Super-stable supported oxygen evolution electrocatalyst based on ripening-embedding method

Abstract

This invention relates to an ultrastable supported oxygen evolution electrocatalyst based on a ripening intercalation method, which is prepared using the following method: using a single metal oxide AO that remains stable under strong acid and strong oxidizing conditions. x Or mixed metal oxide A Y B Z O x Using noble metal atoms M or their alloys as the active component, a ripening-induced intercalation technique is employed to simultaneously control the growth of the support and the nucleation of the active component, thereby embedding noble metal or their alloy nanoparticles into a metal oxide support to obtain a metal oxide-supported catalyst M-AO. x This invention employs a ripening-induced intercalation technique to embed noble metal or alloy nanoparticles into different metal oxide supports, forming a stable and highly efficient supported catalyst. The catalyst developed in this invention maintains high catalytic activity and stability under strong acid and high current density environments, demonstrating broad application prospects, particularly in the field of green hydrogen energy.

Description

Ultrastable supported oxygen evolution electrocatalyst based on ripening intercalation method Technical Field

[0001] This invention belongs to the field of electrochemical catalysis technology, and specifically relates to an ultrastable supported oxygen evolution reaction (OER) electrocatalyst based on a ripening-induced intercalation method, used to improve the efficiency of proton exchange membrane electrolyzers (PEMWE). This invention employs a ripening-induced intercalation technique to embed noble metal or alloy nanoparticles into different metal oxide supports, forming a stable and highly efficient supported catalyst. The catalyst developed in this invention maintains high catalytic activity and stability under strong acid and high current density environments, and has broad application prospects, especially in the field of green hydrogen energy. Background Technology

[0002] Against the backdrop of global efforts to address climate change and reduce carbon emissions, hydrogen has attracted much attention as a clean energy carrier ([1], AM Oliveira, RR Beswick, Y. Yan, A green hydrogen economy for a renewable energy society. Curr. Opin. Chem. Eng.33, 100701 (2021)). Hydrogen is a zero-carbon energy source that produces only water during its use, thus it is pollution-free and has a high energy density ([2], A. Ursua, LM Gandia, P. Sanchis, Hydrogen production from water electrolysis: current status and future trends. Proc. IEEE100, 410-426 (2011)). Among various hydrogen production methods, water splitting is an important pathway, and PEMWE is considered one of the most promising technologies due to its high efficiency and the ability to produce high-purity hydrogen using green electricity ([3], M. Carmo, DL Fritz, J. Mergel, D. Stolten, A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 38, 4901-4934 (2013); [4], SS Kumar, V. Himabindu, Hydrogen production by PEM water electrolysis–A review. Mater. Sci. Energy Technol. 2, 442-454 (2019)). The water splitting process of PEMWE includes two half-reactions: the OER at the anode and the hydrogen evolution reaction (HER) at the cathode. Compared to HER, OER kinetics are more complex because it involves multiple electron transfers and multiple intermediate states, resulting in higher overpotentials ([5], SS Kumar, V. Himabindu, Hydrogen production by PEM water electrolysis–A review. Mater. Sci. Energy Technol.2, 442-454 (2019)). Therefore, improving OER efficiency is key to enhancing the overall performance of PEMWE.Under acidic conditions, iridium-based catalysts (such as IrO₂) are currently considered the best choice due to their excellent chemical stability and high catalytic activity for OER ([6], S, Wang, A. Lu, CJ Zhong. Hydrogen production from water electrolysis: role of catalysts. Nano Convergence, 8, 4 (2021)). However, the high cost of precious metals limits their application in large-scale industries ([7], C. Wang, L. Feng, Recent advances and perspectives of Ir-based anode catalysts in PEM water electrolysis. Energy Adv. 3, 14-29 (2024); [8], Ir market price of April, https: / / strategicmetalsinvest.com / iridium-prices / 8). In addition, noble metal nanoparticles are prone to detachment and aggregation during long-term use, leading to a decrease in catalytic activity ([9], C. Minke, M. Suermann, B. Bensmann, R. Hanke-Rauschenbach, Is iridium demand a potential bottleneck in the realization of large-scale PEM water electrolysis? Int. J. Hydrogen Energy 46, 23581-23590 (2021);

[0010] , H.-S. Ohet al., Electrochemical catalyst–support effects and their stabilizing role for IrO. xnanoparticle catalysts during the oxygen evolution reaction.J. Am. Chem. Soc.138, 12552-12563 (2016);

[0011] , F. Claudelet al., Degradation Mechanisms of Oxygen Evolution Reaction Electrocatalysts: A Combined Identical-Location Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy Study.ACS Catal.9, 4688-4698 (2019)-11).

[0003] Therefore, developing a noble metal-based catalyst with low loading, high activity, and high stability has become an important research hotspot.

[0004] Currently, noble metals IrO₂ and RuO₂ are the most commonly used acidic OER catalysts. However, their high cost limits their application in proton exchange membrane water electrolysis, and their activity and stability have not yet met the requirements for industrial applications (9-11). Studies have shown that loading noble metals such as Ru and Ir, or their oxides (such as IrO₂ and RuO₂), onto metal oxides that are stable under acidic conditions can significantly reduce the amount of noble metals required while maintaining catalyst activity, thereby reducing costs (

[0012] , H.-S. Oh et al., Electrochemical catalyst–support effects and their stabilizing role for IrO₂). xnanoparticle catalysts during the oxygen evolution reaction.J. Am. Chem. Soc.138, 12552-12563 (2016);

[0013] ,E. Oaktonet al., IrO2-TiO2: A High-urface-Area, Active, and Stable Electrocatalyst for the Oxygen Evolution Reaction.ACS Catal.7, 2346-2352 (2017);

[0014] ,H. Ohno, S. Nohara, K. Kakinuma, M. Uchida, H. Uchida, Effect of electronic conductivities of iridium oxide / doped SnO2oxygen-evolving catalysts on the polarization properties in proton exchange membrane water electrolysis.Catalysts9, 74 (2019);

[0015] ,F. Claudelet al., Degradation Mechanisms of Oxygen Evolution Reaction Electrocatalysts: A Combined Identical-Location Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy Study.ACS Catal.9, 4688-4698 (2019)-18;

[0016] ,Z. Shiet al., Enhanced acidic water oxidation by dynamic migration of oxygen species at the Ir / Nb2O 5-xcatalyst / support interfaces.Angew. Chem. Int. Ed.61, e202212341 (2022);

[0017] S. Geet al., A robust chromium–iridium oxide catalyst for high-current–density acidic oxygen evolution in proton exchange membrane electrolyzers.Energy Environ. Sci.16, 3734-3742 (2023);

[0018] Y. Wanget al., Nano-metal diborides-supported anode catalyst with strongly coupled TaOx / IrO2 catalytic layer for low-iridium-loading proton exchange membrane electrolyzer. Nat. Commun. 14, 5119 (2023)). Technical issues

[0005] To address the problems in the prior art, this invention proposes a method for preparing an ultrastable supported oxygen evolution electrocatalyst based on a ripening-in-place method, which utilizes ripening-induced intercalation technology to embed noble metal nanoparticles into a metal oxide support.

