for 3-6 times in step (2); and the drying in step (2) is dried in a 60-80° C. forced air drying oven for 6-18 hours.

[0019] Furthermore, in step (3), the ratio of the amount of selenium powder to the volume of anhydrous ethanol added is 0.020-0.025 mol / L.

[0020] Furthermore, the molar ratio of the selenium powder to sodium borohydride in step (3) is 1:(1-1.3).

[0021] Furthermore, the volume of anhydrous ethanol added in step (3) is 20-25 mL; the volume of deionized water added in step (3) is 10-20 mL.

[0022] Furthermore, in step (3), the inert atmosphere is an atmosphere of nitrogen or argon.

[0023] Furthermore, the temperature of the solvent thermal reaction in step (4) is 180-210° C.; and the time of the solvent thermal reaction in step (4) is 3-5 h.

[0024] Furthermore, the carbon paper is taken out and washed clean in step (4) by washing with deionized water for 3-5 times; and the drying in step (4) is carried out in a 60-80° C. forced air drying oven for 6-18 hours.

[0025] The invention provides a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper and prepared by the preparation method.

[0026] The present invention also provides the use of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper in an electrocatalytic HER reaction.

[0027] Furthermore, the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper is used as a working electrode, mercury-mercuric oxide is used as a reference electrode, a graphite rod is used as a counter electrode, and a 1.0M potassium hydroxide solution is used as an electrolyte to carry out an electrocatalytic hydrogen evolution reaction (HER) in a three-electrode system.

[0028] The present invention has the following advantages and beneficial effects:

[0029] (1) The present invention prepares MoS2 co-doped with nickel and selenium supported on carbon paper through a two-step hydrothermal-solvothermal reaction, and the preparation method is simple and low-cost.

[0030] (2) In the preparation method provided by the present invention, nickel-selenium co-doped molybdenum disulfide is grown vertically in situ on carbon paper, and the edge active sites of the material are fully exposed; the co-doping of nickel and selenium is conducive to the generation of defects; the larger selenium atoms can expand the interlayer spacing of molybdenum disulfide and reduce stacking; these factors are conducive to the nickel-selenium co-doped molybdenum disulfide to exhibit good electrocatalytic hydrogen evolution performance.

[0031] (3) The present invention provides a new method for doping selenium in MoS2-based materials. Different from the previous method of doping selenium into MoS2 using high-temperature gas-solid phase reaction, the present invention first prepares a NaHSe solution and then successfully dopes selenium into MoS2-based materials by solvent thermal selenization. This method has the advantages of mild reaction conditions and environmental friendliness. The prepared Ni-Se co-doped MoS2 catalyst supported on carbon paper reaches 10 mA cm -2 The required overpotential is 130 mV less than that of MoS2. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the SEM characterization image of the washed carbon paper.

[0033] Figure 2 This is a SEM characterization image of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in Example 1.

[0034] Figure 3 This is the SEM-EDS characterization image of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in Example 1.

[0035] Figure 4 This is a TEM characterization image of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in Example 1. Figures a and b are morphology images of this Example 1; and Figure c is a HR-TEM image of this Example 1.

[0036] Figure 5 These are Raman characterization images of the nickel-selenium co-doped MoS2 catalyst loaded on carbon paper obtained in Example 1, the nickel-doped MoS2 catalyst loaded on carbon paper obtained in Comparative Example 1, the selenium-doped MoS2 catalyst loaded on carbon paper obtained in Comparative Example 2, and the MoS2 catalyst loaded on carbon paper obtained in Comparative Example 3.

[0037] Figure 6 The linear sweep voltammetry curves of the electrocatalytic hydrogen evolution reaction using the catalyst prepared in Examples 1-3 as the working electrode are shown.

[0038] Figure 7 The linear sweep voltammetry curves of electrocatalytic hydrogen evolution reaction using the catalysts prepared in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 as working electrodes are shown. DETAILED DESCRIPTION

[0039] The present invention is further explained below in conjunction with specific examples, and those skilled in the art can obtain a more comprehensive and thorough understanding of the invention through the examples. It should be noted that the equipment and reagents used in the experiment are not marked with the manufacturer and can all be purchased from the market.

[0040] A method for preparing clean carbon paper, the preparation method comprising the following steps:

[0041] (1) Cut the purchased carbon paper into a 1 cm × 3 cm rectangle.

[0042] (2) The rectangular carbon paper cut in step (1) is ultrasonically treated in acetone for 15 minutes, in anhydrous ethanol for 10 minutes, and in deionized water for 20 minutes to remove impurities and organic matter on the surface of the carbon paper.

