Process for the preparation of iridium-modified ruthenium-based transition metal-doped oxide catalysts and use thereof

Abstract

The application discloses a preparation method and application of an iridium-modified ruthenium-based transition metal doped oxide catalyst, and the preparation method comprises the following steps: uniformly dispersing a ruthenium source precursor, a soluble salt of a transition metal ion and a carbon powder carrier in a solvent, drying, and then calcining under a hydrogen-argon mixed reducing atmosphere to obtain a carbon-loaded metal intermediate; calcining the carbon-loaded metal intermediate under an air atmosphere to obtain a ruthenium-based transition metal doped oxide; dispersing the ruthenium-based transition metal doped oxide and an iridium precursor in water, adding dropwise into an alkali solution, collecting a precipitate, and calcining to obtain a low-iridium ruthenium-based transition metal oxide catalyst, which can be applied to an acidic oxygen evolution reaction of proton exchange membrane electrolysis water. The carbon powder is used as the carrier, the catalyst has small and uniform particle sizes through the hydrogen reduction and air oxidation processes, the carbon source and the metal source have interaction to stabilize active elements, and the catalytic activity is effectively improved; a small amount of iridium is deposited on the surface to reduce the iridium content and improve the stability, and the low-iridium ruthenium-based transition metal oxide catalyst is high in efficiency and stability.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy, specifically relating to the preparation method and application of iridium-modified ruthenium-based transition metal doped oxide catalysts. Background Technology

[0002] With increasing global warming and environmental pollution, the resulting fossil fuel crisis and global climate change have garnered growing international attention, making the utilization of renewable energy and energy conservation and emission reduction increasingly important. However, common renewable energy sources such as solar and wind power are characterized by randomness and instability, making peak-shaving in the power grid difficult and hindering large-scale grid integration—one of the main challenges currently facing renewable energy development. Therefore, successfully integrating renewable energy into the existing energy system and improving its utilization rate has become a key issue in achieving a carbon neutrality strategy.

[0003] Proton exchange membrane (PEM) water electrolysis is one of the most promising technologies for hydrogen production from renewable energy sources, boasting advantages such as high current density, fast response speed, low permeability, and a wide operating temperature range. The acidic oxygen evolution reaction in PEM water electrolysis exhibits slow kinetics, which significantly impacts overall efficiency and energy consumption, necessitating the application of highly efficient and stable catalysts to accelerate its reaction. However, the commonly used catalyst, iridium oxide, faces challenges due to its high cost and limited reserves, becoming a key factor restricting the development of PEM water electrolysis. Ruthenium oxide catalysts are considered a potential alternative to iridium-based catalysts, possessing excellent catalytic activity and a price advantage, but its stability in acidic environments is extremely poor.

[0004] To reduce the iridium content in acidic oxygen evolution catalysts and ensure catalyst stability, three main methods are employed: 1. Improving iridium utilization by constructing special surface morphologies, thereby reducing the iridium loading while maintaining structural stability; 2. Replacing iridium with other noble metals, such as ruthenium; 3. Doping with non-noble metals (generally transition metals) to reduce the proportion of iridium in the catalyst and constructing special structures to maintain stability and catalytic activity. Among these, transition metal-doped ruthenium-based oxide catalysts are considered potential substitutes for pure iridium oxide. However, due to the acidic oxygen evolution reaction environment and high overpotential, transition metals are prone to dissolution during operation, affecting catalyst stability, and the doping of transition metals may also affect the intrinsic activity of the catalyst. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, the main objective of this invention is to provide a method for preparing iridium-modified ruthenium-based transition metal doped oxide catalysts. The method employs a carbon powder impregnation method, using two steps—reduction followed by oxidation—to synthesize a ruthenium-based catalyst with highly efficient oxygen evolution catalytic performance. Finally, a low-iridium ruthenium-based catalyst with highly efficient and stable catalytic performance is synthesized using a deposition method.

[0006] This method is convenient and simple to operate. Ruthenium and transition metal compounds are impregnated onto carbon powder. The carbon powder serves as an important support in the synthesis process. On the one hand, it allows for the uniform distribution of different metal atoms, which helps to form the final structure and stabilize the metal atoms. On the other hand, after the carbon powder is oxidized, it forms nanoscale catalyst particles, increasing the specific surface area and active site utilization of the catalyst and promoting catalysis. In addition, iridium oxide is deposited on the surface of the ruthenium-based catalyst, which greatly reduces the amount of iridium used in the catalyst. At the same time, the formation of protection for the internal transition metal atoms and ruthenium atoms improves the overall stability of the catalyst.

