Metal nitrogen-doped carbon catalyst, preparation method thereof and application of metal nitrogen-doped carbon catalyst in hydrogen evolution reaction

Abstract

The invention provides a metal nitrogen-doped carbon catalyst, a preparation method thereof and application of the metal nitrogen-doped carbon catalyst in a hydrogen evolution reaction, and relates to the technical field of hydrogen evolution catalysts. The method provided by the invention comprises the following steps: stirring and dissolving a transition metal salt, an organic nitrogen source and a morphology regulating agent in a solvent, evaporating to dryness of the solvent, grinding, and carbonizing at 800-1000 DEG C to obtain the metal nitrogen-doped carbon catalyst in the form of a two-dimensional nanosheet. The organic nitrogen source and the morphology regulating agent are mixed and then subjected to one-step pyrolysis, nitrogen doping, porous structure construction and confinement packaging of transition metal element particles can be achieved, and therefore the catalyst with high catalytic activity and ultra-long service life is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen evolution catalysts, and particularly to a metal-nitrogen-doped carbon catalyst, a preparation method thereof, and an application thereof in hydrogen evolution reaction. Background Art

[0002] As a core carrier for green energy transformation, high-efficiency and low-cost production technology of hydrogen energy is the key. Hydrogen production by electrolyzing water has become the mainstream technical route due to advantages such as environmental friendliness and high product purity. Among them, the kinetic performance of the hydrogen evolution reaction (HER) directly affects the overall efficiency. In an alkaline electrolysis system, HER needs to undergo multiple steps of water dissociation and hydrogen adsorption / desorption reactions, resulting in a significantly higher overpotential than in an acidic system. There is an urgent need to develop non-precious metal electrocatalysts with both high activity and durability to replace scarce platinum-based materials.

[0003] In recent years, transition metal and nitrogen co-doped carbon-based composites (M-N-C) have become a research hotspot due to their tunable electronic structure, abundant active sites, and good electrical conductivity. By introducing transition metals (such as Fe, Co, Ni, etc.) to synergistically interact with the nitrogen-doped carbon support, the adsorption energy of hydrogen intermediates can be effectively optimized and charge transfer can be accelerated. However, the existing technologies still have the following limitations: Firstly, traditional preparation methods mostly rely on complex template methods or post-modification processes, with cumbersome steps and difficulty in precisely regulating active sites; Secondly, a single metal system is difficult to systematically reveal the optimization mechanism of metal types on the interfacial electronic structure, resulting in a lack of general guiding principles for catalyst design; Thirdly, conventional carbon supports are prone to embedding active sites due to insufficient porosity or structural collapse, and metal particles are prone to agglomeration or dissolution during long-term operation, severely restricting catalytic stability.

[0004] In response to the above problems, existing technologies have tried to improve performance through porous structure design or heteroatom doping, but still face the challenge of being difficult to balance activity and stability. For example, some methods increase the specific surface area by introducing pore-forming agents, but the conductive network of the carbon skeleton is damaged due to excessive etching; Another some solutions enhance the metal-support interaction by using nitrogen doping, but are limited by the compatibility of metal precursors and pyrolysis processes, and it is difficult to achieve flexible adaptation of multiple transition metals. Therefore, there is an urgent need to provide a solution to improve the above problems. Summary of the Invention

[0005] The purpose of the present invention is to provide a metal-nitrogen-doped carbon catalyst, a preparation method thereof, and an application thereof in hydrogen evolution reaction.

[0006] In the first aspect, a preparation method of a metal-nitrogen-doped carbon catalyst provided by the present invention includes stirring and dissolving a transition metal salt, an organic nitrogen source, and a morphology regulator in a solvent, then evaporating the solvent, grinding, and carbonizing at 800°C - 1000°C to obtain a metal-nitrogen-doped carbon catalyst in the form of two-dimensional nanosheets.

[0007] Optionally, the transition metal salt includes one of nitrate, acetate, chloride, and ammonium salt.

[0008] Optionally, the transition metal element in the transition metal salt includes one of cobalt, nickel, molybdenum, and iron.

[0009] Optionally, the organic nitrogen source includes one of urea, dicyandiamide, and melamine.

[0010] Optionally, the morphology regulator includes one of polyethylene glycol, Triton X-100, and polyvinyl alcohol.