[0006] Another object of the present invention is to provide a product prepared by the above method.

[0007] Another object of the present invention is to provide applications of the above-mentioned products. Technical solutions

[0008] To achieve the above objectives, the present invention employs the following technical solution: a method for preparing an ultrastable supported oxygen evolution electrocatalyst based on a ripening and intercalation method, which maintains stability of a single metal oxide AO under strong acid and strong oxidizing conditions. x Or mixed metal oxide A Y B Z O x Using noble metal atoms M or their alloys as the active component, the growth of the support and the nucleation of the active component are simultaneously controlled by a ripening-induced intercalation technique. This allows for the embedding of noble metal or alloy nanoparticles into a metal oxide support, resulting in a metal oxide-supported catalyst M-AO. x It includes the following steps:

[0009] A solution is obtained by dissolving a noble metal M, or its noble metal alloy, or an alloy salt formed with other non-noble metal elements, in a polyol solvent. The noble metal M alloy is at least one of iridium (Ir), ruthenium (Ru), and platinum (Pt). The alloy with other non-noble metal elements is at least one of tungsten (W), molybdenum (Mo), palladium (Pd), silver (Ag), manganese (Mn), lead (Pb), tin (Sn), antimony (Sb), zirconium (Zr), tantalum (Ta), niobium (Nb), titanium (Ti), chromium (Cr), cobalt (Co), indium (In), lanthanum (La), or cerium (Ce).

[0010] The metal oxide powder is added to the above solution and dispersed evenly to form a mixed solution. The metal oxide is composed of a single metal oxide AO. x Or a combination of mixed metal oxides;

[0011] Under ultrasonic treatment, the mixed solution is heated at 80 ℃ - 200 ℃ for 1 h - 6 h, and then filtered to obtain a precipitate. The precipitate can be washed with ethanol and water to obtain a supported metal oxide catalyst. During the heating and ultrasonication process, the metal oxide support particles mature, that is, their size increases, which leads to the embedding of noble metal or its alloy particles nucleated on the support surface into the support, thus obtaining an ultrastable supported oxygen evolution electrocatalyst based on the maturation embedding method.

[0012] This invention successfully prepared a highly efficient and stable oxygen evolution reaction catalyst by rationally selecting materials and optimizing the preparation process. It effectively prevents the shedding and agglomeration of precious metals or their alloy particles and significantly enhances the stability of the catalyst.

[0013] Preferably, the metal atoms in the carrier component are selected from transition metals or main group metals other than noble metals, wherein,

[0014] Single metal oxide AO x The metal atom A in the atom is at least one or more metal oxides selected from tungsten (W), molybdenum (Mo), palladium (Pd), silver (Ag), manganese (Mn), lead (Pb), tin (Sn), antimony (Sb), zirconium (Zr), tantalum (Ta), niobium (Nb), titanium (Ti), chromium (Cr), cobalt (Co), indium (In), lanthanum (La), or cerium (Ce).

[0015] The mixed metal oxide comprises two metal oxides A Y B Z O x It consists of one or more different metal oxides, and metal atoms A and B are different from each other, where Y and Z are the stoichiometric ratios of elements A and B.

[0016] Preferably, the noble metal salt is a Ru salt, an Ir salt, or a Pt salt. The Ru salt is selected from at least one of anhydrous ruthenium chloride, hydrated ruthenium chloride, ruthenium chloride trihydrate, ruthenium acetylacetonate, and ruthenium nitrite. The Ir salt is selected from at least one of anhydrous iridium trichloride, iridium trichloride hydrate, iridium tetrachloride hydrate, iridium acetylacetonate, and sodium hexachloroacetate. The Pt salt is selected from at least one of chloroplatinic acid hydrate, chloroplatinic acid hexahydrate, platinum hexahydroxide, sodium platinum hexahydroxide, platinum acetylacetonate, potassium hexachloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinate, potassium chloroplatinate, ammonium chloroplatinate, potassium trichloroplatinate hydrate, and tetrabutylammonium chloroplatinate.

[0017] Preferably, the salt of the precious metal and other non-precious metal alloy is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, ammonium paratungstate, sodium tungstate, ammonium molybdate, molybdenum trioxide, palladium nitrate, palladium acetate, palladium chloride, silver nitrate, silver acetate, manganese nitrate, manganese acetate, manganese chloride, lead nitrate, lead acetate, tin chloride, antimony chloride, antimony acetate, zirconium nitrate, zirconium oxychloride, tantalum chloride, tantalum ethoxide, niobium chloride, niobium ethoxide, cerium nitrate, cerium sulfate, and cerium ammonium nitrate.

[0018] A method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the above-described ripening intercalation method, wherein the amounts of the active component, support, and polyol solvent are as follows:

[0019] A solution is prepared by dissolving 0.5 g to 5 g of a precious metal salt, or an alloy thereof, or an alloy with other non-precious metals in 50 mL to 200 mL of a polyol solvent, and then mixing it with 1 g to 20 g of a metal oxide, wherein the polyol solvent is one of ethylene glycol, glycerol, 1,2-propanediol, and pentaerythritol.

[0020] Specifically, follow these steps:

[0021] S1.1, the metal precursor salt and carbon powder are added to a polyol solvent and dispersed evenly to obtain a mixture. The metal precursor is selected from at least one of W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Co, and Ce. Under ultrasonic treatment, the precursor salt is rapidly decomposed, and a suspension is obtained after several hours. The suspension is then treated by centrifugation or filtration to obtain a precipitate.

[0022] S1.2, After drying the obtained precipitate, place it in a tube furnace and calcine it to 200℃-1000℃ in a hydrogen-argon mixture or air atmosphere at a heating rate of 1℃ / min-20℃ / min for 1 h-6 h to obtain the metal oxide AO. x ;

[0023] S1.3, take 0.5 g-5 g of a noble metal salt, such as ruthenium, iridium, or platinum, or an alloy thereof, or an alloy salt with other non-noble metals; 50 mL-200 mL of polyol solvent; and 1 g-20 g of metal oxide AO. x The noble metal salt is dissolved in a polyol solvent selected from ethylene glycol, glycerol, 1,2-propanediol, and pentaerythritol, and then a metal oxide AO is added. x This ensures uniform dispersion, resulting in a mixed solution.

[0024] S1.4 The mixed solution was ultrasonically heated for 1 h to 5 h under preset conditions of 80 ℃ - 200 ℃ and then filtered to obtain a precipitated product, which is a metal oxide supported catalyst.

[0025] The present invention also provides an ultrastable supported oxygen evolution electrocatalyst prepared by the above method based on the ripening and intercalation method, wherein the content of noble metal M in the active component is 1%-50% by mass, and the total content of other metal atoms A is 50%-99%.