[0007] Another object of the present invention is to provide the application of iridium-modified ruthenium-based transition metal doped oxide catalysts.

[0008] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing an iridium-modified ruthenium-based transition metal-doped oxide catalyst, comprising the following steps:

[0010] Step A: The ruthenium source precursor, the soluble salt of transition metal ions, and the carbon powder carrier are uniformly dispersed in the solvent;

[0011] Step B: After drying, the solid powder precursor is calcined in a hydrogen-argon mixed reducing atmosphere to obtain a carbon-supported metal intermediate.

[0012] Step C: The carbon-supported metal intermediate is calcined in air to obtain a ruthenium-based transition metal-doped oxide;

[0013] Step D: The ruthenium-based transition metal doped oxide and iridium precursor are dispersed in water, added dropwise to an alkaline solution, filtered to collect the precipitate, and calcined to obtain a low-iridium ruthenium-based transition metal oxide catalyst.

[0014] Preferably, in step A, the soluble salt of the transition metal ion is selected from one of cobalt, manganese, iron, and nickel.

[0015] Preferably, in step A, the soluble salt of the transition metal ion is selected from one of chloride, nitrate, sulfate, and acetate.

[0016] Preferably, in step A, the molar ratio of the ruthenium source precursor to the soluble salt of the transition metal ion is 1-5:1. Choosing this molar ratio ensures that: on the one hand, sufficient transition metal is added to guarantee successful doping; on the other hand, excessive transition metal can prevent the formation of a stable ruthenium oxide characteristic crystal structure, affecting catalytic activity. The catalyst with the optimal catalyst performance is obtained by balancing these two points in the intermediate molar ratio.

[0017] Preferably, in step A, the mass ratio of the soluble salt of the transition metal ions to the carbon powder carrier is 1:1-2. Choosing this mass ratio ensures that metal atoms can be uniformly adsorbed onto the carbon powder and that an effective transition metal-doped crystal structure can be formed.

[0018] Preferably, in step B, the calcination temperature is 800-1000℃, and the calcination time is 1-2 hours. If the calcination temperature is below 800℃, the metal atoms cannot be completely reduced to elemental form; if it is above 1000℃, the experimental temperature will be too high, increasing energy consumption and hazard.

[0019] Preferably, in step C, the calcination temperature is 400-600℃, and the calcination time is 3-5 hours. If the calcination temperature is below 400℃, the carbon powder and elemental metals cannot be completely oxidized; if it is above 600℃, the catalyst will sinter into lumps, affecting its catalytic activity.

[0020] Preferably, in step D, the iridium precursor is chloroiridium acid, with a mass percentage of 2%-10%. Choosing this mass percentage ensures that: on the one hand, there is sufficient iridium oxide to protect the catalyst and improve its stability; on the other hand, too much iridium will reduce catalytic activity. The catalyst with the optimal performance is obtained by balancing these two points in the intermediate mass percentage.

[0021] Preferably, in step D, the calcination temperature is 300-500℃, and the calcination time is 1-3 hours. If the calcination temperature is below 300℃, hydrated iridium hydroxide cannot be completely converted into iridium oxide; if it is above 500℃, the catalyst particles will agglomerate, reducing catalytic activity.

[0022] This invention improves the interaction between metal atoms by using carbon powder as an intermediate carrier to effectively promote the adsorption of metal atoms and improve utilization. It also utilizes two heat treatments, reduction and oxidation, to dope transition metal atoms into the ruthenium oxide lattice structure. Simultaneously, it deposits iridium oxide on the catalyst surface to stabilize the catalyst structure, thereby further improving stability.

[0023] Secondly, the present invention provides an iridium-modified ruthenium-based transition metal doped oxide catalyst, which is prepared by the aforementioned method for preparing iridium-modified ruthenium-based transition metal doped oxide catalysts.