[0011] Optionally, the solvent includes deionized water.

[0012] Optionally, the mass ratio of the transition metal salt to the organic nitrogen source is (0.5 - 1.5):(4 - 6).

[0013] Optionally, the mass ratio of the organic nitrogen source to the morphology regulator is (4 - 6):(0.3 - 0.7).

[0014] Optionally, after stirring and dissolving, it is evaporated to dryness at 80°C - 100°C.

[0015] Optionally, it includes the following steps: stirring and dissolving the transition metal salt, the organic nitrogen source, and the morphology regulator in a solvent to obtain a precursor solution; grinding the precursor solution after evaporation to dryness to obtain an intermediate; carbonizing the intermediate in an inert atmosphere at 800°C - 1000°C to obtain a metal-nitrogen-doped carbon catalyst.

[0016] Optionally, the metal particle size of the metal-nitrogen-doped carbon catalyst is 3nm - 60nm.

[0017] Optionally, the precursor solution is evaporated to dryness and the solvent is recovered.

[0018] Optionally, the inert atmosphere includes one of nitrogen, helium, neon, and argon.

[0019] Optionally, carbonization is carried out in an inert atmosphere of 0.1MPa - 0.5MPa.

[0020] Optionally, the intermediate is heated to 800°C - 1000°C at a rate of 5°C / min - 10°C / min.

[0021] Optionally, carbonization treatment is carried out at 800°C - 1000°C for 1h - 3h.

[0022] Optionally, the precursor solution is evaporated to dryness at 80°C - 100°C.

[0023] Optionally, after grinding, it is pre-carbonized at 300°C - 500°C to obtain an intermediate.

[0024] Second aspect, the present invention also provides a metal-nitrogen-doped carbon catalyst prepared by any of the above optional preparation methods.

[0025] Third aspect, the present invention also provides an application of a metal-nitrogen-doped carbon catalyst prepared by any of the above optional preparation methods in a hydrogen evolution reaction.

[0026] Fourth aspect, the present invention also provides a hydrogen evolution electrode loaded with a metal-nitrogen-doped carbon catalyst prepared by any of the above optional preparation methods. Description of the Drawings

[0027] Figure 1 is a flowchart of a preparation method of a metal-nitrogen-doped carbon catalyst provided by the present invention;

[0028] Figure 2 is a diffraction pattern of the metal-nitrogen-doped carbon catalyst prepared in Example 1 of the present invention;

[0029] Figure 3 is a diffraction pattern of the metal-nitrogen-doped carbon catalyst prepared in Example 2 of the present invention;

[0030] Figure 4 is a diffraction pattern of the metal-nitrogen-doped carbon catalyst prepared in Example 3 of the present invention;

[0031] Figure 5 is a diffraction pattern of the metal-nitrogen-doped carbon catalyst prepared in Example 4 of the present invention;

[0032] Figure 6 is an N1s XPS peak fitting spectrum of the metal-nitrogen-doped carbon catalysts prepared in Examples 1 to 4 of the present invention;

[0033] Figure 7 is an LSV curve graph of the metal-nitrogen-doped carbon catalysts prepared in Examples 1 to 4 of the present invention during an electrochemical hydrogen evolution process;

[0034] Figure 8 is a transmission electron microscope image of the metal-nitrogen-doped carbon catalysts prepared in Examples 1 to 4 of the present invention;

[0035] Figure 9 is a long-term cycling stability test graph of the metal-nitrogen-doped carbon catalyst prepared in Example 1 of the present invention. Detailed Embodiments

[0036] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein shall have the ordinary meanings as understood by those of ordinary skill in the art to which the present invention pertains.

[0037] The present invention provides a method for preparing a metal-nitrogen-doped carbon catalyst, comprising: stirring and dissolving a transition metal salt, an organic nitrogen source and a morphology regulator in a solvent, then evaporating the solvent to dryness, grinding, and carbonizing at 800°C - 1000°C to obtain a metal-nitrogen-doped carbon catalyst in the form of two-dimensional nanosheets. In fact, by mixing the organic nitrogen source and the morphology regulator and performing one-step pyrolysis, nitrogen doping, porous structure construction, and confinement encapsulation of transition metal element particles can be achieved, thereby preparing a catalyst (M / NC) with high catalytic activity and ultra-long lifespan.

