A PEM water electrolysis hydrogen production catalyst material and its preparation method

Abstract

This invention relates to the field of catalyst preparation, specifically disclosing a PEM water electrolysis hydrogen production catalyst material and its preparation method. Using a manganese-cobalt-samarium metal composite oxide as a support, iridium oxide is loaded onto it, forming a unique catalyst composite material structure. During the preparation process, by precisely adjusting the metal addition ratio and optimizing process parameters and preparation sequence, not only is a low iridium content ensured, but the catalyst's activity and stability are also significantly improved. The excellent electrical conductivity of the manganese-cobalt-samarium metal composite oxide, along with the crystallization of iridium oxide on its substrate, effectively improves electron binding, increases binding sites, and optimizes oxygen adsorption capacity. This allows the catalyst composite material to maintain high catalytic performance while achieving effective cost control, laying a solid foundation for its widespread application.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation, specifically to a PEM water electrolysis hydrogen production catalyst material and its preparation method. Background Technology

[0002] PEM (Proton Exchange Membrane) water electrolysis for hydrogen production is a technology that uses a proton exchange membrane (PEM) to electrolyze water to produce hydrogen gas. This technology utilizes an electrochemical process to produce hydrogen gas by electrolyzing water, while simultaneously generating oxygen. Specifically, at the anode, water molecules are subjected to an applied electric field and electrolyzed into hydrogen ions and oxygen atoms. The oxygen atoms further combine to form oxygen gas, releasing electrons. The generated oxygen gas is released into the gas phase through the gas diffusion layer at the anode. The hydrogen ions produced at the anode travel through the PEM to the cathode, where they receive electrons conducted from the anode via an external circuit. The hydrogen ions combine with the electrons to form hydrogen gas. PEM water electrolysis for hydrogen production has wide applications in hydrogen fuel cell vehicles, hydrogen power plants, and hydrogen storage.

[0003] In the typical PEM water electrolysis hydrogen production process, anolyte and cathode catalysts are required. Their main function is to accelerate the electrode reactions, lower the activation energy, and thus improve electrolysis efficiency. Currently, commercially available anolyte redox catalysts are primarily iridium oxide (OER). However, metallic iridium is a non-renewable precious metal, making it expensive and limiting the large-scale industrial application of PEM water electrolysis. The development of an OER catalyst with low iridium content and high activity and stability is of great significance for reducing costs and conserving resources. Summary of the Invention

[0004] The purpose of this invention is to address the aforementioned problems by providing a PEM (Potentially Oxygen Evolution) water electrolysis hydrogen production catalyst material and its preparation method. This catalyst material uses a manganese-cobalt-samarium metal composite oxide as a support, on which iridium oxide is loaded. During the preparation process, by precisely adjusting the proportions of each metal, optimizing the preparation process parameters, and adjusting the preparation sequence, a low-iridium-content oxygen evolution reaction (OER) catalyst with high activity and high stability was successfully prepared.

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

[0006] A method for preparing a PEM water electrolysis hydrogen production catalyst material includes the following steps:

[0007] S1. Preparation of manganese-cobalt-samarium metal composite oxides:

[0008] Cobalt nitrate, manganese nitrate, samarium nitrate, and citric acid were dissolved in water and stirred for more than 12 hours to obtain the first mixed solution;

[0009] The first mixed solution undergoes a redox reaction in an air-injected reactor.

[0010] The obtained reactants were filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxides.

[0011] The molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 75–85:6–10:10–15.

[0012] S2, perform iridium oxide loading:

[0013] Manganese-cobalt-samarium metal composite oxide, iridium chloride and water were mixed and stirred for more than 12 hours;

[0014] Next, adjust the pH of the mixed solution to above 9;

[0015] The solution was then dried and ground to obtain the first powder.

[0016] The first powder was calcined at high temperature, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0017] The mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5 to 3.

[0018] This invention provides a method for preparing a PEM (Potassium Efflorum) water electrolysis hydrogen production catalyst material. Using a manganese-cobalt-samarium metal composite oxide as a support, iridium oxide is loaded onto it, forming a unique catalyst composite material structure. During the preparation process, by precisely adjusting the metal addition ratio and optimizing process parameters and preparation sequence, not only is a low iridium content ensured, but the catalyst's activity and stability are also significantly improved. The excellent electrical conductivity of the manganese-cobalt-samarium metal composite oxide, along with the crystallization of iridium oxide on its substrate, effectively improves electron binding, increases binding sites, and optimizes oxygen adsorption capacity. This allows the catalyst composite material to maintain high catalytic performance while achieving effective cost control, laying a solid foundation for its widespread application.