[0024] Thirdly, the present invention provides an application of an iridium-modified ruthenium-based transition metal doped oxide catalyst in electrode catalysis, for example, as a catalyst material for oxygen evolution in an acidic environment during proton exchange membrane water electrolysis.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The method of this invention uses low-cost raw materials and is simple and easy to synthesize. It employs two processes: impregnation adsorption and reduction followed by oxidation, to introduce transition metal atoms into the ruthenium oxide crystal structure. This establishes an effective interaction between ruthenium and transition metal atoms, stabilizing the catalyst structure and exposing more catalytic active sites, thus enhancing catalytic activity. Furthermore, the carbon powder support has a high specific surface area, which is beneficial for forming small-particle nanoscale catalysts and increasing the catalyst's specific surface area.

[0027] 2. In this invention, iridium oxide is modified onto the catalyst surface using a deposition method. The process is simple and convenient, and iridium oxide modification helps to stabilize the overall crystal structure of the catalyst and improve its durability. Furthermore, this method effectively reduces the amount of iridium used in the catalyst, significantly lowering the catalyst cost. Attached Figure Description

[0028] Figure 1 The image shows the XRD pattern of the iridium-modified ruthenium-based transition metal doped oxide catalyst prepared in Example 1.

[0029] Figure 2 This is a TEM image of the iridium-modified ruthenium-based transition metal doped oxide catalyst prepared in Example 1.

[0030] Figure 3 The linear sweep voltammetry curves of the iridium-modified ruthenium-based transition metal doped oxide catalyst prepared in Example 1 are compared with those of a common commercial iridium oxide catalyst.

[0031] Figure 4 The linear sweep voltammetry curves of the oxide catalysts with different transition metal doped in Examples 1 and 4 are compared.

[0032] Figure 5 The constant current stability test curves of the iridium-modified ruthenium-based transition metal doped oxide catalyst prepared in Example 4 are shown. Detailed Implementation

[0033] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several changes and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0034] The preparation methods of iridium-modified ruthenium-based transition metal doped oxide catalysts in the following embodiments include the following steps:

[0035] Step A: The ruthenium source precursor, the soluble salt of transition metal ions, and the carbon powder carrier are uniformly dispersed in the solvent;

[0036] Step B: After drying, the solid powder precursor is calcined in a hydrogen-argon mixed reducing atmosphere to obtain a carbon-supported metal intermediate.

[0037] Step C: The carbon-supported metal intermediate is calcined in air to obtain ruthenium-based transition metal-doped oxide;

[0038] Step D: The ruthenium-based transition metal doped oxide and iridium precursor are dispersed in water, added dropwise to an alkaline solution, filtered to collect the precipitate, and calcined to obtain a low-iridium ruthenium-based transition metal oxide catalyst.

[0039] In step A, the soluble salt of the transition metal ion is selected from one of cobalt, manganese, iron, and nickel.

[0040] In step A, the soluble salt of the transition metal ion is selected from one of the following: chloride, nitrate, sulfate, and acetate.

[0041] In step A, the molar ratio of the ruthenium source precursor to the soluble salt of the transition metal ion is 1-5:1.

[0042] In step A, the mass ratio of the soluble salt of the transition metal ion to the carbon powder carrier is 1:1-2.

[0043] In step B, the calcination temperature is 800-1000℃ and the calcination time is 1-2 hours.

[0044] In step C, the calcination temperature is 400-600℃ and the calcination time is 3-5h.

[0045] In step D, the iridium precursor is chloroiridium acid, with a mass percentage of 2%-10%.

[0046] In step D, the calcination temperature is 300-500℃ and the calcination time is 1-3h.

[0047] Example 1

[0048] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this embodiment are as follows:

[0049] 1. Weigh 1.732 g of 10% RuCl3 solution, 0.1626 g of MnCl2·6H2O, and 0.4 g of carbon powder using an electronic balance, and measure 5 mL of ultrapure water, then add them to a 50 mL beaker.

[0050] 2. Place the beaker in the ultrasonic cleaner and mix ultrasonically for 1 hour;

[0051] 3. After the ultrasound is completed, place the beaker in a fume hood and let it stand at room temperature for 2 hours;

[0052] 4. Place the beaker in a 60 ℃ oven and dry for 6 hours. After it is completely dry, grind the sample into a fine powder using a mortar and pestle.

