Polymetallic sulfide electrocatalysts, methods of preparation, and applications

Abstract

The embodiment of the present application discloses a multimetallic sulfide electrocatalyst, a preparation method and application. The preparation method comprises the following steps: S1, a solution containing a first transition metal salt and a second transition metal salt is mixed with an organic ligand solution to obtain a first mixed solution; wherein the first transition metal salt and the second transition metal salt are XY with the same acid radical ion and different cations, X is Co, Fe, Ni, Mn, Zn or Cu, and Y is NO3 2‑ , Cl ‑ or SO4 2‑ ; a foam nickel is immersed in the first mixed solution to react to obtain a bimetallic MOF; S2, the bimetallic MOF is immersed in a second mixed solution to carry out a double excessive metal ion doping / replacement reaction, and a multimetallic hydroxide nanostructure is grown on the bimetallic MOF; wherein the second mixed solution contains a third transition metal salt and a fourth transition metal salt different from the first transition metal salt and the second transition metal salt; S3, the multimetallic hydroxide nanostructure is sulfur-doped to obtain a nitrogen-doped carbon loaded multimetallic sulfide electrocatalyst.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalyst technology, specifically relating to polymetallic sulfide electrocatalysts, their preparation methods, and applications. Background Technology

[0002] Urea is a ubiquitous basic metabolite found in nature, abundant in agricultural environments and industrial wastewater. Utilizing advanced electrocatalysis technology to convert biomass resources and industrial wastewater into valuable substances is crucial for environmental protection and promoting sustainable energy pathways. However, the slow kinetics and high overpotentials of the electrochemical processes in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR) significantly hinder the achievement of high energy efficiency and power output in various related applications. Therefore, ideal electrocatalysts with high activity, high stability, and low cost are extremely important for accelerating the redox kinetics of electrochemical processes.

[0003] Currently existing trifunctional catalysts for HER, OER, and UOR include noble metal-based catalysts, layered hydroxide catalysts, carbon-based catalysts, and transition metal-based catalysts. Noble metal-based catalysts exhibit excellent performance, but their high cost hinders their application; layered hydroxide catalysts have insufficient conductivity, which is detrimental to electron transport in the products; carbon-based materials are easily oxidized during high-current reactions, reducing current efficiency; transition metal-based materials have been extensively studied and show promising application prospects, but their structural instability leads to a significant performance degradation after a period of use, making them unsuitable for practical applications. Summary of the Invention

[0004] In view of this, some embodiments disclose a method for preparing polymetallic sulfide electrocatalysts, including the following steps:

[0005] S1, Preparation of bimetallic MOFs;

[0006] A solution containing a first transition metal salt and a second transition metal salt is mixed with an organic ligand solution to obtain a first mixed solution; wherein the first transition metal salt and the second transition metal salt are XY of the same anion but different cations, where X is Co, Fe, Ni, Mn, Zn or Cu, and Y is NO3. 2- Cl - or SO4 2- ;

[0007] Nickel foam is immersed in a first mixed solution to react and obtain a bimetallic MOF grown on nickel foam;

[0008] S2. The bimetallic MOF grown on nickel foam is immersed in a second mixed solution to undergo a doping / substitution reaction of two transition metal ions, resulting in the growth of a multimetal hydroxide nanostructure on the bimetallic MOF. The second mixed solution contains a third and a fourth transition metal salt, different from the first and second transition metal salts. The third and fourth transition metal salts are XY, representing the same anion but different cations, where X is Co, Fe, Ni, Mn, Zn, or Cu, and Y is NO3. 2- Cl - or SO4 2- ;

[0009] S3. Sulfide doping of multimetal hydroxide nanostructures yields nitrogen-doped carbon-supported multimetal sulfide electrocatalysts.

[0010] Furthermore, in the preparation method of the multi-metal sulfide electrocatalyst disclosed in some embodiments, in step S1, the molar concentration ratio of the first transition metal salt to the second transition metal salt in the first mixed solution is 2:3-5, the molar concentration of the organic ligand solution is 0.2-0.4M, and the reaction time of the nickel foam in the first mixed solution is 2-6h.

[0011] In some embodiments of the preparation method of polymetallic sulfide electrocatalysts, in step S2, the concentration ratio of the third transition metal salt to the fourth transition metal salt in the second mixed solution is 3:1 to 4.