[0019] Furthermore, in the process of preparing manganese-cobalt-samarium metal composite oxides in S1, the molar ratio of citric acid to cobalt nitrate is 6-10:1.

[0020] Furthermore, in the process of preparing manganese-cobalt-samarium metal composite oxide in S1, the temperature of the redox reaction in the reactor is 450℃~550℃, and the reaction time is 30min~90min.

[0021] Furthermore, in the process of preparing manganese-cobalt-samarium metal composite oxide in S1, the molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 80-85:8-10:10-12.

[0022] Furthermore, during the preparation of manganese-cobalt-samarium metal composite oxides in S1, stirring was carried out for 12 to 24 hours.

[0023] Furthermore, in S2, the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5 to 2.

[0024] Furthermore, in S2, the stirring time is 12h to 24h.

[0025] Furthermore, in S2, the first powder is calcined at a high temperature of 400℃-600℃ for 1h to 3h.

[0026] The second objective of this invention is to protect the catalyst material prepared by the above method.

[0027] The catalyst material was prepared using the above-described method for preparing PEM water electrolysis hydrogen production catalyst material.

[0028] A third objective of this invention is to provide applications of the aforementioned catalyst materials.

[0029] The aforementioned catalyst materials are used as anolyte oxygen evolution catalysts in PEM water electrolysis.

[0030] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0031] This invention provides a method for preparing a PEM (Potassium Efflorum) water electrolysis hydrogen production catalyst material. Using a manganese-cobalt-samarium metal composite oxide as a support, iridium oxide is loaded onto it, forming a unique catalyst composite material structure. During the preparation process, by precisely adjusting the metal addition ratio and optimizing process parameters and preparation sequence, not only is a low iridium content ensured, but the catalyst's activity and stability are also significantly improved. The excellent electrical conductivity of the manganese-cobalt-samarium metal composite oxide, along with the crystallization of iridium oxide on its substrate, effectively improves electron binding, increases binding sites, and optimizes oxygen adsorption capacity. This allows the catalyst composite material to maintain high catalytic performance while achieving effective cost control, laying a solid foundation for its widespread application. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the following embodiments provide a more detailed description of the invention. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.

[0033] Unless otherwise specified, the use of terms such as "upper," "lower," "left," "right," "center," "inner," and "outer" to indicate orientation or positional relationships in the description of specific embodiments of the present invention is based on the expression of orientation or positional relationships, or the orientation or positional relationship in which the product / equipment / device of the invention is usually placed during use. These terms of orientation or positional relationships are merely for the purpose of facilitating the description of the present invention or simplifying the description in specific embodiments, and for enabling those skilled in the art to quickly understand the solution, and do not indicate or imply that a particular device / component / element must have a specific orientation, or be constructed and operated in a specific positional relationship, and therefore should not be construed as a limitation of the present invention.

[0034] Furthermore, the use of terms such as "horizontal," "vertical," "suspended," and "parallel" does not imply that the corresponding device / component / element must be absolutely horizontal, vertical, suspended, or parallel, but rather that it can be slightly tilted or have a deviation. For example, "horizontal" merely means that its direction is more horizontal relative to "vertical," not that the structure must be completely horizontal, but that it can be slightly tilted. Alternatively, it can be simplified to mean that the corresponding device / component / element, when set in a "horizontal," "vertical," "suspended," or "parallel" direction, can have an error / deviation of ±10% relative to the corresponding direction, more preferably within ±8%, more preferably within ±6%, more preferably within ±5%, and more preferably within ±4%. As long as the corresponding device / component / element is within the error / deviation range, it can still achieve its function in the present invention.

[0035] Furthermore, the use of terms such as "first," "second," "third," etc. in terminology is merely for distinguishing identical or similar components and should not be interpreted as emphasizing or implying the relative importance of a particular component.

[0036] Furthermore, in the description of the embodiments of the present invention, "several", "more than", and "a number of" represent at least two. The number can be any number, such as 2, 3, 4, 5, 6, 7, 8, or 9, and can even exceed nine.