[0038] Specifically, the transition metal element in the transition metal salt used in preparing the metal-nitrogen-doped carbon catalyst includes one of cobalt, nickel, molybdenum, and iron. In fact, by adjusting the type of transition metal element, the electronic structure of the catalyst can be regulated to meet the requirements of different working conditions. In addition, multiple different transition metal elements can be used in combination, so that different metal pure phases and / or composite phases can be formed in the catalyst.

[0039] For example, when the transition metal element is cobalt or nickel, cobalt nanoparticle pure phase or nickel nanoparticle pure phase can be formed in the catalyst during pyrolysis. When the transition metal element is iron, part of the iron element forms Fe3C with carbon and further forms an Fe-Fe3C composite shell during pyrolysis. When the transition metal element is molybdenum, Mo2C particles are formed during pyrolysis.

[0040] In some embodiments, the transition metal salt used includes one of nitrates, acetates, chlorides, and ammonium salts. Specifically, the transition metal salt can be iron nitrate, cobalt nitrate, nickel nitrate, or ammonium molybdate. In fact, the transition metal salt used must be able to completely dissolve in the solvent. By dissolving the transition metal salt to form a homogeneous solution, it is beneficial to form a uniform composite after evaporation to dryness. Specifically, the solvent used includes deionized water.

[0041] In some embodiments, the organic nitrogen source used includes one of urea, dicyandiamide, and melamine. In fact, during pyrolysis, the organic nitrogen source can not only provide nitrogen elements to bond with carbon elements to form C-N bonds, but also act as a pore-forming agent to form a porous structure.

[0042] Specifically, the organic nitrogen source is preferably urea, which can generate gases such as ammonia and carbon dioxide during pyrolysis. Through gas etching, a through mesoporous structure can be formed in the carbon layer. At the same time, urea can generate reducing substances to reduce the transition metal salt.

[0043] In some embodiments, the morphology regulator used includes one of polyethylene glycol, Triton X-100, and polyvinyl alcohol. In fact, the purpose of adding the morphology regulator is to directionally induce the formation of two-dimensional nanosheet structures during pyrolytic carbonization.

[0044] Specifically, the morphology regulator is preferably polyethylene glycol, which can complex with metal ions through hydrogen bonding to inhibit the local crystallization of metal salts and ensure the uniform dispersion of metal species within the carbon framework. Further, the polyethylene glycol can be PEG-2000.

[0045] In some embodiments, the mass ratio of the transition metal salt to the organic nitrogen source is (0.5 - 1.5):(4 - 6). In fact, by adjusting the amounts of the transition metal salt and the organic nitrogen source, a metal nanoparticle confined encapsulation structure with a porous structure and nitrogen doping can be constructed in one step during pyrolysis. In addition, the mass ratio of the organic nitrogen source to the morphology regulator is (4 - 6):(0.3 - 0.7), which is beneficial for directionally inducing two-dimensional nanosheet-like catalysts during pyrolysis.

[0046] In fact, referring to Figure 1 , the preparation method provided by the present invention includes the following steps:

[0047] S1. Stir and dissolve the transition metal salt, the organic nitrogen source, and the morphology regulator in a solvent to obtain a precursor solution;

[0048] S2. After evaporating the precursor solution, grind it to obtain an intermediate;

[0049] S3. Carbonize the intermediate in an inert atmosphere at 800°C - 1000°C to obtain a metal-nitrogen-doped carbon catalyst. In fact, by preparing a precursor solution from the transition metal salt, the organic nitrogen source, and the morphology regulator in step S1, it is beneficial for the three substances to be uniformly mixed in the solution environment, thereby improving the uniform dispersion of nitrogen elements and transition metal elements in the prepared catalyst and being beneficial for improving the catalytic activity of the catalyst.

[0050] In some embodiments, when performing steps S1 and S2, after stirring and dissolving the transition metal salt, the organic nitrogen source, and the morphology regulator in a solvent, evaporate and recover the solvent at 80°C - 100°C for reuse. In fact, during the stirring and dissolving process, common promotion methods in the art, such as heating and stirring, can be used to improve the dissolution rate.