[0012] In some embodiments, the preparation method of polymetallic sulfide electrocatalysts disclosed includes step S2, in which the polymetallic hydroxide nanostructure is nanoparticle, nanosheet, nanowire, or nanocluster.

[0013] In some embodiments, the preparation method of polymetallic sulfide electrocatalysts is disclosed. In step S2, the doping / substitution reaction is carried out at 15-40°C for 30-120 min, and then the obtained sample is vacuum dried at 60-90°C to grow polymetallic hydroxide nanostructures on bimetallic MOF.

[0014] In some embodiments, the preparation method of the multi-metal sulfide electrocatalyst is disclosed. In step S3, the multi-metal hydroxide nanostructure is sulfided and doped with dopants C2H5SH, S(CH3)2 or C2H5NS to obtain a nitrogen-doped carbon-supported multi-metal sulfide electrocatalyst.

[0015] In some embodiments, the preparation method of the polymetallic sulfide electrocatalyst is disclosed. In step S3, the sulfide doping includes: immersing the polymetallic hydroxide nanostructure in a dopant alcohol solution with a concentration of 0.25 to 1 mg / mL, hydrothermally heating the reaction at 60 to 200°C for 3 to 15 hours, cooling down, and drying.

[0016] In some embodiments, the preparation method of polymetallic sulfide electrocatalysts is disclosed, in step S3, the solvent of the alcohol solution is methanol, ethanol or propanol.

[0017] On the other hand, some embodiments disclose polymetallic sulfide electrocatalysts obtained by the preparation method of polymetallic sulfide electrocatalysts disclosed in the embodiments of the present invention.

[0018] On the other hand, some embodiments disclose the application of polymetallic sulfide catalysts as electrocatalysts for hydrogen evolution reaction, oxygen evolution reaction or urea oxidation reaction.

[0019] The nitrogen-doped carbon-supported multimetal sulfide electrocatalyst prepared by the method disclosed in this invention exhibits a stable structure. The three-dimensional nickel foam provides a porous structure, which not only facilitates contact between the catalyst and reactants but also gas transport. Sulfide nanoclusters are stably anchored on the nickel foam, maintaining a low urea oxidation overpotential. It also possesses excellent urea catalytic performance, high electron transport efficiency, and ultra-long stability, exhibiting ultra-stable performance that meets the demands of industrial applications. It displays three catalytic activities: HER, OER, and UOR, with low overpotentials for HER, OER, and UOR. Therefore, it can be used in various application fields, such as as a catalyst for water electrolysis to produce hydrogen and oxygen, and for urea degradation in environmental remediation. This multifunctionality gives metal sulfide electrocatalysts broad potential in practical applications and allows them to adapt to diverse needs. Furthermore, transition metals are abundant in the Earth's crust, inexpensive, and the preparation method is simple, making it highly scalable for the preparation and utilization of multimetal sulfide electrocatalysts. Attached Figure Description

[0020] Figure 1 Flowchart of the preparation of the polymetallic sulfide catalyst in Example 1;

[0021] Figure 2 SEM image of CoZn-MOF in Example 1;

[0022] Figure 3 SEM image of NiFe-CoZn-LDH in Example 1;

[0023] Figure 4 SEM image of NiFeCoZn-S / NC in Example 1;

[0024] Figure 5 LSV curve of NiFeCoZn-S / NC subjected to HER test in Example 1;

[0025] Figure 6LSV curve of NiFeCoZn-S / NC subjected to OER test in Example 1;

[0026] Figure 7 LSV curve of NiFeCoZn-S / NC subjected to UOR test in Example 1;

[0027] Figure 8 In Example 1, NiFeCoZn-S / NC was tested at 10 mA·cm⁻¹. -2 Stability test results at current density. Detailed Implementation

[0028] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in these embodiments of the invention, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in these embodiments is merely for describing particular implementations and is not intended to limit the scope of the disclosure of these embodiments.

