Electrolytic water sulfide porous electrode, preparation and application thereof

Abstract

The application discloses an electrolytic water sulfide porous electrode, preparation and application thereof, relates to the field of electrode preparation, and comprises the following steps: S1, pretreatment of a substrate; S2, constant-voltage deposition of copper in a copper salt solution; S3, mixing of a mixed aqueous solution of thioacetamide, a transition metal salt and a Ce salt, and magnetic stirring for 30 min; and S4, washing and drying of the obtained electrolytic water sulfide porous electrode semi-finished product. In the application, the electrolytic water sulfide porous electrode obtained through the preparation method has enhanced electrochemical effect and improved electrolytic water performance, the catalyst placed in a hydrothermal reaction kettle is a transition metal sulfide composite catalyst such as CeMCuS, and the transition metal sulfide composite catalyst such as cerium is introduced through a hydrothermal method, so that the electrolytic water sulfide porous electrode is obtained.

Description

Technical Field

[0001] This invention relates to the field of electrode preparation, and particularly to a porous electrode for water electrolysis sulfide, its preparation, and its application. Background Technology

[0002] To mitigate global climate change, countries are vigorously developing clean energy, including wind power, solar power, tidal power, and biomass power, while reducing and limiting the use of traditional fossil fuels and actively seeking alternative energy sources. Hydrogen can be used directly as fuel, replacing gasoline and diesel, or it can be added to natural gas pipelines to achieve energy conservation and emission reduction. Furthermore, hydrogen is an important raw material in modern chemical and metallurgical industries. Combined with renewable energy power generation, it can enable large-scale energy storage applications. Transition metal chalcogenides, due to their excellent electronic conductivity, low cost, adjustable composition, and good hydrogen evolution performance, are used in fuel cells, solar cells, sensors, and supercapacitors. The differences between different coordinating elements expand the applications of transition metal sulfides, which also show excellent performance in the field of water electrolysis for hydrogen production.

[0003] Existing electrodes require current collectors and additional binders, which greatly reduces the overall performance of the electrocatalyst and makes it difficult to ensure sufficient wetting of the electrolyte, which is not conducive to the transport of reactants and products.

[0004] Therefore, it is necessary to propose a porous electrode for water electrolysis sulfide, its preparation, and its application to solve the above problems. Summary of the Invention

[0005] The purpose of this invention is to provide a porous electrode for water electrolysis using sulfides, its preparation, and its application, in order to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a porous electrode for water electrolysis using sulfides, comprising a substrate layer, an electroplated Cu layer, and a cerium transition metal composite sulfide layer, wherein the thickness of the substrate layer is 300–500 μm, the thickness of the electroplated Cu layer is 300–500 nm, and the loading of the cerium transition metal composite sulfide layer for nano-electrocatalysis is 5 mg / cm³. 2 ~50mg / cm 2 In this case, 0.1% to 10% of Ce in the cerium transition metal complex sulfide layer exists in the form of oxides.

[0007] This invention also discloses a method for preparing a porous electrode for water electrolysis sulfide, comprising the following steps:

[0008] S1: Substrate pretreatment: The foamed copper, copper mesh, and foamed nickel substrates were treated sequentially with ultrapure water, hydrochloric acid, and ethanol. They were ultrasonically cleaned for 15-30 minutes each. After cleaning, the substrates were placed in a vacuum oven at 60°C and dried for 2 hours. The molar concentration of hydrochloric acid was 0.1M-2M.

[0009] S2: Copper is deposited in a copper salt solution under a constant voltage. A copper salt solution and a copper precursor solution are prepared. The copper precursor solution is mixed evenly with a copper to template agent molar ratio of 10:1 to 1:10 to obtain a mixture solution. The pH of the mixture solution is adjusted. The mixture solution is magnetically stirred for more than 30 minutes. A layer of metallic Cu is electrodeposited on the substrate surface under a constant voltage condition of 50℃ to 90℃ using the copper salt solution as the electrolyte. After cleaning, it is dried. The molar concentration of the template agent is 0.01M to 2.0M.

[0010] S3: Mix an aqueous solution of thioacetamide, transition metal salt, and Ce salt using magnetic stirring for 30 minutes until homogeneous. Then, add the substrate layer: CuO. x -Cu is placed in a mixed solution and then placed in a hydrothermal reactor. A catalyst is placed in the hydrothermal reactor and the reactor is dried in an oven at 100℃~300℃ to form a semi-finished product of a porous electrode of water electrolysis sulfide. The molar concentration of thioacetamide is 0.02M~0.1M and the molar concentration of transition metal salt is 0.05M~0.2M.

[0011] S4: After washing and drying the obtained semi-finished product of water electrolysis sulfide porous electrode, heat-treat it under inert gas protection at 200-500℃ for 1-5 hours to obtain the water electrolysis sulfide porous electrode.

[0012] Preferably, the copper salt solution in S2 is one or more of copper nitrate solution, copper chloride solution, and copper acetate solution, the molar concentration of the copper salt solution is 0.005M to 2.0M, the pH value of the copper salt solution is adjusted by sulfuric acid to be between 0.2 and 3.5, and the template agent is one or more of KCl, KBr, and KI.

[0013] Preferably, in the variable constant voltage deposition, the deposition potential is -0.5V to -3.0V, and the electrodeposition time is 50s to 2000s.