[0043] (3) Collect the cleaned carbon paper for subsequent experiments.

[0044] Figure 1 The SEM image of the clean carbon paper obtained is Figure 1 The smooth surface of the washed carbon paper can be observed.

[0045] Example 1

[0046] This embodiment provides a method for preparing a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, the preparation method comprising the following steps:

[0047] (1) 1 mmol of sodium molybdate, 5 mmol of thiourea and 0.12 mmol of nickel nitrate hexahydrate were added to 30 mL of deionized water in sequence and stirred evenly. The solution was then transferred to a polytetrafluoroethylene-lined autoclave together with the cleaned carbon paper and placed in an oven for a hydrothermal reaction at 200 °C for 22 h.

[0048] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain Ni-MoS2 loaded on the carbon paper.

[0049] (3) Under nitrogen protection, add 0.5 mmol of selenium powder and 0.6 mmol of sodium borohydride to 20 mL of anhydrous ethanol and stir for 10 minutes. After sufficient reaction, add 15 mL of deionized water. Continue stirring until the solution turns wine red. This solution is NaHSe solution.

[0050] (4) The Ni-MoS2 loaded on the carbon paper in step (2) is placed in a polytetrafluoroethylene liner, the NaHSe solution obtained in step (3) is transferred to the polytetrafluoroethylene liner, and the solution is placed in an oven for a solvothermal reaction. The temperature of the solvothermal reaction is 200°C and the time of the solvothermal reaction is 4 hours.

[0051] (5) After the reaction is completed, the carbon black paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, which is labeled as Ni-Se-MoS2-1.

[0052] Example 2

[0053] This embodiment provides a method for preparing a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, the preparation method comprising the following steps:

[0054] (1) 0.8 mmol of ammonium molybdate, 3.2 mmol of thiourea and 0.08 mmol of nickel nitrate hexahydrate were added to 20 mL of deionized water in sequence and stirred evenly. The solution was then transferred to a polytetrafluoroethylene-lined autoclave together with the cleaned carbon paper and placed in an oven for a hydrothermal reaction at 190° C. for 24 h.

[0055] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water three times, and placed in a forced air drying oven at 60°C for 6 h to obtain Ni-MoS2 loaded on the carbon paper.

[0056] (3) Under argon protection, add 0.5 mmol of selenium powder and 0.5 mmol of sodium borohydride to 22 mL of anhydrous ethanol and stir for 15 minutes. After sufficient reaction, add 10 mL of deionized water. Continue stirring until the solution turns wine red. This solution is NaHSe solution.

[0057] (4) The Ni-MoS2 loaded on the carbon paper in step (2) is placed in a polytetrafluoroethylene liner, the NaHSe solution obtained in step (3) is transferred to the polytetrafluoroethylene liner, and the solution is placed in an oven for a solvothermal reaction. The temperature of the solvothermal reaction is 180°C, and the time of the solvothermal reaction is 3 hours.

[0058] (5) After the reaction is completed, the carbon black paper is taken out, washed with deionized water three times, and placed in a forced air drying oven at 60°C for 18 h to obtain a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, which is labeled as Ni-Se-MoS2-2.

[0059] Example 3

[0060] This embodiment provides a method for preparing a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, the preparation method comprising the following steps:

[0061] (1) 2 mmol potassium molybdate, 12 mmol thiourea and 0.4 mmol nickel chloride hexahydrate were added to 64 mL deionized water in sequence and stirred evenly. The solution was transferred to a polytetrafluoroethylene-lined autoclave together with clean carbon paper and placed in an oven for hydrothermal reaction at 210° C. for 18 hours.

[0062] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 6 times, and placed in a forced air drying oven at 80°C for 18 hours to obtain Ni-MoS2 loaded on the carbon paper.

[0063] (3) Under argon protection, add 0.50 mmol of selenium powder and 0.65 mmol of sodium borohydride to 25 mL of anhydrous ethanol and stir for 15 minutes. After sufficient reaction, add 20 mL of deionized water. Continue stirring until the solution turns wine red. This solution is NaHSe solution.

[0064] (4) The Ni-MoS2 loaded on the carbon paper in step (2) is placed in a polytetrafluoroethylene liner, and the NaHSe solution obtained in step (3) is transferred to the polytetrafluoroethylene liner, and placed in an oven for a solvothermal reaction. The temperature of the solvothermal reaction is 210°C, and the time of the solvothermal reaction is 5 hours.