[0029] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of this invention pertain; other experimental methods and technical means not specifically noted in the embodiments of this invention refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0030] The terms “basic” and “approximately” used in this document are to describe small fluctuations. For example, they can mean less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. Numerical data presented or expressed in range format in this document are used for convenience and brevity only, and should therefore be flexibly interpreted to include not only the explicitly listed values ​​that define the range, but also all independent values ​​or subranges contained within that range. For example, a numerical range of “1–5%” should be interpreted to include not only the explicitly listed values ​​from 1% to 5%, but also the independent values ​​and subranges within the indicated range. Thus, this numerical range includes independent values ​​such as 2%, 3.5%, and 4%, and subranges such as 1%–3%, 2%–4%, and 3%–5%, etc. This principle also applies to ranges that list only one value. Furthermore, this interpretation applies regardless of the width of the range or the characteristics described.

[0031] In this document, including in the claims, conjunctions such as "comprising," "including," "with," "having," "containing," "involving," and "accommodating" are understood to be open-ended, meaning "including but not limited to." Only the conjunctions "consisting of" and "composed of" are closed conjunctions.

[0032] To better illustrate the content of this invention, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that the invention can be practiced even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail, in order to highlight the main points of the invention.

[0033] Without conflict, the technical features disclosed in the embodiments of the present invention can be combined arbitrarily, and the resulting technical solutions belong to the content disclosed in the embodiments of the present invention.

[0034] In some embodiments, the preparation method of the polymetallic sulfide electrocatalyst includes the steps of:

[0035] S1, Preparation of bimetallic MOFs;

[0036] A solution containing a first transition metal salt and a second transition metal salt is mixed with an organic ligand solution to obtain a first mixed solution; wherein the first transition metal salt and the second transition metal salt are two different cations of the same acid radical ion, XY, where X is Co, Fe, Ni, Mn, Zn or Cu, and Y is NO3, Cl... - or SO4 2- Different cation salts of the same anion can be Co(NO3)2, Fe(NO3)2, Ni(NO3)2, Mn(NO3)2, Zn(NO3)2 or Cu(NO3)2, or CoCl2, FeCl2, NiCl2, MnCl2, ZnCl2 or CuCl2, or CoSO4, FeSO4, NiSO4, MnSO4, ZnSO4 or CuSO4;

[0037] Nickel foam is immersed in a first mixed solution to react and obtain a bimetallic MOF grown on nickel foam.

[0038] Typically, a first transition metal salt and a second transition metal salt can be selected and prepared into an aqueous solution according to a set ratio. Then, the aqueous solutions of the two salts are mixed to obtain a first mixed solution. The cleaned nickel foam is then immersed in the first mixed solution and reacted at room temperature. The reaction usually ends after 2-6 hours. The nickel foam is then removed, washed with deionized water, and dried to obtain a bimetallic MOF sample grown on a nickel foam substrate.

[0039] Generally, this is achieved by controlling the types of metal ions, such as copper salts, manganese salts, and iron salts, as well as the types of non-metallic particles, such as NO3. - Cl - SO4 2- Conditions such as reaction time can be used to regulate the morphology and properties of the formed MOFs. For example, by selecting different anions, bimetallic MOF products can exhibit different morphological changes such as nanosheets, nanorods, and nanoflowers. By selecting different metal ions, the performance of HER / OER / UOR can be regulated and optimized.

[0040] In some embodiments, the molar concentration ratio of the first transition metal salt to the second transition metal salt in the first mixed solution is 2:3 to 5, the molar concentration of the organic ligand solution is 0.2 to 0.4 M, and the reaction time of the nickel foam in the first mixed solution is 2 to 6 h; wherein, the organic ligand solution may be dimethylimidazole, 1,2,4-benzenetricarboxylic acid, or 2,2'-biphenyldicarboxylic acid.

[0041] Typically, nickel foam can be washed with hydrochloric acid, ethanol, and water in sequence to remove impurities from its surface, resulting in pure nickel foam that can be used as a base material.

[0042] S2. The bimetallic MOF grown on nickel foam is immersed in a second mixed solution to undergo a doping and substitution reaction of two transition metal ions, resulting in the growth of a multimetal hydroxide nanostructure on the bimetallic MOF. The second mixed solution contains a third and a fourth transition metal salt, different from the first and second transition metal salts. The third and fourth transition metal salts are two different cations of the same anion, X and Y, where X is Co, Fe, Ni, Mn, Zn, or Cu, and Y is NO3. 2- Cl - or SO4 2- Different cation salts of the same anion can be Co(NO3)2, Fe(NO3)2, Ni(NO3)2, Mn(NO3)2, Zn(NO3)2 or Cu(NO3)2, or CoCl2, FeCl2, NiCl2, MnCl2, ZnCl2 or CuCl2, or CoSO4, FeSO4, NiSO4, MnSO4, ZnSO4 or CuSO4.