[0051] In some embodiments, after performing step S2 to evaporate the precursor solution and grind it, the dried precursor powder has a porous preformed structure, which is conducive to providing an active site anchoring basis during the subsequent pyrolysis process. In fact, a gel-like substance can be obtained after evaporating the precursor solution, and the gel-like substance can be continuously dried.

[0052] In some embodiments, after evaporating and grinding in step S2 to obtain an intermediate. In fact, by performing the grinding treatment, the specific surface area of the intermediate can be increased, and more defects can be introduced on the surface, which is conducive to providing an active site anchoring basis during the pyrolysis process.

[0053] In some embodiments, when performing step S2, after grinding, a pre-carbonization treatment is carried out at 300°C - 500°C to obtain an intermediate. In fact, by performing the pre-carbonization treatment at 300°C - 500°C, a carbon nanosheet prototype can be formed. In addition, when polyethylene glycol is used as a morphology regulator, polyethylene glycol can pyrolyze to generate reducing gases within this temperature range, thereby preliminarily reducing the transition metal salt.

[0054] In some embodiments, the inert atmosphere used when performing step S3 includes one of nitrogen and argon. In fact, using an inert atmosphere is conducive to the pyrolysis of the organic nitrogen source and the morphology regulator at high temperature. In addition, the pre-carbonization can also be carried out under an inert atmosphere. Specifically, the pressure of the inert atmosphere used is 0.1MPa - 0.5MPa.

[0055] In some embodiments, when performing step S3, the intermediate is heated to 800°C - 1000°C at a rate of 5°C / min - 10°C / min and carbonized at 800°C - 1000°C for 1h - 3h. In fact, when urea is used as the organic nitrogen source, urea generates reducing species at 800°C - 1000°C, thereby reducing the transition metal salt. At the same time, during the high-temperature process, some types of transition metals can bond with carbon to form composite particles.

[0056] The present invention also provides a metal-nitrogen-doped carbon catalyst prepared by any of the above embodiments, whose morphology is metal nanoparticles supported on nitrogen-doped carbon nanosheets and the size of the metal nanoparticles is 3nm - 60nm.

[0057] The present invention also provides an application of the metal-nitrogen-doped carbon catalyst prepared by any of the above embodiments in the hydrogen evolution reaction. Specifically, the application in the alkaline hydrogen evolution reaction. In fact, the present invention also provides a hydrogen evolution electrode loaded with the metal-nitrogen-doped carbon catalyst prepared by any of the above embodiments. Further, the metal-nitrogen-doped carbon catalyst can be coated and solidified on the electrode substrate to form a hydrogen evolution electrode. Specifically, the electrode substrate can include a glassy carbon electrode, carbon paper, and nickel mesh.

[0058] Example 1

[0059] Example 1 provides a method for preparing a metal-nitrogen-doped carbon catalyst, comprising the following steps:

[0060] S1. Add 0.582 g of cobalt nitrate hexahydrate, 5 g of urea and 0.5 g of polyethylene glycol (PEG-2000) into 50 mL of deionized water, stir and dissolve to obtain a purple homogeneous precursor solution;

[0061] S2. Continuously heat the precursor solution on a heating table at 90 °C until it is evaporated to dryness to obtain a purple gel solid, grind and crush the solid to obtain an intermediate;

[0062] S3. Place the intermediate in a tubular furnace under a nitrogen atmosphere, heat it to 900 °C at a rate of 5 °C / min and keep it calcined at a constant temperature for 2 h, then cool it to room temperature with the furnace to obtain a metal-nitrogen-doped carbon catalyst (Co / NC).

[0063] Example 2

[0064] Example 2 provides a method for preparing a metal-nitrogen-doped carbon catalyst, which is different from Example 1 in that in step S1, 0.582 g of nickel nitrate hexahydrate, 5 g of urea and 0.5 g of polyethylene glycol (PEG-2000) are added into 50 mL of deionized water; in step S3, a metal-nitrogen-doped carbon catalyst (Ni / NC) is obtained.

[0065] Example 3

[0066] Example 3 provides a method for preparing a metal-nitrogen-doped carbon catalyst, which is different from Example 1 in that in step S1, 0.352 g of ammonium molybdate tetrahydrate, 5 g of urea and 0.5 g of polyethylene glycol (PEG-2000) are added into 50 mL of deionized water; in step S3, a metal-nitrogen-doped carbon catalyst (Mo2C / NC) is obtained.