[0065] (5) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 5 times, and placed in a forced air drying oven at 80°C for 6 h to obtain a nickel-selenium co-doped MoS2 catalyst supported on carbon paper, which is labeled as Ni-Se-MoS2-3.

[0066] Figure 2 The scanning electron microscope (SEM) image of the nickel-selenium co-doped MoS2 catalyst supported on carbon paper obtained in Example 1 is shown in FIG. Figure 2It can be seen that the prepared catalyst is evenly loaded on the surface of carbon paper. Figure 3 is a scanning electron microscope-energy spectrum (SEM-EDS) of the nickel-selenium co-doped MoS2 catalyst supported on carbon paper obtained in Example 1. Figure 3 The presence of four elements, Mo, S, Se and Ni, can be seen in the MgO, indicating the successful doping of Ni and Se elements. Figure 4 is a transmission electron microscope (TEM) image of the nickel-selenium co-doped MoS2 catalyst supported on carbon paper obtained in Example 1. Figure 4 As can be seen in Figure (c), defects exist, which are caused by nickel-selenium co-doping.

[0067] Comparative Example 1

[0068] This comparative example provides a method for preparing a nickel-doped molybdenum disulfide (Ni-MoS2) catalyst supported on carbon paper, the preparation method comprising the following steps:

[0069] (1) 1 mmol of sodium molybdate, 5 mmol of thiourea and 0.12 mmol of nickel nitrate hexahydrate were added to 30 mL of deionized water in sequence and stirred evenly. The solution was then transferred to a polytetrafluoroethylene-lined autoclave together with the cleaned carbon paper and placed in an oven for a hydrothermal reaction at 200 °C for 22 h.

[0070] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain Ni-MoS2 loaded on the carbon paper, which is marked as Ni-MoS2.

[0071] Comparative Example 2

[0072] This comparative example provides a method for preparing a selenium-doped MoS2 catalyst supported on carbon paper, the preparation method comprising the following steps:

[0073] (1) 1 mmol of sodium molybdate and 5 mmol of thiourea were added to 30 mL of deionized water in sequence, and after being stirred evenly, the solution and the cleaned carbon paper were transferred to a polytetrafluoroethylene-lined autoclave and placed in an oven for hydrothermal reaction at 200 °C for 22 h.

[0074] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain MoS2 loaded on the carbon paper.

[0075] (3) Under nitrogen protection, add 0.5 mmol of selenium powder and 0.6 mmol of sodium borohydride to 20 mL of anhydrous ethanol and stir for 10 minutes. After sufficient reaction, add 15 mL of deionized water. Continue stirring until the solution turns wine red. This solution is NaHSe solution.

[0076] (4) The MoS2 loaded on the carbon paper in step (2) is placed in a polytetrafluoroethylene liner, the NaHSe solution obtained in step (3) is transferred to the polytetrafluoroethylene liner, and the solution is placed in an oven for a solvothermal reaction. The temperature of the solvothermal reaction is 200°C and the time of the solvothermal reaction is 4 hours.

[0077] (5) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain selenium-doped MoS2 loaded on the carbon paper, which is labeled as Se-MoS2.

[0078] Comparative Example 3

[0079] This comparative example provides a method for preparing a catalyst of MoS2 supported on carbon paper, the preparation method comprising the following steps:

[0080] (1) 1 mmol of sodium molybdate and 5 mmol of thiourea were added to 30 mL of deionized water in sequence, and after being stirred evenly, the solution and the cleaned carbon paper were transferred to a polytetrafluoroethylene-lined autoclave and placed in an oven for hydrothermal reaction at 200 °C for 22 h.

[0081] (2) After the reaction is completed, the black carbon paper is taken out, washed with deionized water for 4 times, and placed in a forced air drying oven at 70°C for 10 h to obtain MoS2 loaded on the carbon paper, which is marked as MoS2.

[0082] The Raman characterization images of the Ni-Se-MoS2-1 catalyst loaded on carbon paper obtained in Example 1, the Ni-MoS2 catalyst loaded on carbon paper obtained in Comparative Example 1, the Se-MoS2 catalyst loaded on carbon paper obtained in Comparative Example 2, and the MoS2 catalyst loaded on carbon paper obtained in Comparative Example 3 are as follows: Figure 5 As shown, 406cm -1 and 377cm -1 Corresponding to the out-of-plane A of MoS2 1g With the in-plane E 2g The vibration mode indicates that the main phase composition of Comparative Examples 1 and 3 is 2HMoS2, while for Example 1 and Comparative Example 2, at 406 cm -1 and 377cm -1 The out-of-plane A of MoS2 appears 1g With the in-plane E 2gVibration mode, at 200-300cm -1 A Mo-Se related vibration mode appears in the low frequency region, which indicates that the selenium element has been successfully incorporated in Example 1 and Comparative Example 2.