[0043] Generally, two different cations of the same anion salt can be selected as the third and fourth transition metal salts, and they are prepared into an aqueous solution according to a set ratio to obtain a second mixed solution. Then, the obtained polymetallic hydroxide nanostructure is immersed in the second mixed solution and reacted at an ambient temperature of 15-40°C. The third and fourth transition metal ions are incorporated into the bimetallic MOF structure by doping or substitution. After a reaction time of 30-120 min, the obtained sample is vacuum dried at 60-90°C, and the polymetallic hydroxide nanostructure is grown on the bimetallic MOF. Typically, the third transition metal ion is different from the first and second transition metal ions, and the fourth transition metal ion is different from the first and second transition metal ions.

[0044] Typically, the multimetallic hydroxide nanostructures grown on bimetallic MOFs use the bimetallic MOF organic framework as a matrix, and generate nanostructures with different morphologies such as nanoparticles, nanosheets, nanowires or nanoclusters on the surface. These nanostructures are usually layered double hydroxide nanosheets, i.e., LDH nanosheets, and the shapes of LDH nanosheets are usually triangular, rhomboid, rectangular, etc.

[0045] Generally, the selection of the type of doped / substituted salt ions has a significant impact on the shape of LDH nanosheets formed on the MOF surface. The immersion time in the solution has a great influence on the density and size of the LDH nanosheets and nanowires formed. If the immersion time is too short, nanosheets of the required size and density cannot be formed. If the immersion time is too long, the density of the grown nanosheets will be too high, which is not conducive to the next reaction. Usually, the appropriate density of the nanosheets has an important influence on the morphology and position of the loaded material formed in the next reaction. Therefore, the reaction time should be controlled within a reasonable range, such as 30 to 120 min.

[0046] In some embodiments, the molar ratio of the third transition metal salt to the fourth transition metal salt in the second mixed solution is 3:1 to 4.

[0047] S3. Sulfide doping of multimetal hydroxide nanostructures yields nitrogen-doped carbon-supported multimetal sulfide electrocatalysts. Typically, nitrogen-doped carbon-supported multimetal sulfides are sulfide nanoclusters formed on LDH nanosheets, with sizes ranging from 200 to 400 nm.

[0048] Generally, the concentration of the dopant has a significant impact on the size and number of sulfide clusters formed. Too low or too high a concentration is not conducive to the formation of nanoclusters of suitable size. The time of the sulfur substitution reaction has a significant impact on whether nanoclusters can be formed, as well as the size and density of the nanoclusters. If the sulfidation time is insufficient, the morphology of the polymetallic hydroxide nanostructure sample remains basically unchanged, and the desired nanoclusters cannot be obtained. If the sulfidation time is too long, the formed nanoclusters will gradually aggregate and fall off, which is not conducive to the formation of multi-layered nanoclusters. In short, it is necessary to control the concentration of the sulfiding agent and the sulfidation time to prepare sulfide nanoclusters of suitable size and load. Only when the sulfidation time is appropriate will the prepared material have excellent stability. The sulfidation temperature also has an important impact on the morphology of the formed sample. When the temperature is too high, it will destroy the morphology of the original polymetallic hydroxide nanostructure, while when the temperature is too low, the sulfidation effect is not obvious.

[0049] In some embodiments, polymetallic hydroxide nanostructures are sulfide-doped using dopants C2H5SH, S(CH3)2, or C2H5NS to obtain nitrogen-doped carbon-supported polymetallic sulfide electrocatalysts. Typically, polymetallic hydroxide nanostructures are hybridized using aldolothermic or hydrothermal methods with dopants C2H5SH, S(CH3)2, or C2H5NS, allowing carbon, sulfur, and nitrogen elements from the dopants to enter the polymetallic hydroxide nanostructure, resulting in nitrogen-doped carbon-supported polymetallic sulfides. These nitrogen-doped carbon-supported polymetallic sulfides can then be used as electrocatalysts, i.e., nitrogen-doped carbon-supported polymetallic sulfide electrocatalysts.