[0053] 5. Place the solid obtained in step 4 into a tube furnace, pre-purge for 60 mins in a hydrogen-argon mixed atmosphere, set the heating temperature to 900 ℃, hold the temperature for 2 h, and the heating rate to 10 ℃ / min.

[0054] 6. After step 5 is completed, in an air atmosphere, set the heating temperature to 450 ℃, the temperature holding time to 3 hours, and the heating rate to 10 ℃ / min.

[0055] 7. Take 100 mg of the solid obtained in step 6, weigh 10 mg of chloroiridium acid, and mix them with 10 mL of ultrapure water in a beaker;

[0056] 8. Measure 4.6 mL of 0.038 M NaOH solution, add it to a multi-necked flask, heat it in a 40 ℃ water bath and introduce nitrogen gas into it;

[0057] 9. Add the mixed liquid from step 7 dropwise into the flask from step 8, and maintain the temperature in a water bath for 4 hours.

[0058] 10. After filtering, washing and drying the solution, the solid was calcined in a muffle furnace for 1 h at a temperature of 400℃.

[0059] 11. The solid obtained in step 10 is the iridium-modified ruthenium-based manganese-doped oxide catalyst.

[0060] The prepared samples were subjected to various characteristic tests, and the results are shown in [reference needed]. Figure 1 , 2 3, 4:

[0061] XRD analysis: See Figure 1 The X-ray diffraction was performed on a Rigaku D / max-2550 X-ray diffractometer in Japan, using CuKα diffraction. As can be seen from the figure, the main crystal form of the obtained catalyst is ruthenium oxide phase.

[0062] TEM analysis: See Figure 2 The morphology of the material was observed using a JSM-2100F transmission electron microscope manufactured by Nippon Electron Ltd. The TEM images revealed an iridium-modified ruthenium-based manganese-doped oxide catalyst.

[0063] Iridium-modified ruthenium-based manganese-doped oxide catalysts serve as acidic oxygen evolution catalysts. The electrochemical performance of the materials was measured, such as... Figure 3 As shown in the figure, the Ir-MnRuO xCom-IrO2 represents the catalyst prepared in Example 1 and a common commercial iridium oxide catalyst, respectively. Linear sweep spectroscopy was performed in 0.5 M H2SO4 electrolyte solution. The results show that the iridium-modified ruthenium-based manganese-doped oxide catalyst exhibits better oxygen evolution activity. In the linear sweep curve, the catalyst prepared in Example 1 showed better activity at 10 mA cm⁻¹. -2 At the given current density, the overpotential is 250 mV, which is lower than the 314 mV of ordinary commercial iridium oxide catalysts.

[0064] Example 2

[0065] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this embodiment are as follows:

[0066] 1. Weigh 1.732 g of 10% RuCl3 solution, 0.0543 g of MnCl2·6H2O, and 0.4 g of carbon powder using an electronic balance, and measure 5 mL of ultrapure water, then add them to a 50 mL beaker.

[0067] 2. Place the beaker in the ultrasonic cleaner and mix ultrasonically for 1 hour;

[0068] 3. After the ultrasound is completed, place the beaker in a fume hood and let it stand at room temperature for 2 hours;

[0069] 4. Place the beaker in a 60 ℃ oven and dry for 6 hours. After it is completely dry, grind the sample into a fine powder using a mortar and pestle.

[0070] 5. Place the solid obtained in step 4 into a tube furnace, pre-purge for 60 mins in a hydrogen-argon mixed atmosphere, set the heating temperature to 900 ℃, hold the temperature for 2 h, and the heating rate to 10 ℃ / min.

[0071] 6. After step 5 is completed, in an air atmosphere, set the heating temperature to 450 ℃, the temperature holding time to 3 hours, and the heating rate to 10 ℃ / min.

[0072] 7. Take 100 mg of the solid obtained in step 6, weigh 10 mg of chloroiridium acid, and mix them with 10 mL of ultrapure water in a beaker;

[0073] 8. Measure 4.6 mL of 0.038 M NaOH solution, add it to a multi-necked flask, heat it in a 40 ℃ water bath and introduce nitrogen gas into it;

[0074] 9. Add the mixed liquid from step 7 dropwise into the flask from step 8, and maintain the temperature in a water bath for 4 hours.