[0014] Preferably, the transition metal in the transition metal salt in S3 includes Fe and Co, the transition metal salt is represented by M, the Ce salt is Ce(NO3)3·6H2O, the molar ratio of Ce:M is 1:10 to 5:1, and the copper precursor solution is one of the copper halide, sulfate, and acetate.

[0015] Preferably, in S3, the hydrothermal temperature is 100℃~300℃, the heating time is 6~48 hours, the molar ratio of thioacetamide to transition metal salt is 5:1~1:10, and the molar concentration of thioacetamide is 0.02~0.10M.

[0016] Preferably, the molar concentration of the hydrochloric acid is 0.5M to 1.2M, the molar concentration of the template agent is 0.2M to 1.0M, the molar ratio of copper to template agent is 3:1 to 1:8, the molar concentration of the copper salt solution is 0.1M to 1.0M, and the pH value of the salt solution is between 0.2 and 3.0.

[0017] Preferably, the deposition potential in the variable constant voltage deposition is -1.0V to -2.0V, and the electrodeposition time is 600s to 1200s.

[0018] Preferably, the molar ratio of Ce:M is 1:1 to 1:7, the hydrothermal temperature in S3 is 140℃ to 180℃, the heating time is 8 to 12 hours, the molar ratio of thioacetamide to transition metal salt is 2:1 to 1:5, and the molar concentration of thioacetamide is 0.05M to 0.10M.

[0019] The present invention also discloses an application of a porous electrode for water electrolysis sulfide, comprising the porous electrode for water electrolysis sulfide as described above. The porous electrode for water electrolysis sulfide is prepared by the preparation method of the porous electrode for water electrolysis sulfide as described above. The porous electrode for water electrolysis sulfide is applied in the electrocatalytic alkaline oxygen evolution reaction.

[0020] The technical effects and advantages of this invention are as follows:

[0021] 1. The electrochemical effect of the porous electrode obtained by the preparation method of water electrolysis sulfide porous electrode in this invention is enhanced and the water electrolysis performance is improved. The catalyst placed in the hydrothermal reactor is a transition metal sulfide composite catalyst such as CeMCuS. The transition metal sulfide composite catalyst such as cerium is introduced by hydrothermal method to obtain the porous electrode of water electrolysis sulfide.

[0022] 2. The Cu and CuO electrodeposited in situ grown on the substrate surface of the electrolytic water sulfide porous electrode of the present invention. x The composite forms the base layer: CuO x-Cu is beneficial for improving catalyst dispersion and anchoring metal sulfides. During the formation of transition metal sulfide composite catalysts, some Cu substances are sulfidated to form sulfides, which is beneficial for oxygen evolution reactions. Most of the oxides on the Cu surface can also be reduced to newly grown Cu, and a small amount of unreduced Cu2O is also beneficial for promoting oxygen generation. The introduction of transition metal elements such as Ce and the synergistic effect between metal and sulfur elements form a more compact metal composite sulfide. Compared with other sulfides, Cu / Cu2O / CeMCuS transition metal sulfide composite catalysts have higher specific surface area, more active sites and higher conductivity. By modifying and regulating the sulfide surface through the doping of different metal elements, the stability and catalytic activity of the catalyst can be enhanced. This porous electrode of water electrolysis sulfide can be used to prepare electrodes for water electrolysis oxygen evolution reaction, carbon dioxide electroreduction oxygen evolution reaction, and air oxygen evolution reaction, etc., in electrocatalytic alkaline oxygen evolution reactions.

[0023] 3. Because the preparation process uses a combination of electrodeposition and hydrothermal methods, the entire synthesis process is simple and convenient, and the raw materials are inexpensive and widely available, making it suitable for large-scale production.

[0024] 4. Test results show that the transition metal sulfide composite catalyst has excellent catalytic activity at a current density of 50 mA / cm². -2 The overpotential was only 275 mV, indicating that introducing Cu via electrodeposition can better control the catalyst's structural thickness and prevent active sites from being covered. Simultaneously, the hydrothermal method introduced elements such as S and Ce, significantly influencing the structure and morphology of the nanocatalyst, promoting uniform dispersion of active sites on its surface, forming a denser nanostructure, and improving the catalyst's catalytic activity and stability. The three-dimensional transition metal sulfide catalyst exhibited good performance in the electrocatalytic oxygen evolution reaction under alkaline conditions. Currently, the preparation process of this invention is relatively simple, and sulfur and transition metal raw materials are relatively cheaper and more abundant than precious metals, which is beneficial for improving the efficiency of hydrogen production through water electrolysis and promoting the development of hydrogen energy. Attached Figure Description

[0025] Figure 1 Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 of the present invention and Comparative Example 1 in a 1M KOH solution.

[0026] Figure 2 Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 and Comparative Example 2 in a 1M KOH solution.

[0027] Figure 3Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 and Comparative Example 3 in a 1M KOH solution.

[0028] Figure 4 Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 of the present invention and Comparative Example 4 in a 1M KOH solution.

[0029] Figure 5 Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 of the present invention and Comparative Example 5 in a 1M KOH solution.

[0030] Figure 6 Linear scan voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 of the present invention and Comparative Example 6 in a 1M KOH solution.

[0031] Figure 7 The linear sweep voltammetry plots of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst of Example 1 of the present invention and Example 1 in a KOH solution with a molar concentration of 1M are shown.

[0032] Figure 8 The linear sweep voltammogram of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst and foamed nickel in a 1M KOH solution according to Example 1 of the present invention.

[0033] Figure 9 This is a SEM image of the three-dimensional nickel-copper doped cerium-iron metal sulfide oxygen evolution reaction catalyst of the present invention.