[0050] In some embodiments, sulfidation doping involves immersing a polymetallic hydroxide nanostructure in a dopant alcohol solution with a concentration of 0.25–1 mg / mL, followed by hydrothermal heating of the dopant and the polymetallic hydroxide nanostructure at 60–200 °C for 3–15 h, followed by cooling and drying.

[0051] In some embodiments, the solvent for the alcohol solution is methanol, ethanol, or propanol. Typically, the dopant C2H5SH, S(CH3)2, or C2H5NS is prepared into an alcohol solution with a solvent, such as a C2H5SH ethanol solution, an S(CH3)2 ethanol solution, or a C2H5NS ethanol solution.

[0052] Some embodiments disclose polymetallic sulfide electrocatalysts obtained by the preparation method of polymetallic sulfide electrocatalysts disclosed in the embodiments of the present invention.

[0053] Some embodiments disclose the use of polymetallic sulfide catalysts as electrocatalysts for hydrogen evolution reaction, oxygen evolution reaction or urea oxidation reaction.

[0054] Typically, nitrogen-doped nitrogen-supported polymetallic sulfide electrocatalysts prepared by polymetallic sulfide electrocatalyst preparation methods can be used as electrocatalysts for hydrogen evolution reaction, oxygen evolution reaction, or urea oxidation reaction.

[0055] The technical details are further illustrated below with reference to the embodiments.

[0056] Example 1

[0057] In Example 1, the preparation method of the polymetallic sulfide electrocatalyst includes the following steps:

[0058] S1, Preparation of bimetallic MOFs;

[0059] Cobalt salt Co(NO3)2 and zinc salt Zn(NO3)2 are dissolved in water to prepare solution A;

[0060] The organic ligand is prepared as solution B;

[0061] Solution A and solution B are mixed to obtain a homogeneous mixed solution; wherein the molar ratio of Co(NO3)2 to Zn(NO3)2 is 2:3, and the molar concentration of the organic ligand solution dimethylimidazole is 0.2M;

[0062] The nickel foam was washed sequentially with 3M HCl, C2H5OH, and deionized water.

[0063] Nickel foam was immersed in a homogeneous mixture for reaction, and the reaction was carried out at room temperature for 6 hours. Sample X, namely CoZnMOF, was grown on the nickel foam. Figure 2 SEM image of CoZnMOF;

[0064] S2. The bimetallic MOF grown on nickel foam is immersed in the second mixed solution to carry out the doping / substitution reaction of dual transition metal ions.

[0065] Nickel salt Ni(NO3)2 and iron salt Fe(NO3)2 are dissolved in water to prepare solution C; the molar ratio of nickel salt Ni(NO3)2 to iron salt Fe(NO3)2 is 3:1.

[0066] Sample X was introduced into solution C and reacted at room temperature for 120 min. The resulting sample was then vacuum dried at 60–90 °C to obtain sample Y, which is the multimetallic hydroxide nanowire NiFe-CoZnLDH grown on a bimetallic MOF. Figure 3 SEM image of NiFe-CoZnLDH;

[0067] S3. Sulfide doping of multimetal hydroxide nanostructures yields nitrogen-doped carbon-supported multimetal sulfide electrocatalysts. The multimetal hydroxide nanostructures are sulfide-doped using a C2H5SH ethanol solution at a concentration of 0.25 mg / mL. The reaction is carried out hydrothermally at 60 °C for 3 h, followed by cooling and drying. This yields sulfide nanoclusters with a size of 200 nm, forming the nitrogen-doped carbon-supported multimetal sulfide electrocatalyst NiFeCoZn-S / NC. Figure 4 This is a SEM image of NiFeCoZn-S / N.

[0068] The performance of the nitrogen-doped carbon-supported multimetallic sulfide electrocatalyst NiFeCoZn-S / NC obtained in Example 1 was tested, and its catalytic performance as an electrocatalyst for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR) was evaluated. Figure 5 The LSV curve for the HER test. Figure 6 The LSV curve for OER testing. Figure 7 LSV curve for UOR testing. Figure 8 For a current density of 10 mA·cm -2 The following is a stability test chart.