[0075] 10. After filtering, washing and drying the solution, the solid was calcined in a muffle furnace for 1 h at a temperature of 400℃.

[0076] 11. The solid obtained in step 10 is the iridium-modified ruthenium-based manganese-doped oxide catalyst.

[0077] XRD and TEM characterization were similar to those in Example 1, at 10 mAcm -2 At the current density, the overpotential is 261 mV.

[0078] Example 3

[0079] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this embodiment are as follows:

[0080] 1. Weigh 1.732 g of 10% RuCl3 solution, 1.626 g of MnCl2·6H2O, and 0.4 g of carbon powder using an electronic balance, and measure 5 mL of ultrapure water, then add them to a 50 mL beaker.

[0081] 2. Place the beaker in the ultrasonic cleaner and mix ultrasonically for 1 hour;

[0082] 3. After the ultrasound is completed, place the beaker in a fume hood and let it stand at room temperature for 2 hours;

[0083] 4. Place the beaker in a 60 ℃ oven and dry for 6 hours. After it is completely dry, grind the sample into a fine powder using a mortar and pestle.

[0084] 5. Place the solid obtained in step 4 into a tube furnace, pre-purge for 60 mins in a hydrogen-argon mixed atmosphere, set the heating temperature to 900 ℃, hold the temperature for 2 h, and the heating rate to 10 ℃ / min.

[0085] 6. After step 5 is completed, in an air atmosphere, set the heating temperature to 550 ℃, the temperature holding time to 3 hours, and the heating rate to 10 ℃ / min.

[0086] 7. Take 100 mg of the solid obtained in step 6, weigh 10 mg of chloroiridium acid, and mix them with 10 mL of ultrapure water in a beaker;

[0087] 8. Measure 4.6 mL of 0.038 M NaOH solution, add it to a multi-necked flask, heat it in a 40 ℃ water bath and introduce nitrogen gas into it;

[0088] 9. Add the mixed liquid from step 7 dropwise into the flask from step 8, and maintain the temperature in a water bath for 4 hours.

[0089] 10. After filtering, washing and drying the solution, the solid was calcined in a muffle furnace for 1 h at a temperature of 400℃.

[0090] 11. The solid obtained in step 10 is the iridium-modified ruthenium-based manganese-doped oxide catalyst.

[0091] XRD and TEM characterization were similar to those in Example 1, at 10 mAcm -2 At the given current density, the overpotential is 265 mV.

[0092] Example 4

[0093] The preparation steps of the iridium-modified ruthenium-based cobalt-doped oxide catalyst in this embodiment are as follows:

[0094] 1. Weigh 1.732 g of 10% RuCl3 solution, 0.0657 g of CoCl2·6H2O, and 0.4 g of carbon powder using an electronic balance, and measure 5 mL of ultrapure water, then add them to a 50 mL beaker.

[0095] 2. Place the beaker in the ultrasonic cleaner and mix ultrasonically for 1 hour;

[0096] 3. After the ultrasound is completed, place the beaker in a fume hood and let it stand at room temperature for 2 hours;

[0097] 4. Place the beaker in a 60 ℃ oven and dry for 6 hours. After it is completely dry, grind the sample into a fine powder using a mortar and pestle.

[0098] 5. Place the solid obtained in step 4 into a tube furnace, pre-purge for 60 mins in a hydrogen-argon mixed atmosphere, set the heating temperature to 900 ℃, hold the temperature for 2 h, and the heating rate to 10 ℃ / min.

[0099] 6. After step 5 is completed, in an air atmosphere, set the heating temperature to 450 ℃, hold the temperature for 3 hours, and the heating rate to 10 ℃ / min.

[0100] 7. Take 100 mg of the solid obtained in step 6, weigh 10 mg of chloroiridium acid, and mix them with 10 mL of ultrapure water in a beaker;

[0101] 8. Measure 4.6 mL of 0.038 M NaOH solution, add it to a multi-necked flask, heat it in a 40 ℃ water bath and introduce nitrogen gas into it;

[0102] 9. Add the mixed liquid from step 7 dropwise into the flask from step 8, and maintain the temperature in a water bath for 4 hours.

[0103] 10. After filtering, washing and drying the solution, the solid was calcined in a muffle furnace for 1 h at a temperature of 400℃.