[0034] In the diagram: NF represents nickel foam. Detailed Implementation

[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] This invention provides, for example Figures 1-9 The illustrated porous electrode for water electrolysis using sulfides comprises a substrate layer, an electroplated Cu layer, and a cerium transition metal composite sulfide layer. The substrate layer has a thickness of 300–500 μm, the electroplated Cu layer has a thickness of 300–500 nm, and the cerium transition metal composite sulfide layer has a nano-electrocatalytic loading of 5 mg / cm³. 2 ~50mg / cm 2In this case, 0.1% to 10% of Ce in the cerium transition metal complex sulfide layer exists in the form of oxides.

[0037] This invention also discloses a method for preparing a porous electrode for water electrolysis sulfide, comprising the following steps:

[0038] S1: Substrate pretreatment: The foamed copper, copper mesh, and foamed nickel substrates were treated sequentially with ultrapure water, hydrochloric acid, and ethanol. They were ultrasonically cleaned for 15-30 minutes each. After cleaning, the substrates were placed in a vacuum oven at 60°C and dried for 2 hours. The molar concentration of hydrochloric acid was 0.1M-2M.

[0039] S2: Copper is deposited in a copper salt solution under a constant voltage. A copper salt solution and a copper precursor solution are prepared. The copper precursor solution is mixed evenly with a copper to template agent molar ratio of 10:1 to 1:10 to obtain a mixture solution. The pH of the mixture solution is adjusted. The mixture solution is magnetically stirred for more than 30 minutes. A layer of metallic Cu is electrodeposited on the substrate surface under a constant voltage condition of 50℃ to 90℃ using the copper salt solution as the electrolyte. After cleaning, it is dried. The molar concentration of the template agent is 0.01M to 2.0M.

[0040] S3: Mix an aqueous solution of thioacetamide, transition metal salt, and Ce salt using magnetic stirring for 30 minutes until homogeneous. Then, add the substrate layer: CuO. x -Cu is placed in a mixed solution and then placed in a hydrothermal reactor. A catalyst is placed in the hydrothermal reactor and the reactor is dried in an oven at 100℃~300℃ to form a semi-finished product of a porous electrode of water electrolysis sulfide. The molar concentration of thioacetamide is 0.02M~0.1M and the molar concentration of transition metal salt is 0.05M~0.2M.

[0041] S4: After washing and drying the obtained semi-finished product of water electrolysis sulfide porous electrode, heat-treat it under inert gas protection at 200-500℃ for 1-5 hours to obtain the water electrolysis sulfide porous electrode.

[0042] In this invention, the electrochemical effect of the water electrolysis sulfide porous electrode obtained by the preparation method of water electrolysis sulfide porous electrode is enhanced and the water electrolysis performance is improved. The catalyst placed in the hydrothermal reactor is a transition metal sulfide composite catalyst such as CeMCuS. The cerium and other transition metal sulfide composite catalyst is introduced by hydrothermal method to obtain the water electrolysis sulfide porous electrode.

[0043] The Cu and CuO electrodeposited in situ grown on the substrate surface of the water electrolysis sulfide porous electrode of the present invention are used x The composite forms the base layer: CuO x-Cu is beneficial for improving catalyst dispersion and anchoring metal sulfides. During the formation of transition metal sulfide composite catalysts, some Cu substances are sulfidated to form sulfides, which is beneficial for oxygen evolution reactions. Most of the oxides on the Cu surface can also be reduced to newly grown Cu, and a small amount of unreduced Cu2O is also beneficial for promoting oxygen generation. The introduction of transition metal elements such as Ce and the synergistic effect between metal and sulfur elements form a more compact metal composite sulfide. Compared with other sulfides, Cu / Cu2O / CeMCuS transition metal sulfide composite catalysts have higher specific surface area, more active sites and higher conductivity. By modifying and regulating the sulfide surface through the doping of different metal elements, the stability and catalytic activity of the catalyst can be enhanced. This porous electrode of water electrolysis sulfide can be used to prepare electrodes for water electrolysis oxygen evolution reaction, carbon dioxide electroreduction oxygen evolution reaction, and air oxygen evolution reaction, etc., in electrocatalytic alkaline oxygen evolution reactions.

[0044] Because the preparation process uses a combination of electrodeposition and hydrothermal methods, the entire synthesis process is simple and convenient, and the raw materials are inexpensive and widely available, making it suitable for large-scale production.

[0045] Test results show that the transition metal sulfide composite catalyst exhibits excellent catalytic activity at a current density of 50 mA / cm². -2 The overpotential was only 275 mV, indicating that introducing Cu via electrodeposition can better control the catalyst's structural thickness and prevent active sites from being covered. Simultaneously, the hydrothermal method introduced elements such as S and Ce, significantly influencing the structure and morphology of the nanocatalyst, promoting uniform dispersion of active sites on its surface, forming a denser nanostructure, and improving the catalyst's catalytic activity and stability. The three-dimensional transition metal sulfide catalyst exhibited good performance in the electrocatalytic oxygen evolution reaction under alkaline conditions. Currently, the preparation process of this invention is relatively simple, and sulfur and transition metal raw materials are relatively cheaper and more abundant than precious metals, which is beneficial for improving the efficiency of hydrogen production through water electrolysis and promoting the development of hydrogen energy.