[0067] Example 4

[0068] Example 4 provides a method for preparing a metal-nitrogen-doped carbon catalyst, which is different from Example 1 in that in step S1, 0.828 g of ferric nitrate nonahydrate, 5 g of urea and 0.5 g of polyethylene glycol (PEG-2000) are added into 50 mL of deionized water; in step S3, a metal-nitrogen-doped carbon catalyst (Fe-Fe3C / NC) is obtained.

[0069] The metal-nitrogen-doped carbon catalysts prepared in Examples 1 to 4 are characterized by XRD, as shown respectively in Figures 2 to 5 as follows

[0070] From Figure 2It can be seen that the characteristic peaks appearing at 44.3°, 51.6°, and 76.1° correspond to the (111), (200), and (220) crystal planes of face-centered cubic metallic cobalt (JCPDS 15-0806), respectively. This indicates that the metallic cobalt nanoparticles in the Co / NC catalyst prepared in Example 1 have high crystallinity and no impurity phase.

[0071] From Figure 3 it can be seen that the characteristic peaks appearing at 44.3°, 51.6°, and 76.1° correspond to the (111), (200), and (220) crystal planes of face-centered cubic metallic nickel (JCPDS 89-7128), respectively. This indicates the high crystallinity of the metallic nickel nanoparticles in the Ni / NC catalyst prepared in Example 2, and no other impurity phase is detected. This shows that the method provided by the present invention can effectively achieve the formation of pure-phase nickel nanoparticles.

[0072] From Figure 4 it can be seen that the characteristic peaks appearing at 34.4°, 38.0°, and 39.4° correspond to the (100), (002), and (101) crystal planes of hexagonal Mo2C (JCPDS 35-0787), respectively. This indicates that ammonium molybdate reacts with carbon at high temperature in Example 3 to form pure-phase Mo2C nanoparticles.

[0073] From Figure 5 it can be seen that the characteristic peaks appearing at 44.7° and 65.0° correspond to the (110) and (200) crystal planes of body-centered cubic metallic iron (JCPDS 89-4186), respectively, while the peaks at 45.8° and 49.1° correspond to the (121) and (210) crystal planes of the Fe3C phase (JCPDS 03-411). This indicates that Fe-Fe3C composite nanoparticles are formed during the high-temperature pyrolysis process in Example 4.

[0074] The N1s XPS analysis and peak fitting were performed on the metal-nitrogen-doped carbon catalysts prepared in Examples 1 to 4, as shown in Figure 6 a to d respectively. From Figure 6 it can be seen that there is a metal-nitrogen (M-N x ) bonding structure in the catalysts of Examples 1 to 4. This shows that the method provided by the present invention can successfully construct a strong interaction by forming metal-nitrogen bonds through one-step pyrolysis. In this way, the migration and aggregation of metal particles can be effectively inhibited, and the hydrogen adsorption free energy can be optimized through electron transfer, thus providing a key guarantee for the high stability of the catalyst.

[0075] The linear sweep voltammetry (LSV) curves of the catalysts in Examples 1 to 4 during hydrogen evolution were tested in a 1 mol / L KOH solution using a three-electrode system (a glassy carbon electrode (5 mm in diameter) as the working electrode; a carbon rod as the counter electrode; Hg / HgO (1 M KOH) as the reference electrode), as Figure 7 shown. It can be seen from Figure 7 that the overpotential of the catalyst prepared in Example 1 is the lowest (230 mV) at a current density of 10 mA / cm 2 , significantly lower than that of Example 2 (276 mV), Example 3 (295 mV), and Example 4 (304 mV), indicating that the cobalt-based catalyst has excellent hydrogen evolution activity.