[0037] Furthermore, in the description of the technical solution of this invention, unless otherwise explicitly specified / limited / restricted, the terms "set up," "install," "connect," "link," "provided with," "laid out," and "arranged" should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to common connection methods in the art, such as welding, riveting, bolting, and threaded connections. Such connections can be mechanical, electrical, or communication connections; they can be direct connections or indirect connections through an intermediate medium; and they can refer to the internal communication between two components.

[0038] Currently, commercially available anodic oxidation-reduction catalysts are mainly iridium oxide. However, metallic iridium is a non-renewable precious metal, and its high price limits the large-scale industrial application of PEM hydrolysis. The development of an OER catalyst with low iridium content and high activity and stability is of great significance for reducing costs and conserving resources.

[0039] This invention provides a method for preparing a PEM (Polymerized Iron-Alkali) water electrolysis hydrogen production catalyst material. The method utilizes iridium oxide supported on a manganese-cobalt-samarium metal composite oxide carrier. The excellent conductivity of the manganese-cobalt-samarium metal composite oxide, combined with the crystallization of iridium oxide on the substrate, effectively improves electron binding, increases binding sites, and thus optimizes oxygen adsorption capacity. These improvements enable the catalyst composite material to maintain high catalytic performance while achieving effective cost control.

[0040] Includes the following steps:

[0041] S1. Preparation of manganese-cobalt-samarium metal composite oxides:

[0042] Cobalt nitrate, manganese nitrate, samarium nitrate, and citric acid are dissolved in water and stirred for more than 12 hours. In some embodiments, the stirring time is 12-24 hours to obtain a first mixed solution.

[0043] The first mixed solution was subjected to an oxidation-reduction reaction in an air-injected reactor; the temperature of the oxidation-reduction reaction was 450℃~550℃, and the reaction time was 30min~90min.

[0044] The obtained reactants were filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxides.

[0045] The molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 75–85:6–10:10–15.

[0046] In some embodiments, the molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 80–85:8–10:10–12. Studies have found that the ratio of cobalt, manganese, and samarium is a key factor affecting the overall performance of the catalyst material; both excessively low and excessively high ratios will cause a significant decrease in performance.

[0047] In some embodiments, the molar ratio of citric acid to cobalt nitrate is 6-10:1. The main functions of citric acid are complexation, precipitation, and pH adjustment.

[0048] S2, perform iridium oxide loading:

[0049] Manganese-cobalt-samarium metal composite oxide, iridium chloride and water are mixed and stirred for more than 12 hours. In some embodiments, the stirring time is 12-24 hours to obtain a first mixed solution.

[0050] Next, adjust the pH of the mixed solution to above 9;

[0051] The solution was then dried and ground to obtain the first powder.

[0052] The first powder was calcined at 400℃-600℃ for 1h-3h, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0053] The mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5–3. This mass ratio is a key factor affecting product performance; too little or too much metal composite oxide results in minimal improvement. Preferably, the mass ratio is 1:1.5–2.

[0054] Example 1

[0055] Preparation of catalyst materials

[0056] S1. Preparation of manganese-cobalt-samarium metal composite oxides:

[0057] S11. Dissolve cobalt nitrate, manganese nitrate, samarium nitrate, and citric acid in water and stir for 15 hours to obtain a first mixed solution; wherein the molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 80:8:10. The molar ratio of citric acid to cobalt nitrate is 8:1, and water is added until cobalt nitrate and samarium nitrate are completely dissolved.

[0058] S12. The first mixed solution is subjected to an oxidation-reduction reaction in an air-injected reactor at a temperature of 500°C for 60 minutes.

[0059] S13. The obtained reactants are filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxide;

[0060] S2, perform iridium oxide loading:

[0061] S21. Mix manganese-cobalt-samarium metal composite oxide, iridium chloride and water, and stir for 15 hours; the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:2.

[0062] S22. Adjust the pH of the mixed solution to 9;

[0063] S23. Dry the solution and grind it to obtain the first powder;

[0064] S24. The first powder is calcined at 500°C for 2 hours, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0065] Perform performance testing:

[0066] A 1:1 mixture of Nafion solution, isopropanol, and water was prepared. The catalyst material was then added to the mixture and thoroughly mixed. The mixture was then ball-milled and ultrasonically treated. The catalyst suspension was sprayed onto an active surface with a surface area of ​​1 cm² at 75°C. 2 The loading of catalyst material was recorded on polytetrafluoroethylene. The sprayed catalyst material and a commercially available cathode Pt / C catalyst were then transferred onto a proton exchange membrane.