[0046] The copper salt solution in S2 is one or more of copper nitrate solution, copper chloride solution, and copper acetate solution, with a molar concentration of 0.005M to 2.0M. The pH value of the copper salt solution is adjusted by sulfuric acid to be between 0.2 and 3.5. The template agent is one or more of KCl (potassium chloride), KBr (potassium bromide), and KI (potassium iodide).

[0047] In constant voltage deposition, the deposition potential is -0.5V to -3.0V, and the electrodeposition time is 50s to 2000s.

[0048] The transition metals in S3 include Fe and Co. The transition metal salt is represented by M. The Ce salt is Ce(NO3)3·6H2O (cerium nitrate). The molar ratio of Ce to M is 1:10 to 5:1. The copper precursor solution is one of copper halide, sulfate, or acetate.

[0049] The hydrothermal temperature in S3 is 100℃~300℃, the heating time is 6~48 hours, the molar ratio of thioacetamide to transition metal salt is 5:1~1:10, and the molar concentration of thioacetamide is 0.02~0.10M.

[0050] The molar concentration of hydrochloric acid is 0.5M to 1.2M, the molar concentration of the template agent is 0.2M to 1.0M, the molar ratio of copper to template agent is 3:1 to 1:8, the molar concentration of copper salt solution is 0.1M to 1.0M, and the pH value of the salt solution is between 0.2 and 3.0.

[0051] In constant voltage deposition, the deposition potential is -1.0V to -2.0V, and the electrodeposition time is 600s to 1200s.

[0052] The molar ratio of Ce:M is 1:1 to 1:7, the hydrothermal temperature in S3 is 140℃ to 180℃, the heating time is 8 to 12 hours, the molar ratio of thioacetamide to transition metal salt is 2:1 to 1:5, and the molar concentration of thioacetamide is 0.05M to 0.10M.

[0053] This invention also discloses an application of a porous water electrolysis sulfide electrode, comprising the porous water electrolysis sulfide electrode as described above. The porous water electrolysis sulfide electrode is prepared by the preparation method of the porous water electrolysis sulfide electrode as described above, and the porous water electrolysis sulfide electrode is applied in the electrocatalytic alkaline oxygen evolution reaction.

[0054] In the following specific embodiments and comparative examples:

[0055] Example 1: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol, and ultrasonically cleaned for 15–30 minutes each. After cleaning, it was dried in a 60°C vacuum oven for 2 hours. A 0.8M copper acetate solution was used as the electrodeposition solution, and the pH of the copper salt solution was adjusted to 2.0 (±0.1) using sulfuric acid. 0.6M KCl was used as the template agent, and a mixture of copper and KCl in a 1:1 molar ratio was prepared. The electrodeposition was carried out at 60°C with a constant voltage of -1.4V (vs. Ag / AgCl) and a depth of 1×1 cm⁻¹. 2 Using a Pt sheet as the counter electrode, electrodeposition was performed at a depth of 1×1 cm under a time of 600 s. 2 Electrodeposition of a layer of metallic Cu / Cu on the surface of the nickel foam substrate xAfter cleaning and drying, the Ce:Fe molar ratio was 1:5. Ce(NO3)3·6H2O, Fe(NO3)3·9H2O, and 0.08M thioacetamide were prepared into a 50mL solution, which was magnetically stirred for 30min to obtain a mixed solution. The above mixed solution and copper-deposited nickel foam were placed in a hydrothermal reactor and heated continuously in an oven at 160℃ for 10 hours. The reacted electrodes were rinsed several times with ethanol and ultrapure water, and then dried at room temperature in an oven to prepare the CeMCuS three-dimensional nickel-based composite metal sulfide catalyst.

[0056] Figures 1-8 This embodiment describes the oxygen evolution performance of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst prepared in this example, as well as comparative examples 1, 2, 3, 4, 5, and 6, and nickel foam alone. Figures 1-8 As can be seen, the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions. During the alkaline water electrolysis reaction at a current density of 50 mA / cm², [the catalyst shows high activity]. -2 The overpotential is only 275mV, which is 80mV lower than that of Comparative Example 1; 56mV lower than that of Comparative Example 2; 14mV lower than that of Comparative Example 3; 6mV lower than that of Comparative Example 4; 32mV lower than that of Comparative Example 5; 32mV lower than that of Comparative Example 6; and 134mV lower than that of nickel foam alone, which is close to the lowest potential value of alkaline water electrolysis reaction in the prior art.

[0057] The synergistic and electronic coupling effects between Cu and Ni atoms in CeFeCuS result in abundant active sites on the surface structure and optimize the electronic structure of the OER. The introduction of Ce and Fe atoms lowers the hydrogen adsorption free energy of the catalyst. Without any polymer binder, the in-situ grown catalyst nanostructure forms a strong combination between the network nanospheres and the Ni foam framework, promoting not only water splitting but also generating activated hydrogen, exhibiting a higher specific surface area, and optimizing the catalytic stability of CeFeCuS. Simultaneously, the electron-withdrawing effect of Ce modulates the electronic structure of Ni, playing a significant role in the formation of high-valence Ni.

[0058] Example 2: The difference between Example 2 and Example 1 is that the copper acetate solution is replaced with copper chloride solution and copper nitrate solution, while the rest is the same as Example 1.