[0026] Optionally, when the metal oxide AO x CeO x The noble metal atom M is Ir, and the metal oxide supported catalyst M-AO x For Ir-CeO x ;

[0027] Or, when metal oxide AO x MnO x The noble metal atom M is Ru, and the metal oxide supported catalyst M-AO x Ru-MnO x ;

[0028] Or, when metal oxide AO x MnO x The noble metal atoms M are Ru and Ir, and the metal oxide supported catalyst M-AO x for RuIr-MnO x .

[0029] This invention also provides an application of a metal oxide supported catalyst. The catalyst developed in this invention exhibits excellent performance, lower overpotential and higher long-term stability in the application of a proton exchange membrane electrolyzer (PEMWE).

[0030] Especially as an anode electrode catalyst in proton exchange membrane electrolysis devices.

[0031] This invention employs a ripening-induced intercalation technique to achieve simultaneous control over the growth of the support and the nucleation of the active component, ensuring uniform particle distribution on the support. Compared to traditional surface-loading methods, this significantly improves catalyst stability. The method is simple and easy to implement, suitable for large-scale production, and is expected to reduce the cost of using precious metal-based catalysts and improve the economics of hydrogen production technology. Beneficial effects

[0032] Improved stability: The embedded structure effectively prevents the shedding and aggregation of noble metal nanoparticles, thereby enhancing the structural stability of the catalyst.

[0033] Enhanced catalytic activity: By optimizing the nanostructure and electron transport pathway, the overpotential of the OER reaction was reduced.

[0034] Cost reduction: While ensuring high performance, the amount of precious metals used was reduced, thus improving economic feasibility.

[0035] The technical solution of the present invention has the following beneficial effects:

[0036] 1. In this invention, noble metals or their alloys (such as Ru, Ir, Pt, or alloys thereof, or alloys with other non-noble metals such as W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La, or Ce) are loaded onto metal oxides stable in acidic and oxidizing environments, embedding noble metal or alloy nanoparticles into the oxide support. This method not only effectively prevents particle detachment and agglomeration but also significantly improves electrochemical performance.

[0037] 2. The content of precious metals is greatly reduced while maintaining the activity of the catalyst, thereby reducing the cost of the catalyst.

[0038] 3. The metal oxide supported catalyst and oxygen evolution reaction catalyst electrode of the present invention have a simple preparation process and low cost, and can realize a highly active and stable oxygen evolution reaction in water electrolysis, and have broad application prospects. Attached Figure Description

[0039] Figure 1 shows the metal oxide CeO. x Transmission electron microscopy (TEM) Figure 1A and schematic diagram of dimensional statistics 1B;

[0040] Figure 2 shows the metal oxide supported catalyst Ir-CeO. x Schematic diagrams of X-ray diffraction (XRD) patterns 2A and TEM images 2B;

[0041] Figure 3 shows Ir-CeO xAberration-corrected high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) images and three-dimensional electron tomography (ET) reconstruction images;

[0042] Figure 4 is a comparison of the linear sweep voltammetry (LSV) curves of metal oxide supported catalysts and commercial catalysts as OER catalyst electrodes.

[0043] Figure 5 shows the metal oxide supported catalyst Ir-CeO. x A schematic diagram of the stability test curve of the anode catalyst in the PEM unit using constant current mode;

[0044] Figure 6 is a flowchart of the preparation method of metal oxide supported catalyst;

[0045] Figure 7 is a flowchart of the preparation method of the OER reaction catalyst electrode. Embodiments of the present invention

[0046] In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention. However, it will be apparent to those skilled in the art that the invention may be practiced without one or more of these details. To avoid confusion with the invention, well-known technical features in the art are not described in detail herein. It should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments provided herein. These embodiments are provided to make the disclosure comprehensive and complete and to fully convey the scope of the invention to those skilled in the art. The singular forms “a,” “an,” and “the” used herein also include the plural forms unless the context clearly indicates the opposite. It should also be understood that the term “comprising” is used to specify the presence of the stated features, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The term “and / or” used herein includes any and all combinations of the listed items.

[0047] The core of this invention lies in forming an intercalated catalyst through a ripening-induced intercalation technique. This design enables the catalyst to achieve high activity and long-term stability while reducing the precious metal content, thereby lowering costs and improving water electrolysis efficiency. This type of catalyst can meet the stability and activity requirements of proton exchange membrane water electrolysis under strongly acidic and highly oxidizing environments.

[0048] The technical solution proposed in this invention will be further described in detail with reference to the accompanying drawings and specific embodiments. The advantages and features of this invention will become clearer from the following description. It should be noted that the drawings are presented in a simplified form and are not to scale; they are only used to facilitate and clearly illustrate the embodiments of this invention.

[0049] One embodiment of the present invention provides a metal oxide supported catalyst, the material of which is abbreviated as M-AO. x The catalyst comprises a support component and an active component. The support component is a metal oxide (AO). x It exhibits stability under strongly acidic and strongly oxidizing conditions; the active component consists of noble metal atoms (M). The noble metal atoms (M) are selected from at least one of Ru, Ir, and Pt, or alloys thereof, or alloys with other non-noble metals such as W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La, or Ce. Metal oxides AO x It consists of another metal A, selected from transition metal atoms or main group metal atoms, but not noble metal atoms, such as W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La, or Ce. AO x The oxides should remain stable under strong acidic and strong oxidizing conditions (such as the acidic conditions of water electrolysis).

[0050] Mixed metal oxides ABO x It can also be used as a support, which consists of two or more different metal oxides, such as AO. x and BO x Both oxides are stable under strong acidic and strong oxidizing conditions (such as the acidic conditions of water electrolysis). Metal atoms A and B are distinct from each other and are selected from transition metals or main group metals other than noble metal atoms M. Metal oxide AO x and BO x It can be any two applicable metal oxides that meet the above conditions. Preferably, A and B can be selected from W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La, or Ce.

[0051] In the embodiments of the present invention, metal oxide AO x CeO x The noble metal atom M is Ir, and the metal oxide supported catalyst M-AO x For Ir-CeO x .

[0052] In this embodiment of the invention, the total content of metal atoms A and M is considered to be 100%, wherein the content of noble metal atoms M (including Ru, Ir, Pt or alloys thereof, or alloys with other non-noble metals such as W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La or Ce) ranges from 1% to 50%, while the total content of metal atoms A ranges from 50% to 99%.

[0053] The following is about Ir-CeO x The performance is analyzed and described in detail.

[0054] Figure 1 shows the metal oxide CeO. x Figure 1A shows a transmission electron microscope (TEM) image of the catalyst, and Figure 1B shows a schematic diagram of the dimensional statistics. Figure 2 shows the metal oxide supported catalyst Ir-CeO. x The X-ray diffraction (XRD) pattern 2A and TEM image schematic 2B are shown. Combining Figures 1 and 2, it can be seen that the metal oxide CeO... x The particles are approximately 7.9 nm in size, and noble metal Ir atoms were successfully loaded onto the metal oxide CeO. x The carrier has a low Ir content and a particle size of about 2 nm.

[0055] Figure 3 shows Ir-CeO x Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images and three-dimensional electron tomography (ET) reconstructions indicate that noble metal Ir nanoparticles were successfully embedded in CeO. x In the carrier. This is due to the curing (i.e., size increase) of the carrier under heating and ultrasonic treatment during Ir loading, resulting in CeO₂... x Surface-nucleated Ir particles are embedded inside the carrier.