[0067] After testing, in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, 10 mA / cm 2 At the given current density, the overpotential of the oxygen evolution reaction is 211 mV; in the membrane electrode test, 1 A*cm -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 3845 hours.

[0068] Example 2

[0069] Preparation of catalyst materials

[0070] S1. Preparation of manganese-cobalt-samarium metal composite oxides:

[0071] S11. Dissolve cobalt nitrate, manganese nitrate, samarium nitrate and citric acid in water and stir for 12 hours to obtain the first mixed solution; wherein the molar ratio of cobalt nitrate, manganese nitrate and samarium nitrate is 75:10:10, the molar ratio of citric acid to cobalt nitrate is 6:1, and the amount of water added is sufficient to completely dissolve cobalt nitrate and samarium nitrate.

[0072] S12. The first mixed solution is subjected to an oxidation-reduction reaction in an air-injected reactor at a temperature of 450°C for 60 minutes.

[0073] S13. The obtained reactants are filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxide;

[0074] S2, perform iridium oxide loading:

[0075] S21. Mix manganese-cobalt-samarium metal composite oxide, iridium chloride and water, and stir for 12 hours; the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5.

[0076] S22. Adjust the pH of the mixed solution to 11;

[0077] S23. Dry the solution and grind it to obtain the first powder;

[0078] S24. The first powder is calcined at 400°C for 3 hours, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0079] The catalyst material prepared in Example 2 was subjected to performance testing using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At the given current density, the overpotential of the oxygen evolution reaction is 238 mV. In the membrane electrode test, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 3500 hours.

[0080] Example 3

[0081] Preparation of catalyst materials

[0082] S1. Preparation of manganese-cobalt-samarium metal composite oxides:

[0083] S11. Dissolve cobalt nitrate, manganese nitrate, samarium nitrate and citric acid in water and stir for 24 hours to obtain the first mixed solution; wherein the molar ratio of cobalt nitrate, manganese nitrate and samarium nitrate is 85:6:15, the molar ratio of citric acid to cobalt nitrate is 10:1, and the amount of water added is sufficient to completely dissolve cobalt nitrate and samarium nitrate.

[0084] S12. The first mixed solution is subjected to an oxidation-reduction reaction in an air-injected reactor at a temperature of 550°C for 90 minutes.

[0085] S13. The obtained reactants are filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxide;

[0086] S2, perform iridium oxide loading:

[0087] S21. Mix manganese-cobalt-samarium metal composite oxide, iridium chloride and water, and stir for 24 hours; the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:3.

[0088] S22. Adjust the pH of the mixed solution to 9;

[0089] S23. Dry the solution and grind it to obtain the first powder;

[0090] S24. The first powder is calcined at 600°C for 3 hours, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0091] The catalyst material prepared in Example 3 was subjected to performance testing using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At the given current density, the overpotential of the oxygen evolution reaction is 226 mV. In the membrane electrode test, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 3220 hours.

[0092] Comparative Example 1

[0093] Commercially available iridium oxide was used directly as a catalyst in the membrane electrode test for PEM water electrolysis to produce hydrogen.

[0094] The catalyst material prepared from commercial iridium oxide in Comparative Example 1 was tested using the same method as in Example 1. The results showed that, in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, and in the membrane electrode test, the performance was [value missing] at 1 A*cm [value missing]. -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 123 hours.

[0095] Comparative Example 2

[0096] The reference document 2 does not use a metal composite oxide, but rather cobalt oxide as a carrier.

[0097] The specific steps are as follows:

[0098] Preparation of catalyst materials

[0099] S21. Mix cobalt oxide, iridium chloride and water, and stir for 15 hours. The sum of the molar amounts of manganese, cobalt and samarium in the manganese-cobalt-samarium metal composite oxide in Example 1 is the molar amount of cobalt oxide added, and the mass of iridium chloride remains unchanged.