[0059] Table 1 compares the performance of three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts prepared with three different Cu salt electrodeposition solutions in Example 2 in a 1M KOH solution. Table 1 shows that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits a significantly lower overpotential when using copper acetate solution as the electrolyte compared to catalysts prepared with other copper salt solutions. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst demonstrates high catalytic activity under alkaline water electrolysis conditions, and the introduction of metallic copper and copper oxide can also significantly improve the catalyst's hydrogen evolution activity. During alkaline water electrolysis, the current density is 50 mA / cm². -2 The overpotential was only 275 mV, which is better than that of other complexes prepared by copper salts. This proves that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has more active sites and higher conductivity when copper acetate solution is selected as the electrolyte, and has the best catalytic activity for the oxygen evolution reaction of water electrolysis.

[0060] Example 3: The difference between Example 3 and Example 1 is that the concentration of the electrodeposition copper salt solution is changed to 0.6M and 1.0M, while the rest is the same as Example 1.

[0061] Table 1 shows the linear voltammetric curves of the three-dimensional nickel-copper composite metal sulfide oxygen evolution reaction catalyst prepared in Example 3 at different concentrations of electrodeposited copper salt solutions in a 1M KOH solution. Table 1 shows that when the copper acetate salt concentration is 0.8M, the overpotential of CeFeCuS is significantly lower than that of catalysts prepared at other copper salt concentrations. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with a current density of 50 mA / cm² during alkaline water electrolysis. -2 The overpotential was only 275 mV, which is better than that of the composite prepared by other copper salt concentrations, thus proving that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when electrodeposited in 0.8 M copper acetate solution.

[0062] Example 4: This Example 4 differs from Example 1 in that the pH of the electrodeposition solution is changed to 1.0 and 3.0, while the rest is the same as Example 1.

[0063] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that at a pH of 2.0 in the electrodeposition solution, the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst is significantly lower than that of catalysts prepared at other deposition potentials. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential at the pH was only 275mV, which is better than that of the composites prepared at other pH conditions. This proves that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has a high current density and a faster oxygen evolution rate when the pH of the electrodeposition solution is changed to 2.0. This pH condition has the best catalytic activity for the oxygen evolution reaction of water electrolysis when used as the electrodeposition condition.

[0064] Example 5: This Example 5 differs from Example 1 in that the template agent concentration is changed to 0.4M and 0.8M, otherwise it is the same as Example 1.

[0065] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that when the molar concentration of the template agent is 0.6 M, the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst is significantly lower than that of other template agent concentrations. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential was only 275 mV, which is better than that of the composites prepared with other concentrations of template agent, thus proving that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when 0.6 MKCl is selected as the template agent.

[0066] Example 6: This Example 6 differs from Example 1 in that the ratio of copper to template agent is changed to 2:1, 1:2, or 1:3, while the rest is the same as Example 1.

[0067] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst is significantly lower than that under copper-template ratios of 2:1, 1:2, and 1:3. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with the overpotential reaching a maximum at a current density of 50 mA / cm² during the alkaline water electrolysis reaction.-2 The overpotential is only 275mV, which is better than the composites prepared by the other three copper-templating agent ratios. This proves that when the copper-templating agent ratio of CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst is 1:1, its surface is more controllable, and it can present spherical particles with a rough morphology, a large specific surface area, and more active sites. It has the best catalytic activity in the oxygen evolution reaction of water electrolysis.

[0068] Example 7: This Example 7 differs from Example 1 in that the deposition potential is changed to -0.8V (vs. Ag / AgCl), -1.2V (vs. Ag / AgCl), and -1.8V (vs. Ag / AgCl), while the rest is the same as Example 1.

[0069] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst at a deposition potential of -1.4V (vs. Ag / AgCl) is significantly lower than that of catalysts prepared at other deposition potentials. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during alkaline water electrolysis. -2 The overpotential was only 275 mV, which is superior to the composites prepared at -0.8 V (vs. Ag / AgCl), -1.2 V (vs. Ag / AgCl), and -1.8 V (vs. Ag / AgCl). Electrodeposition began on the Cu-loaded nickel foam at -0.8 V (vs. Ag / AgCl). As the scanning potential shifted further negative, the current density of the CeFeCuS composite catalyst increased and stabilized at -1.4 V (vs. Ag / AgCl), demonstrating that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibited optimal catalytic activity for the oxygen evolution reaction in water electrolysis when -1.4 V (vs. Ag / AgCl) was selected as the deposition potential.

[0070] Example 8: This Example 8 differs from Example 1 in that the deposition time is changed to 500s and 700s, otherwise it is the same as Example 1.

[0071] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the alloys deposited at 500s and 700s exhibit fine particle structure, resulting in reduced roughness, specific surface area, and fewer electrocatalytic active sites, which is detrimental to oxygen evolution. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst with a deposition time of 600s has a significantly lower overpotential than catalysts prepared at other deposition times. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during alkaline water electrolysis. -2 The overpotential at this time was only 275 mV, which is better than the composites prepared at 500 s and 700 s, thus proving that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when the deposition time is selected as 600 s.

[0072] Example 9: This Example 9 differs from Example 1 in that the transition metal salt ferric nitrate used in hydrothermal treatment is replaced with cobalt nitrate; otherwise, it is the same as Example 1.

[0073] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst, when using ferric nitrate, exhibits a significantly lower overpotential than catalysts prepared at other deposition times. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst demonstrates high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential was only 275 mV, which is better than that of the composite prepared by cobalt nitrate, thus proving that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when iron nitrate is selected.

[0074] Example 10: This Example 10 differs from Example 1 in that the ratio of Ce to Fe metal during hydrothermal treatment is changed to 1:3 or 1:7, otherwise it is the same as Example 1.