[0056] Figure 4 shows a comparison of linear sweep voltammetry (LSV) curves of metal oxide supported catalysts and commercial catalysts as OER catalyst electrodes, with an LSV scan rate of 5 mV / s for each material. As can be seen from Figure 4A, Ir-CeO... x The catalyst requires an overpotential of 240 mV at an oxygen evolution current density of 10 mA / cm², which is significantly better than that of commercial IrO₂ catalysts.

[0057] Figure 5 shows the metal oxide supported catalyst Ir-CeO. x As the anode catalyst in the PEM unit, the stability test curve is shown in the schematic diagram using constant current mode with a current density of 1 A / cm². 2 The temperature was 80℃. The results showed that under operating conditions, Ir-CeO xThe catalyst did not show a significant voltage increase over 500 hours, indicating that the Ir-CeO catalyst... x The catalyst exhibits high stability.

[0058] In summary, the metal oxide supported catalyst Ir-CeO in this embodiment... x Noble metal Ir nanoparticles were embedded into CeO using a ripening-induced intercalation technique. x In a carrier, this method not only effectively prevents particle detachment and aggregation but also significantly improves electrochemical performance. The catalyst developed in this invention exhibits excellent performance in proton exchange membrane water electrolysis applications, including lower overpotential and higher long-term stability.

[0059] This embodiment provides a metal oxide supported catalyst Ir-CeO x Prepare according to the steps in Figure 6:

[0060] S1.1, According to the required ratio, the metal precursor salt and carbon powder are added to the polyol solvent to disperse them evenly and obtain a mixture. The metal precursor is selected from at least one of W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Co, and Ce. Under ultrasonic action, the precursor salt is rapidly decomposed, and a suspension is obtained after several hours. The suspension is treated by centrifugation or filtration to obtain a precipitate.

[0061] S1.2, the precipitate is dried and then calcined in a tube furnace (e.g., in a hydrogen-argon mixture or air atmosphere, heated to 200℃-1000℃ at a heating rate of 1℃ / min-20℃ / min, calcined for 1 h-6 h) to obtain metal oxide AO. x ;

[0062] S1.3, prepare according to the required ratio (e.g., 0.5 g-5 g ruthenium salt, iridium salt, or platinum salt, 50 mL-200 mL polyol solvent, and 1 g-20 g metal oxide AO). x The noble metal salt is dissolved in a polyol solvent selected from ethylene glycol, glycerol, 1,2-propanediol, and pentaerythritol, and then a metal oxide AO is added. xTo achieve uniform dispersion and obtain a mixed solution, the noble metal atom M in the noble metal salt can be at least one of Ru, Ir, or Pt, or an alloy of them, or an alloy of other non-noble metals such as W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Ti, Cr, Co, In, La, or Ce. Wherein, the Ru salt is selected from at least one of anhydrous ruthenium chloride, hydrated ruthenium chloride, ruthenium chloride trihydrate, ruthenium acetylacetonate, and ruthenium nitrite; the Ir salt is selected from at least one of anhydrous iridium trichloride, iridium trichloride hydrate, iridium tetrachloride hydrate, iridium acetylacetonate, and sodium hexachloroacetate; and the Pt salt is selected from at least one of chloroplatinic acid hydrate, chloroplatinic acid hexahydrate, platinum hexahydroxide, sodium platinum hexahydroxide, platinum acetylacetonate, potassium hexachloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinate, potassium chloroplatinate, ammonium chloroplatinate, potassium trichloroplatinate hydrate, and tetrabutylammonium hexachloroplatinate.

[0063] S1.4 The mixed solution is ultrasonically heated under preset conditions (the preset conditions are heating the mixed solution at 80 ℃ - 200 ℃ for 1 h - 5 h) and filtered. The resulting precipitate is the metal oxide supported catalyst.

[0064] The metal oxide supported catalyst prepared in this embodiment can be used as an OER catalyst electrode or as an anode catalyst in a PEM water electrolysis device.

[0065] Figure 7 also provides a method for preparing an OER reaction catalyst electrode, which includes the following steps:

[0066] S2.1, a metal oxide supported catalyst as described in this embodiment will be provided, or a metal oxide supported catalyst will be prepared using the preparation method of the mixed metal oxide supported catalyst described in this embodiment.

[0067] S2.2, the mixed metal oxide supported catalyst described in this embodiment, together with a binder (such as a perfluorosulfonic acid polymer solution) and a conductive agent (which may include at least one of carbon nanotubes, carbon black, or graphene), is added to a mixed solvent of an organic solvent (methanol, ethanol, isopropanol, tetrahydrofuran, or acetone) and water to form a catalyst slurry. Optionally, the binder accounts for 1% to 30% by weight in the catalyst slurry, and the conductive agent accounts for 10% to 30% by weight in the catalyst slurry.

[0068] S2.3, the catalyst slurry is ultrasonically dispersed and then coated onto a conductive substrate, such as carbon felt, carbon film, carbon cloth, metal foam, or metal foil (50 μm – 250 μm conductive carbon film), to form an electrode. Alternatively, the slurry can be coated onto a proton exchange membrane with a thickness of 10 μm – 250 μm to form an anode loaded with the metal oxide catalyst of this embodiment. Another method is to first spray the catalyst slurry onto a support film (such as a PTFE film with a thickness of 10 μm – 250 μm), dry it, and then hot-press it at 100 °C – 260 °C and a pressure of 1 MPa – 20 MPa for 1 – 20 min. After holding the pressure, the film is peeled off to obtain a membrane electrode loaded with the mixed metal oxide catalyst of this embodiment. The loading of the metal oxide supported catalyst in this embodiment is 0.1 mg / cm² – 50 mg / cm², and the mass percentage of the binder is 5% – 40%.

[0069] The preparation methods of the metal oxide supported catalyst and the OER reaction catalyst electrode in this embodiment will be explained in detail below with specific examples. Example 1

[0070] 1) An ultrastable supported oxygen evolution electrocatalyst Ir-CeO based on a ripening intercalation method x Prepare according to the steps in Figure 6:

[0071] S1.1 Weigh 1 g of cerium acetylacetone and 1 g of carbon powder into 50 mL of ethylene glycol, disperse by ultrasonication for 100 min to form a uniformly dispersed suspension, and then centrifuge to obtain the precipitate.

[0072] S1.2, after the precipitate is dried, it is placed in a tube furnace and annealed at 600 °C for 2 h. After cooling to room temperature, the metal oxide CeO is obtained. x ;

[0073] S1.3, 100 mg of CeO metal oxide x Disperse the solution in 50 mL of ethylene glycol, add 70 mg of iridium acetylacetone in ethylene glycol to obtain a mixture;

[0074] S1.4, the mixed solution was placed in an oil bath and heated at 180 °C for 2 h under continuous sonication. After cooling to room temperature, it was filtered to obtain the mixed metal oxide supported catalyst Ir-CeO. x .