[0100] S22. Adjust the pH of the mixed solution to 9;

[0101] S23. Dry the solution and grind it to obtain the first powder;

[0102] S24. The first powder is calcined at 500°C for 2 hours, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0103] The catalyst material prepared in Comparative Example 2 was tested using the same method as in Example 1. The test showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, at a current density of 10 mA / cm², the overpotential of the oxygen evolution reaction was 315 mV. In the membrane electrode test, it could operate stably for 552 h at a current density of 1 A*cm⁻² and an iridium loading of 0.5 mg*cm⁻².

[0104] Comparative Example 3

[0105] The reference document 3 does not use a metal composite oxide, but rather samarium oxide as a carrier.

[0106] The specific steps are as follows:

[0107] Preparation of catalyst materials

[0108] S21. Mix samarium oxide, iridium chloride and water, and stir for 15 hours. The sum of the molar amounts of manganese, cobalt and samarium in the manganese-cobalt-samarium metal composite oxide in Example 1 is the molar amount of samarium oxide added, and the mass of iridium chloride remains unchanged.

[0109] S22. Adjust the pH of the mixed solution to 9;

[0110] S23. Dry the solution and grind it to obtain the first powder;

[0111] S24. The first powder is calcined at 500°C for 2 hours, washed with deionized water until neutral, dried, and ground to obtain the catalyst material.

[0112] The catalyst material prepared in Comparative Example 3 was tested using the same method as in Example 1. The test showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, at a current density of 10 mA / cm², the overpotential of the oxygen evolution reaction was 302 mV. In the membrane electrode test, it could operate stably for 618 h at a current density of 1 A*cm⁻² and an iridium loading of 0.5 mg*cm⁻².

[0113] Meanwhile, this specific method also included a case where only manganese oxide was used as a carrier, and the performance of the prepared catalyst material was significantly lower than that of the catalyst material prepared in Example 1.

[0114] Comparative Example 4

[0115] Comparative Example 4 adjusted the ratio of cobalt to samarium, and two sets of experimental procedures are disclosed below, namely Comparative Example 4-A and Comparative Example 4-B. The following two sets of experimental procedures only changed the ratio of cobalt to samarium in the manganese-cobalt-samarium metal composite oxide; the iridium oxide loading process was completely consistent with Example 1.

[0116] The process for preparing the manganese-cobalt-samarium metal composite oxide was the same as in Example 1, except that in Comparative Example 4-A, the molar ratio of cobalt nitrate to samarium nitrate was 80:30. In Comparative Example 4-B, the molar ratio of cobalt nitrate to samarium nitrate was 80:5; meanwhile, the total molar amounts of manganese nitrate, cobalt nitrate, and samarium nitrate were the same as in Example 1.

[0117] The catalyst material prepared in Comparative Example 4 was tested using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At a current density, the overpotential for the oxygen evolution reaction of the catalyst material in Comparative Example 4-A was 273 mV. In the membrane electrode assay, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium loading, it can operate stably for 2150 hours. The oxygen evolution reaction overpotential of the comparative example 4-B catalyst material is 282 mV. In membrane electrode testing, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 1887 hours.

[0118] Comparative Example 5

[0119] Comparative Example 5 changed the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride. Two sets of experimental procedures are disclosed below, namely Comparative Example 5-A and Comparative Example 5-B. The two sets of experimental procedures only changed the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride. The manganese-cobalt-samarium metal composite oxide prepared using the exact same method as in Example 1, and the operation procedure for iridium oxide loading was completely consistent with Example 1.

[0120] In Comparative Example 5-A, the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride was 1:1. In Comparative Example 5-B, the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride was 1:4.

[0121] The catalyst material prepared in Comparative Example 5 was tested using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At a current density, the overpotential for the oxygen evolution reaction of the catalyst material in Comparative Example 5-A was 254 mV. In membrane electrode testing, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium loading, it can operate stably for 2400 hours. The oxygen evolution reaction overpotential of the comparative example 5-B catalyst material is 280 mV. In membrane electrode testing, at 1 A*cm... -2At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 1700 hours.

[0122] Comparative Example 6

[0123] Comparative Example 6 used the same method as Example 1 to prepare a manganese-cobalt-samarium metal composite oxide, except for the loading process of iridium oxide.

[0124] In Comparative Example 6, the catalyst material was obtained by physically stirring and thoroughly mixing the manganese-cobalt-samarium metal composite oxide and iridium chloride.