[0075] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that iron is a pre-precipitating element in the alloy; a small amount of ferric nitrate is sufficient to obtain a high-iron-content nickel-iron alloy. The electrocatalytic performance of the nickel-iron alloy initially improves and then deteriorates with increasing or decreasing iron content. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst, when prepared hydrothermally with a Ce to Fe metal ratio of 1:5, exhibits a significantly lower overpotential than catalysts prepared with other metal ratios. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst demonstrates high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential was only 275 mV, which is better than the composites prepared when the Ce to Fe metal ratio was 1:3 and 1:7. This proves that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when the Ce to Fe metal ratio is 1:5 during hydrothermal treatment.

[0076] Example 11: This Example 11 differs from Example 1 in that the concentration of thioacetamide is changed to 0.06M or 0.1M, otherwise it is the same as Example 1.

[0077] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst, with an overpotential of 0.08 M thioacetamide, exhibits significantly lower overpotentials than catalysts prepared at other thioacetamide concentrations. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst demonstrates high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential was only 275 mV, which is better than the composites prepared when the concentration of thioacetamide was changed to 0.06 M and 0.1 M. This proves that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when the concentration of thioacetamide is 0.08 M.

[0078] Example 12: This Example 12 differs from Example 1 in that the hydrothermal temperature is changed to 140℃ and 180℃, otherwise it is the same as Example 1.

[0079] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst at a hydrothermal temperature of 160℃ is significantly lower than that of catalysts prepared at other temperatures. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential at 160℃ is only 275mV, which is better than that of the composites prepared at 140℃ and 180℃. This proves that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when 160℃ is selected as the hydrothermal temperature.

[0080] Example 13: This example 13 differs from Example 1 in that the hydrothermal time is changed to 8h or 12h, otherwise it is the same as Example 1.

[0081] Table 1 shows the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalysts in a 1M KOH solution at a current density of 50 mA / cm². -2 A comparison chart of overpotentials (vs. RHE) is presented. Table 1 shows that the overpotential of the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst at 10 h is significantly lower than that of catalysts prepared under other hydrothermal time conditions. The CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst exhibits high catalytic activity under alkaline water electrolysis conditions, with an overpotential of 50 mA / cm² during the alkaline water electrolysis reaction. -2 The overpotential at 10h was only 275mV, which is better than the composites prepared at 8h and 12h, thus proving that the CeFeCuS three-dimensional nickel-based composite metal sulfide catalyst has the best catalytic activity for the oxygen evolution reaction of water electrolysis when 10h is selected as the hydrothermal time.

[0082] Comparative Example 1: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol, and ultrasonicated for 15–30 min in an ultrasonic cleaner. After cleaning, it was dried in a vacuum oven at 60°C for 2 h. A 50 mL solution of Ce(NO3)3·6H2O and 0.08M thioacetamide was prepared and magnetically stirred for 30 min to obtain a mixed solution. The above mixed solution and the pretreated nickel foam were placed in a hydrothermal reactor and heated continuously in an oven at 160°C for 10 h. The electrode after reaction was rinsed several times with ethanol and ultrapure water, and then dried at room temperature in an oven to prepare a CeS three-dimensional nickel-based composite metal sulfide catalyst.

[0083] Comparative Example 2: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol, and ultrasonically cleaned for 15–30 min each. After cleaning, it was dried in a 60℃ vacuum oven for 2 h. A 50 mL solution of Fe(NO3)3·9H2O and 0.08M thioacetamide was prepared and magnetically stirred for 30 min to obtain a mixed solution. The mixed solution and the pretreated nickel foam were placed in a hydrothermal reactor and heated continuously in a 160℃ oven for 10 h. The reacted electrode was rinsed several times with ethanol and ultrapure water, and then dried at room temperature in an oven to prepare a FeS three-dimensional nickel-based composite metal sulfide catalyst.

[0084] Comparative Example 3: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol. Each substrate was ultrasonically cleaned for 15–30 minutes and then dried in a 60℃ vacuum oven for 2 hours. The selected electrodeposition solution was a 0.8M copper acetate solution, with the pH adjusted to 2.0 (±0.1) using sulfuric acid. 0.6M KCl was used as a template agent, and the copper and template agent were mixed uniformly at a 1:1 molar ratio. The electrodeposition was carried out at 60℃, with a constant voltage of -1.4V (vs. Ag / AgCl), using a Pt sheet as the counter electrode, and an electrodeposition time of 600 s at a depth of 1×1 cm. 2 Electrodeposition of a layer of metallic Cu / Cu on the surface of the nickel foam substrate x O, cleaned and dried; prepare 50 mL of 0.08 M thioacetamide and stir magnetically for 30 min to obtain a mixed solution. Place the above mixed solution and copper-deposited nickel foam into a hydrothermal reactor and heat continuously in an oven at 160 °C for 10 hours; rinse the electrode after reaction several times with ethanol and ultrapure water, and dry it in an oven at room temperature to prepare a CuS three-dimensional nickel-based composite metal sulfide catalyst.