[0075] Figure 1A shows the metal oxide CeO. x The transmission electron microscope (TEM) images are shown in Figure 1B, which is a statistical diagram of particle diameter distribution. Figure 2A shows the particle diameter distribution of CeO3 metal oxide. xBefore loading Ir, a supported catalyst Ir-CeO is formed with the loaded Ir. x Comparison of subsequent X-ray diffraction (XRD) spectra; Figure 2B shows Ir-CeO₂. x TEM images. Combining Figures 1 and 2, it can be seen that the metal oxide CeO... x The particles are approximately 7.9 nm in size, and noble metal Ir atoms were successfully loaded onto the metal oxide CeO. x The carrier has a low Ir content and a particle size of about 2 nm.

[0076] Figure 3A shows Ir-CeO x Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images show that Ir is embedded with CeO at the atomic scale. x Inside the carrier, Figure 3B shows Ir-CeO x The electron tomography (ET) 3D reconstruction image further demonstrates that the noble metal Ir nanoparticles were successfully embedded in CeO. x In the carrier. This is due to the curing (i.e., size increase) of the carrier under heating and ultrasonic treatment during Ir loading, resulting in CeO₂... x Surface-nucleated Ir particles are embedded inside the carrier.

[0077] 2) A supported catalyst Ir-CeO based on the above-mentioned metal oxide as a support x The anode electrode for proton exchange membrane water electrolysis is prepared according to the steps shown in Figure 7:

[0078] S2.1, Using the above method, prepare the metal oxide supported catalyst Ir-CeO x ;

[0079] S2.2, Weigh 20 mg of catalyst Ir-CeO x The catalyst slurry was obtained by dispersing it in 10 mL of isopropanol, adding 120 μL of 5 wt% perfluorosulfonic acid resin solution, and ultrasonically dispersing it evenly.

[0080] S2.3, spray the catalyst slurry onto an area of ​​5 cm². 2 On a Nafion® 212 proton exchange membrane. After drying, a metal oxide-supported catalyst Ir-CeO was obtained. x The anode.

[0081] Figure 4A shows that as the voltage increases, Ir-CeO x The rate of increase in catalytic current is significantly better than that of commercial IrO2 catalysts; at an oxygen evolution current density of 10 mA / cm², Ir-CeO… xThe required overpotential is only 240 mV, which is much lower than that of commercial IrO2 catalysts (440 mV), demonstrating its good catalytic activity.

[0082] 3) Based on the above, there is a metal oxide supported catalyst Ir-CeO x Assembly of a water electrolysis device with a proton exchange membrane anode:

[0083] S3.1 Weigh 5 mg of platinum-carbon catalyst with a platinum content of 40% and disperse it in 10 mL of a mixed solution of methanol and water (methanol:water = 9:1). At the same time, add 30 μL of 5wt% perfluorosulfonic acid resin solution and ultrasonically disperse it evenly to obtain another catalyst slurry.

[0084] S3.2, the other catalyst slurry is sprayed onto the already sprayed area with a surface area of ​​5 cm². 2 The anode catalyst is located on the back side of a Nafion® 212 proton exchange membrane, and the platinum-carbon catalyst supported on the back side of the proton exchange membrane has a platinum loading of approximately 0.1 mg. Pt / cm 2 ;

[0085] S3.3, after drying the proton exchange membrane, an anode catalyst (i.e., a metal oxide supported catalyst Ir-CeO) is obtained on both sides. x The proton exchange membrane of the cathode catalyst (platinum-carbon catalyst);

[0086] S3.4, the proton exchange membrane is hot-pressed at 60 °C and 2 MPa for 10 min to obtain the membrane electrode assembly for the water electrolysis device; Step S3.5, sealing rings and porous sintered titanium felt (5 cm² area) are respectively assembled on both sides of the membrane electrode assembly prepared above. 2 ), a titanium bipolar plate with an S-shaped flow channel (5 cm² area) 2 ( ), assemble the proton exchange membrane water electrolysis device; step S3.6, introduce deionized water at 80 ℃ into the anode side of the proton exchange membrane water electrolysis device and perform electrochemical tests.

[0087] Figure 5 shows the metal oxide supported catalyst Ir-CeO. x As the anode catalyst in the PEM unit, the stability test curve is shown in the schematic diagram using constant current mode with a current density of 1 A / cm². 2 The temperature was 80℃. The results showed that under operating conditions, Ir-CeO x The catalyst did not show a significant voltage increase over 500 hours, indicating that the Ir-CeO catalyst... x The catalyst exhibits high stability. When using commercial IrO2 as a catalyst, equipment stability and the use of Ir-CeO2 are comparable. xThe time is approximately the same, but at the same 1 A / cm 2 At current density, the required voltage is higher than that using Ir-CeO x The device operates at nearly 230 mV, resulting in significantly higher energy consumption. This is because the Ir metal loading in commercial IrO2 is much higher than that in Ir-CeO. x This result shows that Ir-CeO x Significant advantages in reducing the cost of hydrogen production through water electrolysis. Example 2

[0088] 1) An ultrastable supported oxygen evolution electrocatalyst Ru-MnO based on a ripening intercalation method x Prepare according to the steps in Figure 6:

[0089] S1.1: Weigh 1 g of manganese acetylacetone and 1 g of carbon powder, add them to 50 ml of ethylene glycol; ultrasonically disperse for 120 min to form a uniformly dispersed suspension; after ultrasonic treatment, centrifuge the suspension and collect the precipitate;

[0090] S1.2: The precipitate obtained in S1.1 was dried and placed in a tube furnace for annealing at 600 °C for 4 h, and then cooled to room temperature to obtain the metal oxide MnO. x ;

[0091] S1.3: Add 100 mg MnO x The metal oxide was dispersed in 50 ml of ethylene glycol, and 80 mg of ethylene glycol solution containing ruthenium acetylacetone was added to form a mixed solution.

[0092] S1.4: The mixed solution was placed in an oil bath and continuously ultrasonically heated at 180 °C for 2.5 h; after cooling to room temperature, it was filtered to obtain the metal oxide supported catalyst Ru-MnO. x .

[0093] 2) A Ru-MnO x The supported catalyst electrode was prepared according to the steps shown in Figure 7:

[0094] S2.1, Prepare the metal oxide supported catalyst Ru-MnO using the above method. x ;

[0095] S2.2: Add 5 mg Ru-MnO x Add 20 μL of 5 wt% perfluorosulfonic acid resin solution to 1 ml of a mixed solvent of ethanol and water (ethanol to water volume ratio of 4:1); ultrasonically disperse the mixture to form a catalyst slurry;

[0096] S2.3: The catalyst slurry is drop-coated onto a glassy carbon electrode with an area of ​​0.0706 cm²; after drying, the OER catalyst electrode is obtained.