[0083] Examples 1-3 and Comparative Examples 1-3 were used for electrocatalytic hydrogen evolution reaction.

[0084] The electrocatalytic hydrogen evolution reaction was carried out in an electrolytic cell of a three-electrode system, with the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 as working electrodes, mercury-mercuric oxide as reference electrodes, graphite rods as counter electrodes, and an electrolyte of 1.0 M KOH solution saturated with N2 (the solvent was deionized water). The scan rate of the linear sweep voltammetry curve was 2 mV / s.

[0085] Depend on Figure 6 It can be seen that Examples 1-3 have good HER catalytic performance. Figure 7 It can be obtained when reaching 10mA / cm 2 At a current density of 1.34 W, the overpotentials of Ni-Se-MoS2-1, Ni-MoS2, Se-MoS2 and MoS2 are 102 mV, 155 mV, 168 mV and 232 mV respectively. This indicates that nickel-selenium co-doping can effectively improve the hydrogen evolution performance of MoS2.

[0086] Finally, it should be added that the description of the above embodiments and related drawings is only used to explain the present invention rather than to limit the present invention. Any changes, equivalent substitutions, modifications, etc. made by relevant researchers in the field without departing from the spirit of the present invention should fall within the protection scope of the present invention.

Claims

1. A method for preparing a nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper, characterized in that: The steps include: (1) Carbon paper pretreatment: The carbon paper is ultrasonically treated in acetone, ethanol solution and water in turn to remove impurities and organic matter on the surface of the carbon paper to obtain clean carbon paper; (2) Preparation of nickel-doped molybdenum disulfide: a molybdenum source, a sulfur source and a nickel source are added to water in sequence, stirred evenly to obtain a mixed solution, and the cleaned carbon paper in step (1) is placed in the mixed solution for hydrothermal reaction. After the reaction is completed, the carbon paper is washed and dried to obtain Ni-MoS2 loaded on the carbon paper; the molar ratio of the molybdenum source, the sulfur source and the nickel source is 1:(4-6):(0.1-0.2), (3) Preparation of NaHSe solution: In an inert atmosphere, add selenium powder and sodium borohydride to anhydrous ethanol and stir. After sufficient reaction, add water and continue stirring to obtain a NaHSe solution; the molar ratio of the selenium powder to sodium borohydride is 1:(1-1.3); (4) Solvothermal selenization: The Ni-MoS2 loaded on the carbon paper in step (2) is placed in the NaHSe solution obtained in step (3) for a solvothermal reaction. After the reaction is completed, the carbon paper is taken out, washed, and dried to obtain a nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper; the temperature of the solvothermal reaction is 180-210°C; the time of the solvothermal reaction is 3-5h.

2. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: The molybdenum source in step (2) is one or more of sodium molybdate, ammonium molybdate, and potassium molybdate; the sulfur source in step (2) is thiourea; the nickel source in step (2) is one or more of nickel chloride hexahydrate, nickel nitrate hexahydrate, and nickel acetylacetonate.

3. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: In step (2), the ratio of the amount of the molybdenum source to the volume of the added water is 0.03125-0.04000 mol / L.

4. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: The temperature of the hydrothermal reaction in step (2) is 190-210° C.; the time of the hydrothermal reaction in step (2) is 18-24 hours.

5. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: The step (2) of washing the carbon paper is washing it with deionized water for 3-6 times; the step (2) of drying is drying it in a forced air drying oven at 60-80°C for 6-18 hours.

6. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: In step (3), the ratio of the amount of the selenium powder to the volume of the added anhydrous ethanol is 0.020-0.025 mol / L, the ratio of the amount of the selenium powder to the volume of the added water is 0.025-0.050 mol / L, and the inert atmosphere is a nitrogen or argon atmosphere.

7. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper according to claim 1, characterized in that: The carbon paper is taken out and washed in step (4) by washing with deionized water for 3-5 times; the drying in step (4) is carried out in a forced air drying oven at 60-80° C. for 6-18 hours.

8. The nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the nickel-selenium co-doped molybdenum disulfide catalyst supported on carbon paper as claimed in claim 8 in an electrocatalytic hydrogen evolution reaction.

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