[0085] Comparative Example 4: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol. Each substrate was ultrasonically cleaned for 15–30 minutes and then dried in a 60℃ vacuum oven for 2 hours. The selected electrodeposition solution was a 0.8M copper acetate solution, with the pH adjusted to 2.0 (±0.1) using sulfuric acid. 0.6M KCl was used as a template agent, and a mixture of copper and template agent in a 1:1 molar ratio was prepared. The electrodeposition was carried out at 60℃, with a constant voltage of -1.4V (vs. Ag / AgCl), using a Pt sheet as the counter electrode, and an electrodeposition time of 600 s at a depth of 1×1 cm. 2 Electrodeposition of a layer of metallic Cu / Cu on the surface of the nickel foam substrate xAfter cleaning and drying, Ce(NO3)3·6H2O and 0.08M thioacetamide were mixed to form a 50mL solution, and the mixture was magnetically stirred for 30min to obtain a mixed solution. The above mixed solution and copper-deposited nickel foam were placed in a hydrothermal reactor and heated continuously in an oven at 160℃ for 10 hours. The electrode after reaction was rinsed several times with ethanol and ultrapure water, and then dried in an oven at room temperature to prepare the CeCuS three-dimensional nickel-based composite metal sulfide catalyst.

[0086] Comparative Example 5: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol, and ultrasonically cleaned for 15–30 min each. After cleaning, it was dried in a 60℃ vacuum oven for 2 h. A Ce:Fe molar ratio of 1:5 was used. Ce(NO3)3·6H2O, Fe(NO3)3·9H2O, and 0.08M thioacetamide were prepared into a 50 mL solution, which was magnetically stirred for 30 min to obtain a mixed solution. The above mixed solution and the pretreated nickel foam were placed in a hydrothermal reactor and heated continuously in a 160℃ oven for 10 hours. The reacted electrode was rinsed several times with ethanol and ultrapure water, and then dried at room temperature in an oven to prepare a CeFeS three-dimensional nickel-based composite metal sulfide catalyst.

[0087] Comparative Example 6: A nickel foam substrate was treated sequentially with ultrapure water, 1M hydrochloric acid, and ethanol. Each substrate was ultrasonically cleaned for 15–30 minutes and then dried in a 60℃ vacuum oven for 2 hours. The selected electrodeposition solution was a 0.8M copper acetate solution, with the pH adjusted to 2.0 (±0.1) using sulfuric acid. 0.6M KCl was used as a template agent, and the copper and template agent were mixed uniformly at a 1:1 molar ratio. The electrodeposition was carried out at 60℃, with a constant voltage of -1.4V (vs. Ag / AgCl), using a Pt sheet as the counter electrode, and an electrodeposition time of 600 s at a depth of 1×1 cm. 2 Electrodeposition of a layer of metallic Cu / Cu on the surface of the nickel foam substrate x After cleaning and drying, Fe(NO3)3·9H2O and 0.08M thioacetamide were mixed to form a 50mL solution, and the mixture was magnetically stirred for 30min to obtain a mixed solution. The above mixed solution and copper-deposited nickel foam were placed in a hydrothermal reactor and heated continuously in an oven at 160℃ for 10 hours. The electrode after the reaction was rinsed several times with ethanol and ultrapure water, and then dried in an oven at room temperature to prepare a CuFeS three-dimensional nickel-based composite metal sulfide catalyst.

[0088] The SEM images of the obtained three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst were obtained using a scanning electron microscope (Quanta 400FEG, manufactured by FEI Corporation, USA), as shown below. Figure 9 As shown. From Figure 9 As can be seen from the results, the obtained three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst has a uniform spherical structure. The ultrathin porous structure can provide a large number of exposed active sites, and has a large specific surface area and good catalytic activity.

[0089] The function and effect of this invention:

[0090] According to the preparation method of the three-dimensional nickel-copper doped transition metal sulfide oxygen evolution reaction catalyst provided in the above embodiments, nickel foam is selected as the support and cerium iron is selected as the metal source. By combining electrodeposition and hydrothermal methods, a core-shell structured three-dimensional nickel-copper doped cerium iron metal sulfide oxygen evolution reaction catalyst is prepared.

[0091] This invention yields a three-dimensional porous electrode by pretreating the substrate, depositing copper at a constant voltage in a copper salt solution, and introducing a cerium-iron transition metal sulfide composite catalyst using a hydrothermal method. The substrate surface utilizes in-situ electrodeposited growth of Cu and CuO. x The composite material is beneficial for improving catalyst dispersion and anchoring metal sulfides. The synergistic effect of strong electronic interactions between nanoparticles endows the nanocomposite with higher conductivity, optimal water adsorption energy, and faster charge transfer capability. Highly conductive nickel foam promotes electron transfer, while the three-dimensional network structure facilitates electrolyte diffusion and penetration, thereby enhancing OER activity. Based on the investigation of copper deposition potential and deposition time, this study prepared a three-dimensional networked composite nanocatalyst by doping with small amounts of sulfur, cerium, and iron. The metal sulfide activity was controllably regulated by changing the hydrothermal temperature and duration. Electrochemical measurements show that the ultrathin porous nickel-cerium-iron nanostructure on the nickel foam provides a large number of exposed active sites, promoting electron and ion transport and enhancing catalyst stability and catalytic activity. This electrode can be used to prepare electrodes for the oxygen evolution reaction of water electrolysis, carbon dioxide electroreduction, and air oxygen evolution. This study provides a framework for the future preparation of highly active and persistently stable OER catalysts.

[0092] Tests showed that the three-dimensional nickel-copper composite metal sulfide oxygen evolution reaction catalyst has excellent catalytic activity (at a current density of 50 mA / cm²). -2 The overpotential is only 275mV, indicating that the three-dimensional nickel-copper composite metal sulfide oxygen evolution reaction catalyst exhibits good electrocatalytic activity for oxygen evolution reaction under alkaline conditions. Compared with existing technologies, the raw materials of this invention are widely available and inexpensive, and the preparation process is simple, which is beneficial to improving the efficiency of hydrogen production through water electrolysis and promoting the development of hydrogen energy.