[0097] Linear sweep voltammetry (LSV) was performed using the OER catalyst electrode in a 0.5 M H₂SO₄ aqueous solution. The LSV curve in Figure 4b shows that Ru-MnO x The performance of the catalyst electrode is significantly better than that of commercial catalyst electrodes. Example 3

[0098] 1) An ultrastable supported oxygen evolution electrocatalyst RuIr-MnO based on a ripening intercalation method x Prepare according to the steps shown in Figure 6:

[0099] S1.1 Weigh 1 g of manganese acetylacetone and 1 g of carbon powder, add them to 50 ml of ethylene glycol; ultrasonically disperse for 120 min to form a uniformly dispersed suspension; after ultrasonic treatment, centrifuge the suspension to obtain the precipitate;

[0100] S1.2, the precipitate was dried and placed in a tube furnace for annealing at 600 °C for 4 h, then cooled to room temperature to obtain the metal oxide MnO. x ;

[0101] S1.3, 100 mg MnO x The metal oxide was dispersed in 50 ml of ethylene glycol, and 40 mg of ethylene glycol solution containing ruthenium acetylacetone and 40 mg of ethylene glycol solution containing iridium acetylacetone were added to form a mixed solution.

[0102] S1.4: The mixed solution was placed in an oil bath and continuously ultrasonically heated at 180°C for 2.5 h; after cooling to room temperature, it was filtered to obtain the metal oxide supported catalyst RuIr-MnO. x .

[0103] 2) A Ru-MnO x The supported catalyst electrode was prepared according to the steps shown in Figure 7:

[0104] S2.1, Prepare the metal oxide supported catalyst RuIr-MnO using the above method. x ;

[0105] S2.2, 5 mg RuIr-MnO x Add 20 μL of 5 wt% perfluorosulfonic acid resin solution to 1 ml of a mixed solvent of ethanol and water (ethanol to water volume ratio of 4:1); ultrasonically disperse the mixture to form a catalyst slurry;

[0106] S2.3, the catalyst slurry is drop-coated onto a glassy carbon electrode with an area of ​​0.0706 cm²; after drying, Ru-MnO is obtained. x Supported catalyst electrode.

[0107] The catalyst was used in a 0.5 M H₂SO₄ aqueous solution for LSV testing. The LSV curves in Figure 4B show that the performance of this catalyst electrode is significantly better than that of commercial catalyst electrodes.

[0108] Figure 4B shows the RuIr-MnO catalyst formed when an alloy of two noble metals, Ru and Ir, is used as the catalyst and MnO2 is used as the support. x The catalyst also exhibits significantly superior catalytic activity compared to commercial IrO2 catalysts, and the stability of this alloy-supported catalyst is also better than that of Ru-MnO prepared using only Ru. x catalyst.

[0109] The above three specific embodiments are merely illustrative of the present invention and do not imply that the technical solution of the present invention is limited to these examples. Any noble metal atom (M) and any metal oxide support (AO) can be combined through a ripening-induced embedding method. x The improved stability of the OER catalyst should be considered within the scope of this invention. Some technical details listed in the specific embodiments of this invention are adjustable. For example, when the prepared metal oxide supported catalyst material is used as the anode catalyst in the PEM device, and the platinum-carbon (Pt / C) catalyst is used as the cathode catalyst, the platinum content in the cathode catalyst can be 20% - 100%. When a perfluorosulfonic acid proton exchange membrane is used as the separator, its thickness can be between 25 μm and 250 μm. Furthermore, the assembled MEA can be equipped with sealing rings on both sides, and porous sintered titanium felt or carbon paper with microporous layers can be used as gas diffusion layers on both the anode and cathode. The bipolar plates can be made of graphite plates, stainless steel plates, or titanium plates. The electrolyte in the water electrolysis device can be a 0.05 M - 2 M sulfuric acid solution or pure water, thus assembling a proton exchange membrane water electrolysis device.

[0110] When using the metal oxide supported catalyst material prepared according to this invention as the MEA of a PEM device, the following method can also be adopted: The metal oxide supported catalyst is dispersed in a mixed solvent of organic solvent and water, a binder is added, and then ultrasonically dispersed to form a uniform catalyst slurry. This slurry can be sprayed onto a proton exchange membrane with a thickness of 10-250 μm. Alternatively, the catalyst slurry can be sprayed onto a PTFE film with a thickness of 10-250 μm, dried, and then transferred onto the proton exchange membrane. The assembly is then hot-pressed at 100 °C – 260 °C and 1-20 MPa for 1-20 min. After holding the pressure, the PTFE film is removed to obtain the membrane anode loaded with the catalyst. In these examples, the catalyst loading is 0.25-5 mg / cm², and the binder mass percentage ranges from 5% to 40%. The catalyst and electrode preparation process of this embodiment is simple, achieving high oxygen evolution activity and stability while reducing the noble metal content in the catalyst, and has broad application prospects.

[0111] In summary, this invention employs a ripening-induced intercalation technique to embed noble metal nanoparticles into an oxide support. This method not only effectively prevents particle detachment and aggregation but also significantly improves electrochemical performance. The catalyst developed in this invention exhibits excellent performance, lower overpotential, and higher long-term stability in PEMWE applications. Furthermore, the preparation process of the metal oxide supported catalyst is simple and has broad application prospects.

[0112] The above description is merely a preferred embodiment of the present invention and does not limit the scope of the invention in any way. Any modifications or alterations based on the disclosed content, if made by those skilled in the art, should be considered within the protection scope of the present invention.

Claims

1. A method for preparing an ultrastable supported oxygen evolution electrocatalyst based on a ripening and intercalation method, characterized in that it uses a single metal oxide AO that remains stable under strong acid and strong oxidizing conditions. x Or mixed metal oxide A Y B Z O x Using noble metal atoms M or their alloys as the active component, a ripening-induced intercalation technique is employed to simultaneously control the growth of the support and the nucleation of the active component, thereby embedding noble metal or their alloy nanoparticles into a metal oxide support to obtain a metal oxide-supported catalyst M-AO. x It includes the following steps: A solution is obtained by dissolving a noble metal M, or its noble metal alloy, or an alloy salt formed with other non-noble metal elements, in a polyol solvent. The noble metal M alloy is at least one of iridium (Ir), ruthenium (Ru), and platinum (Pt). The alloy with other non-noble metal elements is at least one of tungsten (W), molybdenum (Mo), palladium (Pd), silver (Ag), manganese (Mn), lead (Pb), tin (Sn), antimony (Sb), zirconium (Zr), tantalum (Ta), niobium (Nb), titanium (Ti), chromium (Cr), cobalt (Co), indium (In), lanthanum (La), or cerium (Ce). The metal oxide powder is added to the above solution and dispersed evenly to form a mixed solution. The metal oxide is composed of a single metal oxide AO. x Or a combination of mixed metal oxides; Under ultrasonic treatment, the mixed solution was heated at 80 ℃ - 200 ℃ for 1 h - 6 h, and then filtered to obtain a precipitate. During the heating and ultrasonication process, the metal oxide support particles matured, that is, their size increased, which led to the embedding of noble metal or alloy particles nucleated on the support surface into the support, resulting in an ultrastable supported oxygen evolution electrocatalyst based on the maturation embedding method.

2. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening and intercalation method according to claim 1, characterized in that the metal atoms in the support component are selected from transition metals or main group metals other than noble metals, wherein, Single metal oxide AO x The metal atom A in the atom is at least one or more metal oxides selected from tungsten (W), molybdenum (Mo), palladium (Pd), silver (Ag), manganese (Mn), lead (Pb), tin (Sn), antimony (Sb), zirconium (Zr), tantalum (Ta), niobium (Nb), titanium (Ti), chromium (Cr), cobalt (Co), indium (In), lanthanum (La), or cerium (Ce). The mixed metal oxide comprises two metal oxides A Y B Z O x It consists of one or more different metal oxides, and metal atoms A and B are different from each other, where Y and Z are the stoichiometric ratios of elements A and B.

3. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening intercalation method according to claim 1, characterized in that the noble metal salt is a Ru salt, an Ir salt, or a Pt salt, wherein the Ru salt is selected from at least one of anhydrous ruthenium chloride, hydrated ruthenium chloride, ruthenium chloride trihydrate, ruthenium acetylacetonate, and ruthenium nitrite; wherein the Ir salt is selected from at least one of anhydrous iridium trichloride, iridium trichloride hydrate, iridium tetrachloride hydrate, iridium acetylacetonate, and sodium hexachloroacetate; and wherein the Pt salt is selected from at least one of chloroplatinic acid hydrate, chloroplatinic acid hexahydrate, platinum hexahydroxide, sodium platinum hexahydroxide, platinum acetylacetonate, potassium hexachloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinate, potassium chloroplatinate, ammonium chloroplatinate, potassium trichloroplatinate hydrate, and tetrabutylammonium chloroplatinate.

4. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening intercalation method according to claim 1, characterized in that the salt of the noble metal and other non-noble metal alloys is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, ammonium paratungstate, sodium tungstate, ammonium molybdate, molybdenum trioxide, palladium nitrate, palladium acetate, palladium chloride, silver nitrate, silver acetate, manganese nitrate, manganese acetate, manganese chloride, lead nitrate, lead acetate, tin chloride, antimony chloride, antimony acetate, zirconium nitrate, zirconium oxychloride, tantalum chloride, tantalum ethoxide, niobium chloride, niobium ethoxide, cerium nitrate, cerium sulfate, and cerium ammonium nitrate.

5. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on a ripening intercalation method according to any one of claims 1 to 4, characterized in that, A solution is prepared by dissolving 0.5 g to 5 g of a precious metal salt, or an alloy thereof, or an alloy with other non-precious metals in 50 mL to 200 mL of a polyol solvent, and then mixing it with 1 g to 20 g of a metal oxide, wherein the polyol solvent is one of ethylene glycol, glycerol, 1,2-propanediol, and pentaerythritol.

6. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening and embedding method according to claim 5, characterized in that it comprises the following steps: S1.1, the metal precursor salt and carbon powder are added to a polyol solvent and dispersed evenly to obtain a mixture. The metal precursor is selected from at least one of W, Mo, Pd, Ag, Mn, Pb, Sn, Sb, Zr, Ta, Nb, Co, and Ce. Under ultrasonic treatment, the precursor salt is rapidly decomposed, and a suspension is obtained after several hours. The suspension is then treated by centrifugation or filtration to obtain a precipitate. S1.2, After drying the obtained precipitate, place it in a tube furnace and calcine it to 200℃-1000℃ in a hydrogen-argon mixture or air atmosphere at a heating rate of 1℃ / min-20℃ / min for 1 h-6 h to obtain the metal oxide AO. x ; S1.3, take 0.5 g-5 g of a noble metal salt, such as ruthenium, iridium, or platinum, or an alloy thereof, or an alloy salt with other non-noble metals; 50 mL-200 mL of polyol solvent; and 1 g-20 g of metal oxide AO. x The noble metal salt is dissolved in a polyol solvent selected from ethylene glycol, glycerol, 1,2-propanediol, and pentaerythritol, and then a metal oxide AO is added. x This ensures uniform dispersion, resulting in a mixed solution. S1.4 The mixed solution was ultrasonically heated for 1 h to 5 h under preset conditions of 80 ℃ - 200 ℃ and then filtered to obtain a precipitated product, which is a metal oxide supported catalyst.

7. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening and embedding method according to claim 6, characterized in that it comprises the following steps: S1.1 Weigh 1 g of cerium acetylacetone and 1 g of carbon powder into 50 mL of ethylene glycol, disperse by ultrasonication for 100 min to form a uniformly dispersed suspension, and then centrifuge to obtain the precipitate. S1.2 After the obtained precipitate is dried, it is placed in a tube furnace and annealed at 600 °C for 2 h. After cooling to room temperature, the metal oxide CeO is obtained. x ; S1.3, 100 mg of CeO metal oxide x Disperse the solution in 50 mL of ethylene glycol, add 70 mg of iridium acetylacetone in ethylene glycol to obtain a mixture; S1.4, the mixed solution was placed in an oil bath and heated at 180 °C for 2 h under continuous sonication. After cooling to room temperature, it was filtered to obtain the mixed metal oxide supported catalyst Ir-CeO. x .

8. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening and embedding method according to claim 6, characterized in that it comprises the following steps: S1.1: Weigh 1 g of manganese acetylacetone and 1 g of carbon powder into 50 ml of ethylene glycol, and ultrasonically disperse for 120 min to form a uniformly dispersed suspension; after ultrasonic treatment, centrifuge the suspension and collect the precipitate; S1.2: The obtained precipitate was dried and placed in a tube furnace for annealing at 600 °C for 4 h, and then cooled to room temperature to obtain the metal oxide MnO. x ; S1.3: Add 100 mg MnO x The metal oxide was dispersed in 50 ml of ethylene glycol, and 80 mg of ethylene glycol solution containing ruthenium acetylacetone was added to form a mixed solution. S1.4: The mixed solution was placed in an oil bath and continuously ultrasonically heated at 180 °C for 2.5 h. After cooling to room temperature, it was filtered to obtain the metal oxide supported catalyst Ru-MnO. x .

9. The method for preparing an ultrastable supported oxygen evolution electrocatalyst based on the ripening and embedding method according to claim 6, characterized in that it comprises the following steps: S1.1 Weigh 1 g of manganese acetylacetone and 1 g of carbon powder and add them to 50 ml of ethylene glycol. Disperse the mixture by sonication for 120 min to form a uniformly dispersed suspension. After sonication, centrifuge the suspension to obtain the precipitate. S1.2, the precipitate was dried and placed in a tube furnace for annealing at 600 °C for 4 h, then cooled to room temperature to obtain the metal oxide MnO. x ; S1.3, 100 mg MnO x The metal oxide was dispersed in 50 ml of ethylene glycol, and 40 mg of ethylene glycol solution containing ruthenium acetylacetone and 40 mg of ethylene glycol solution containing iridium acetylacetone were added to form a mixed solution. S1.4: The mixed solution was placed in an oil bath and continuously ultrasonically heated at 180°C for 2.5 h. After cooling to room temperature, it was filtered to obtain the metal oxide supported catalyst RuIr-MnO. x .