[0076] The prepared metal-nitrogen-doped carbon catalysts in Examples 1 to 4 were characterized by transmission electron microscopy, as described in a to d of Figure 8 respectively. It can be seen from Figure 8 a that metal cobalt nanoparticles with an average particle size of 16.4 nm are uniformly embedded in nitrogen-doped carbon nanosheets; it can be seen from Figure 8 b that metal nickel nanoparticles with an average particle size of 34.2 nm are dispersed in the carbon carrier; it can be seen from Figure 8 c that ultrafine Mo2C nanoparticles with an average particle size of 4.4 nm are densely distributed in ultrathin carbon nanosheets; it can be seen from Figure 8 d that Fe-Fe3C composite particles with an average particle size of 28.5 nm are surrounded by a carbon layer; in addition, it can be seen from Figure 8 that the catalysts provided by the present invention all exhibit a two-dimensional porous nanosheet structure.

[0077] The long-term cycling stability of the metal-nitrogen-doped carbon catalyst prepared in Example 1 was tested in a 1 mol / L KOH solution using a three-electrode system (a glassy carbon electrode (5 mm in diameter) as the working electrode; a carbon rod as the counter electrode; Hg / HgO (1 M KOH) as the reference electrode). The curve of the current density versus time at a constant overpotential (240 mV, vs. RHE) during the test is shown in Figure 9 . It can be seen from Figure 9 that the current density retention rate exceeds 95% after continuous operation for 135 h, indicating that the confinement effect of the nitrogen-doped carbon layer on cobalt nanoparticles significantly improves the durability of the catalyst, thus meeting the long-term operation requirements of industrial water electrolysis devices.

[0078] Although the embodiments of the present invention have been described in detail above, it is obvious to those skilled in the art that various modifications and changes can be made to these embodiments. However, it should be understood that such modifications and changes are all within the scope and spirit of the present invention described in the claims. Moreover, the present invention described herein can have other embodiments and can be implemented or realized in various ways.

Claims

1. A method for preparing a metal nitrogen-doped carbon catalyst, characterized in that: The method comprises stirring and dissolving a transition metal salt, an organic nitrogen source and a morphology regulator in a solvent, evaporating the solvent, grinding the mixture and carbonizing the mixture at 800-1000°C to obtain a metal nitrogen-doped carbon catalyst in the form of a two-dimensional nanosheet.

2. The preparation method according to claim 1, characterized in that: The transition metal salt includes one of nitrate, acetate, chloride, and ammonium salt; and / or the transition metal element in the transition metal salt includes one of cobalt, nickel, molybdenum, and iron.

3. The preparation method according to claim 1, characterized in that: The organic nitrogen source includes one of urea, dicyandiamide and melamine; and / or the morphology regulator includes one of polyethylene glycol, Triton X-100 and polyvinyl alcohol; and / or the solvent includes deionized water.

4. The preparation method according to claim 1, characterized in that: The mass ratio of the transition metal salt to the organic nitrogen source is (0.5-1.5):(4-6); and / or, the mass ratio of the organic nitrogen source to the morphology control agent is (4-6):(0.3-0.7); and / or, after stirring and dissolving, the mixture is evaporated to dryness at 80°C-100°C.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The following steps are involved: A transition metal salt, an organic nitrogen source and a morphology regulator are stirred and dissolved in a solvent to obtain a precursor solution; the precursor solution is evaporated and then ground to obtain an intermediate; and the intermediate is carbonized under an inert atmosphere at 800° C.-1000° C. to obtain a metal nitrogen-doped carbon catalyst.

6. The preparation method according to claim 5, characterized in that: The metal particle size range of the metal nitrogen-doped carbon catalyst is 3nm-60nm; and / or, the precursor solution is evaporated and the solvent is recovered; and / or, the inert atmosphere includes one of nitrogen, helium, neon, and argon; and / or, carbonization is carried out under an inert atmosphere of 0.1MPa-0.5MPa.

7. The preparation method according to claim 5, characterized in that: The intermediate is heated to 800-1000°C at a rate of 5-10°C / min; and / or, carbonized at 800-1000°C for 1-3h; and / or, the precursor solution is evaporated at 80-100°C; and / or, after grinding, pre-carbonized at 300-500°C to obtain the intermediate.

8. A metal nitrogen-doped carbon catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the metal nitrogen-doped carbon catalyst prepared by the preparation method according to any one of claims 1 to 7 in a hydrogen evolution reaction.

10. A hydrogen evolution electrode, characterized in that: The catalyst is loaded with a metal nitrogen-doped carbon catalyst prepared by the preparation method according to any one of claims 1 to 7 or a metal nitrogen-doped carbon catalyst according to claim 8.

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