[0125] The catalyst material prepared in Comparative Example 6 was subjected to performance testing using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At the given current density, the overpotential of the oxygen evolution reaction is 324 mV. In the membrane electrode test, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 460 hours.

[0126] Comparative Example 7

[0127] In Comparative Example 7, the preparation process of manganese-cobalt-samarium metal oxide was changed, while the loading process of iridium oxide was completely consistent with that in Example 1.

[0128] In Comparative Example 7, manganese oxide, cobalt oxide and iridium oxide were physically mixed to obtain a composite metal oxide.

[0129] The catalyst material prepared in Comparative Example 7 was subjected to performance testing using the same method as in Example 1. The test results showed that in a three-electrode system, in an oxygen-saturated 0.6M sulfuric acid solution, the performance was 10 mA / cm². 2 At the given current density, the overpotential of the oxygen evolution reaction is 355 mV. In the membrane electrode test, at 1 A*cm... -2 At current density and 0.5 mg*cm -2 With an iridium load, it can operate stably for 240 hours.

[0130] In this specific embodiment, three oxides were physically mixed to prepare a material with manganese-cobalt-iridium as the support and samarium oxide as the load, using the same raw material molar ratio as in Example 1; and a material with samarium-iridium as the support and cobalt oxide or manganese oxide as the load, using the same raw material molar ratio as in Example 1. Performance testing showed that the results were significantly unsatisfactory.

[0131] This application utilizes a manganese-cobalt-samarium metal composite oxide as a support to load iridium oxide, forming a unique catalyst composite material structure. During the preparation process, by precisely adjusting the metal addition ratio and optimizing process parameters and preparation sequence, not only was a low iridium content ensured, but the catalyst's activity and stability were also significantly improved, achieving remarkable results.

[0132] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a PEM water electrolysis anode oxygen evolution catalyst material, characterized in that, Includes the following steps: S1. Preparation of manganese-cobalt-samarium metal composite oxides: Cobalt nitrate, manganese nitrate, samarium nitrate, and citric acid were dissolved in water and stirred for more than 12 hours to obtain the first mixed solution; The first mixed solution undergoes a redox reaction in an air-injected reactor. The obtained reactants were filtered, washed with deionized water, dried, and ground to obtain manganese-cobalt-samarium metal composite oxides. The molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 75–85:6–10:10–15. S2, perform iridium oxide loading: Manganese-cobalt-samarium metal composite oxide, iridium chloride and water were mixed and stirred for more than 12 hours; Next, adjust the pH of the mixed solution to above 9; The solution was then dried and ground to obtain the first powder. The first powder was calcined at high temperature, washed with deionized water until neutral, dried, and ground to obtain the catalyst material. The mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5 to 3.

2. The preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to claim 1, characterized in that, In the preparation of manganese-cobalt-samarium metal composite oxides using S1, the molar ratio of citric acid to cobalt nitrate is 6-10:

1.

3. The preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to claim 1, characterized in that, In the preparation of manganese-cobalt-samarium metal composite oxides by S1, the temperature of the redox reaction in the reactor is 450℃~550℃, and the reaction time is 30min~90min.

4. The preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to claim 1, characterized in that, In the preparation of manganese-cobalt-samarium metal composite oxides by S1, the molar ratio of cobalt nitrate, manganese nitrate, and samarium nitrate is 80-85:8-10:10-12.

5. The preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to claim 1, characterized in that, During the preparation of manganese-cobalt-samarium metal composite oxides using S1, stirring is carried out for 12 to 24 hours.

6. The method for preparing the PEM water electrolysis anode oxygen evolution catalyst material according to any one of claims 1-5, characterized in that, In S2, the mass ratio of manganese-cobalt-samarium metal composite oxide to iridium chloride is 1:1.5 to 2.

7. The preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to claim 6, characterized in that, In S2, the stirring time is 12h to 24h.

8. The method for preparing the PEM water electrolysis anode oxygen evolution catalyst material according to claim 7, characterized in that, In S2, the first powder is calcined at a high temperature of 400℃-600℃ for 1h to 3h.

9. The catalyst material prepared by the preparation method of the PEM water electrolysis anode oxygen evolution catalyst material according to any one of claims 1-8.

10. The application of the catalyst material as described in claim 9 as an anode oxygen evolution catalyst in PEM water electrolysis.