[0069] The nitrogen-doped carbon-supported multimetal sulfide electrocatalyst prepared by the method disclosed in this invention exhibits a stable structure. The three-dimensional nickel foam provides a porous structure, which not only facilitates contact between the catalyst and reactants but also gas transport. Sulfide nanoclusters are stably anchored on the nickel foam, maintaining a low urea oxidation overpotential. It also possesses excellent urea catalytic performance, high electron transport efficiency, and ultra-long stability, exhibiting ultra-stable performance that meets the demands of industrial applications. It displays three catalytic activities: HER, OER, and UOR, with low overpotentials for HER, OER, and UOR. Therefore, it can be used in various application fields, such as as a catalyst for water electrolysis to produce hydrogen and oxygen, and for urea degradation in environmental remediation. This multifunctionality gives metal sulfide electrocatalysts broad potential in practical applications and allows them to adapt to diverse needs. Furthermore, transition metals are abundant in the Earth's crust, inexpensive, and the preparation method is simple, making it highly scalable for the preparation and utilization of multimetal sulfide electrocatalysts.

[0070] The technical solutions and technical details disclosed in the embodiments of this invention are merely illustrative of the inventive concept of this invention and do not constitute a limitation on the technical solutions of the embodiments of this invention. Any conventional changes, substitutions, or combinations made to the technical details disclosed in the embodiments of this invention have the same inventive concept as this invention and are within the protection scope of the claims of this invention.

Claims

1. A method for preparing nitrogen-doped carbon-supported polymetallic sulfide electrocatalysts, characterized in that, Including the following steps: S1, Preparation of bimetallic MOFs; A solution containing a first transition metal salt and a second transition metal salt is mixed with an organic ligand solution to obtain a first mixed solution; wherein the first transition metal salt and the second transition metal salt are XY of the same anion but different cations, where X is Co or Zn and Y is NO3. - Cl - or SO4 2- The first mixed solution contains a first transition metal salt to a second transition metal salt with a molar concentration ratio of 2:3 to 5, and an organic ligand solution with a molar concentration of 0.2 to 0.4 M. The organic ligand is dimethylimidazole. Nickel foam is immersed in a first mixed solution to react and obtain a bimetallic MOF grown on nickel foam; wherein the reaction time of nickel foam in the first mixed solution is 2-6 hours. S2. The bimetallic MOF grown on nickel foam is immersed in a second mixed solution to undergo a doping / substitution reaction of two transition metal ions, resulting in the growth of a multimetal hydroxide nanostructure on the bimetallic MOF. The second mixed solution contains a third and a fourth transition metal salt, different from the first and second transition metal salts. The third and fourth transition metal salts are XY, representing the same anion but different cations, where X is Fe or Ni and Y is NO3. - Cl - or SO4 2- The molar ratio of the third transition metal salt to the fourth transition metal salt in the second mixed solution is 3:1~4. S3. Sulfide doping of the polymetallic hydroxide nanostructure yields a nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst, which exhibits three catalytic activities: HER, OER, and UOR. The sulfide doping process involves immersing the polymetallic hydroxide nanostructure in a dopant alcohol solution with a concentration of 0.25–1 mg / mL, hydrothermally heating the reaction at 60–200 °C for 3–15 h, followed by cooling and drying.

2. The method for preparing the nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst according to claim 1, characterized in that, In step S2, the doping / substitution reaction is carried out at 15~40℃ for 30~120 min, and then the obtained sample is vacuum dried at 60~90℃ to grow a multimetallic hydroxide nanostructure on a bimetallic MOF.

3. The method for preparing the nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst according to claim 1, characterized in that, In step S3, the polymetallic hydroxide nanostructure is sulfided and doped with dopants C2H5SH, S(CH3)2 or C2H5NS to obtain a nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst.

4. The method for preparing the nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst according to claim 1, characterized in that, In step S3, the solvent for the alcohol solution is methanol, ethanol, or propanol.

5. A nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst, characterized in that, It is obtained by the preparation method according to any one of claims 1 to 4.

6. The application of the nitrogen-doped carbon-supported polymetallic sulfide electrocatalyst according to claim 5, characterized in that, The nitrogen-doped carbon-supported multimetallic sulfide electrocatalyst is used for hydrogen evolution reaction, oxygen evolution reaction or urea oxidation reaction.

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