10. An ultrastable supported oxygen evolution electrocatalyst based on a ripening intercalation method, obtained by the method according to any one of claims 1 to 9, characterized in that the content of noble metal M in the active component is 1% to 50% by mass, while the total content of other metal atoms A is 50% to 99%.

11. The ultrastable supported oxygen evolution electrocatalyst based on the ripening intercalation method according to claim 10, characterized in that, When metal oxide AO x CeO x The noble metal atom M is Ir, and the metal oxide supported catalyst M-AO x For Ir-CeO x ; Or, when metal oxide AO x MnO x The noble metal atom M is Ru, and the metal oxide supported catalyst M-AO x Ru-MnO x ; Or, when metal oxide AO x MnO x The noble metal atoms M are Ru and Ir, and the metal oxide supported catalyst M-AO x for RuIr-MnO x .

12. The application of a supported oxygen evolution electrocatalyst according to claim 10 or 11 in a proton exchange membrane electrolyzer (PEMWE).

13. The application according to claim 12, characterized in that, A supported catalyst based on a metal oxide support is used in the preparation of the anode electrode for proton exchange membrane water electrolysis, comprising the following steps: S2.1, Preparation of metal oxide supported catalyst Ir-CeO x ; S2.2, Weigh 20 mg of catalyst Ir-CeO x The catalyst slurry was obtained by dispersing it in 10 mL of isopropanol, adding 120 μL of 5 wt% perfluorosulfonic acid resin solution, and ultrasonically dispersing it evenly. S2.3, spray the catalyst slurry onto an area of ​​5 cm². 2 After drying, a metal oxide-supported catalyst, Ir-CeO, was obtained on a Nafion® 212 proton exchange membrane. x The anode electrode.

14. The application according to claim 13, characterized in that, based on the aforementioned supported metal oxide catalyst Ir-CeO x The assembly of the water electrolysis device with the anode electrode is performed according to the following steps: S3.1 Weigh 5 mg of platinum-carbon catalyst (Pt / C) with a platinum content of 40%, disperse it in a 10 mL mixed solution of methanol and water, making the methanol:water ratio 9:1, and add 30 μL of 5wt% perfluorosulfonic acid resin solution. After ultrasonic dispersion, another platinum-carbon catalyst slurry is obtained. S3.2, the platinum-carbon catalyst slurry is sprayed onto a surface that has already been sprayed with a 5 cm² area. 2 The anode catalyst is located on the back side of a Nafion® 212 proton exchange membrane, and the platinum-carbon catalyst supported on the back side of the proton exchange membrane has a platinum loading of approximately 0.1 mg. Pt / cm 2 ; S3.3, After drying the proton exchange membrane, Ir-CeO₂ catalyst is loaded on both sides. x Proton exchange membrane for cathode platinum-carbon catalyst; S3.4 The proton exchange membrane was hot-pressed at 60 °C and 2 MPa for 10 min to obtain the membrane electrode assembly of the water electrolysis device. S3.5, Seal rings with an area of ​​5 cm² are respectively installed on both sides of the assembled membrane electrode assembly. 2 Porous sintered titanium felt, with an area of ​​5 cm² 2 A proton exchange membrane water electrolysis device is assembled from titanium bipolar plates with S-shaped flow channels.

15. The application according to claim 14, characterized in that, in S3.5, porous sintered titanium felt or carbon paper with microporous layers is used as a gas diffusion layer in both the anode and cathode; the bipolar plate is made of graphite plate, stainless steel plate or titanium plate; the electrolyte of the water electrolysis device is a 0.05 M-2 M sulfuric acid solution or pure water.

16. The application according to claim 14, characterized in that, when the prepared metal oxide supported catalyst material is used as the anode catalyst in the PEM device and the platinum-carbon (Pt / C) catalyst is used as the cathode catalyst, the platinum content in the cathode catalyst is 20%-100%.

17. The application according to claim 12, characterized in that a Ru-MnO is prepared. x Methods for supported catalyst electrodes: S2.1, Preparation of metal oxide supported catalyst Ru-MnO x ; S2.2: Add 5 mg Ru-MnO x 20 μL of 5 wt% perfluorosulfonic acid resin solution was added to 1 ml of a mixed solvent of ethanol and water to make the volume ratio of ethanol to water 4:

1. The mixture was then ultrasonically dispersed to form a catalyst slurry. S2.3: The catalyst slurry is drop-coated onto a glassy carbon electrode with an area of ​​0.0706 cm², and after drying, an OER catalyst electrode is obtained.

18. The application according to claim 12, characterized in that a method for preparing an OER reaction catalyst electrode comprises the following steps: S2.1, Provide a metal oxide supported catalyst, or prepare a metal oxide supported catalyst using a method for preparing mixed metal oxide supported catalysts; S2.2, the mixed metal oxide supported catalyst, a binder perfluorosulfonic acid polymer solution, and a conductive agent, wherein the conductive agent includes at least one of carbon nanotubes, carbon black, or graphene, are added together to a mixed solvent of an organic solvent including methanol, ethanol, isopropanol, tetrahydrofuran, or acetone and water to form a catalyst slurry; the binder in the catalyst slurry has a weight percentage of 1wt%-40wt%, and the conductive agent in the catalyst slurry has a weight percentage of 10wt%-30wt%. S2.3, the catalyst slurry is ultrasonically dispersed and then coated onto a conductive substrate, wherein the conductive substrate is carbon felt, carbon film, carbon cloth, metal foam, or metal foil, i.e., a conductive carbon film of 50 μm – 250 μm, to form an electrode; or, the slurry is coated onto a proton exchange membrane of 10 μm – 250 μm thickness to form an anode loaded with a metal oxide catalyst; or, another method is to first spray the catalyst slurry onto a support film of PTFE film of 10 μm – 250 μm thickness, dry it, and then hot-press it at 100 °C – 260 °C and 1 MPa – 20 MPa for 1 – 20 min; after holding the pressure, the film is peeled off to obtain a membrane electrode loaded with a mixed metal oxide catalyst; wherein, the loading of the metal oxide supported catalyst is 0.1 mg / cm² – 50 mg / cm², and the mass percentage of the binder is 5 wt% – 40 wt%.

19. The application according to claim 18, characterized in that, when a perfluorosulfonic acid proton exchange membrane is used as the diaphragm, its thickness is between 25 μm and 250 μm.

20. The application according to claim 12, characterized in that a RuIr-MnO is prepared. x Supported catalyst electrodes are manufactured according to the following steps: S2.1, Preparation of metal oxide supported catalyst RuIr-MnO x ; S2.2, 5 mg RuIr-MnO x Add 20 μL of 5 wt% perfluorosulfonic acid resin solution to 1 ml of a mixed solvent of ethanol and water to make the volume ratio of ethanol to water 4:1, and ultrasonically disperse the mixture to form a catalyst slurry. S2.3, the catalyst slurry is drop-coated onto a glassy carbon electrode with an area of ​​0.0706 cm², and after drying, RuIr-MnO is obtained. x Supported catalyst electrode.

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