[0093] Table 1 shows the results of Examples 1-13, nickel foam, and Comparative Examples 1-6 in a 1M KOH solution with a current density of 50 mA / cm². -2 100mAcm -2 Comparison chart of oxygen evolution performance under overpotential (vs. RHE)

[0094]

[0095]

Claims

1. A method for preparing a porous electrode for water electrolysis using sulfides, characterized in that: Includes the following steps: S1: Substrate pretreatment. The foamed copper, copper mesh, and foamed nickel substrates were treated sequentially with ultrapure water, hydrochloric acid, and ethanol. They were ultrasonically cleaned for 15-30 minutes each. After cleaning, the substrates were placed in a vacuum oven at 60°C and dried for 2 hours. The molar concentration of hydrochloric acid was 0.1M-2M. S2: Copper is deposited in a copper salt solution under a constant voltage. A copper salt solution and a copper precursor solution are prepared. The copper precursor solution is mixed evenly with a copper to template agent molar ratio of 10:1 to 1:10 to obtain a mixture solution. The pH of the mixture solution is adjusted. The mixture solution is magnetically stirred for more than 30 minutes. A layer of metallic Cu is electrodeposited on the substrate surface under a constant voltage condition of 50℃ to 90℃ using the copper salt solution as the electrolyte. After cleaning, it is dried. The molar concentration of the template agent is 0.01M to 2.0M. S3: Mix an aqueous solution of thioacetamide, transition metal salt, and Ce salt using magnetic stirring for 30 minutes until homogeneous. Then, add the substrate layer: CuO. x -Cu is placed in a mixed solution and then placed in a hydrothermal reactor. A catalyst is placed in the hydrothermal reactor and subjected to a hydrothermal reaction in an oven at 100℃~300℃ to form a semi-finished product of a porous electrode made of water electrolysis sulfide. The molar concentration of thioacetamide is 0.02M~0.1M, and the molar concentration of transition metal salt is 0.05M~0.2M. The transition metal salt in S3 includes Fe and Co, and the transition metal salt is represented by M. The Ce salt is Ce(NO3)3·6H2O, and the molar ratio of Ce:M is 1:10~5:

1. The copper precursor solution is one of the copper halide, sulfate, and acetate. S4: After washing and drying the obtained semi-finished product of water electrolysis sulfide porous electrode, heat-treat it under inert gas protection at 200-500℃ for 1-5 hours to obtain the water electrolysis sulfide porous electrode.

2. The method for preparing a porous electrode for water electrolysis sulfide according to claim 1, characterized in that: The copper salt solution in S2 is one or more of copper nitrate solution, copper chloride solution, and copper acetate solution. The molar concentration of the copper salt solution is 0.005M~2.0M. The pH value of the copper salt solution is adjusted by sulfuric acid to be between 0.2 and 3.

5. The template agent is one or more of KCl, KBr, and KI.

3. The method for preparing a porous electrode for water electrolysis sulfide according to claim 1, characterized in that: In the variable constant voltage deposition, the deposition potential is -0.5V to -3.0V, and the electrodeposition time is 50s to 2000s.

4. The method for preparing a porous electrode for water electrolysis sulfide according to claim 1, characterized in that: The hydrothermal temperature in S3 is 100℃~300℃, the heating time is 6~48 hours, the molar ratio of thioacetamide to transition metal salt is 5:1~1:10, and the molar concentration of thioacetamide is 0.02~0.10M.

5. The method for preparing a porous electrode for water electrolysis sulfide according to claim 2, characterized in that: The hydrochloric acid has a molar concentration of 0.5M to 1.2M, the template agent has a molar concentration of 0.2M to 1.0M, the copper to template agent molar ratio is 3:1 to 1:8, the copper salt solution has a molar concentration of 0.1M to 1.0M, and the pH value of the salt solution is between 0.2 and 3.

0.

6. The method for preparing a porous electrode for water electrolysis sulfide according to claim 3, characterized in that: In the variable constant voltage deposition, the deposition potential is -1.0V to -2.0V, and the electrodeposition time is 600s to 1200s.

7. The method for preparing a porous electrode for water electrolysis sulfide according to claim 4, characterized in that: The molar ratio of Ce:M is 1:1 to 1:7, the hydrothermal temperature in S3 is 140℃ to 180℃, the heating time is 8 to 12 hours, the molar ratio of thioacetamide to transition metal salt is 2:1 to 1:5, and the molar concentration of thioacetamide is 0.05M to 0.10M.

8. A porous electrode for water electrolysis using sulfides, characterized in that: The electrode is fabricated using the method described in any one of claims 1-7, comprising a substrate layer, an electroplated Cu layer, and a cerium transition metal composite sulfide layer. The substrate layer has a thickness of 300-500 μm, the electroplated Cu layer has a thickness of 300-500 nm, and the cerium transition metal composite sulfide layer has a nano-electrocatalytic loading of 5 mg / cm³. 2 ~50mg / cm 2 In this case, 0.1-10% of Ce in the cerium transition metal complex sulfide layer exists in the form of oxides.

9. An application of a porous electrode for water electrolysis sulfide, characterized in that: The invention includes the porous electrode for water electrolysis sulfide as described in claim 8, which is prepared by the method for preparing the porous electrode for water electrolysis sulfide as described in claim 1, and is used in the electrocatalytic alkaline oxygen evolution reaction.

Images