[0104] 11. The solid obtained in step 10 is the iridium-modified ruthenium-based manganese-doped oxide catalyst.

[0105] XRD and TEM characterization were similar to those in Example 1, at 10 mAcm -2 At the current density, the overpotential is 247 mV. For example... Figure 4 As shown in the figure, the Ir-MnRuO x Ir-Co-RuO2 represents the manganese-doped catalyst prepared in Example 1 and the cobalt-doped catalyst prepared in Example 4, respectively. The linear sweep voltammetry curves show that their oxygen evolution performance is similar. The catalyst prepared in Example 4 was subjected to a constant current stability test, as shown... Figure 5 As shown, it was at 200 h, 10 mAcm -2 Under the operating current, the overpotential increase does not exceed 5%, demonstrating excellent stability.

[0106] Comparative Example 1

[0107] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this comparative example are basically the same as those in Example 1, except that the mass of MnCl2.6H2O in step 1 of this comparative example is 3.252 g.

[0108] The catalyst prepared by this step did not have manganese atoms entering the ruthenium oxide lattice, and its oxygen evolution performance was far lower than that in Example 1.

[0109] Comparative Example 2

[0110] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this comparative example are basically the same as those in Example 1, except that MnCl2·6H2O is not added in step 1 of this comparative example.

[0111] The catalyst prepared in this way did not contain any transition metals, and its oxygen evolution performance and stability were not as good as those in Example 1.

[0112] Comparative Example 3

[0113] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this comparative example are basically the same as those in Example 4, except that the heating temperature in step 6 of this comparative example is 650 °C.

[0114] The iridium-modified ruthenium-based manganese-doped oxide catalyst prepared in this way has large particles, and its oxygen evolution activity is much lower than that in Example 1, at 10 mAcm⁻¹. -2 At the current density, the overpotential is 302 mV.

[0115] Comparative Example 4

[0116] The preparation steps of the iridium-modified ruthenium-based manganese-doped oxide catalyst in this comparative example are basically the same as those in Example 1, except that the calcination temperature in step 10 of this comparative example is 250 °C.

[0117] This step cannot form an iridium oxide surface modification, and the stability is lower than that in Example 1.

[0118] In summary, the method of this invention uses inexpensive raw materials and is simple and easy to perform. It employs two processes—impregnation adsorption and reduction followed by oxidation—to introduce transition metal atoms into the ruthenium oxide crystal structure. This establishes an effective interaction between ruthenium and transition metal atoms, stabilizing the catalyst structure and exposing more catalytic active sites, thus enhancing catalytic activity. Furthermore, the carbon powder support has a high specific surface area, which is beneficial for forming small-particle nanoscale catalysts and increasing the catalyst's specific surface area. Simultaneously, the deposition method modifies the catalyst surface with iridium oxide, ensuring catalytic stability and reducing the iridium loading, significantly lowering costs.

[0119] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing an iridium-modified ruthenium-based transition metal-doped oxide catalyst, characterized in that, Includes the following steps: Step A: The ruthenium source precursor, the soluble salt of transition metal ions, and the carbon powder carrier are uniformly dispersed in the solvent; Step B: After drying, the solid powder precursor is calcined in a hydrogen-argon mixed reducing atmosphere to obtain a carbon-supported metal intermediate. Step C: The carbon-supported metal intermediate is calcined in air to obtain a ruthenium-based transition metal-doped oxide; Step D: The ruthenium-based transition metal doped oxide and iridium precursor are dispersed in water, added dropwise to an alkaline solution, the precipitate is collected by filtration, and calcined to obtain a low-iridium ruthenium-based transition metal oxide catalyst. In step A, the soluble salt of the transition metal ion is selected from one of cobalt, manganese, iron, and nickel; the soluble salt of the transition metal ion is selected from one of chloride, nitrate, sulfate, and acetate. The molar ratio of the ruthenium source precursor to the soluble salt of the transition metal ion is 1-5:

1. The mass ratio of the soluble salt of the transition metal ion to the carbon powder carrier is 1:1-2. In step C, the calcination temperature is 400-600℃ and the calcination time is 3-5h; In step D, the calcination temperature is 300-500℃ and the calcination time is 1-3h.

2. The method for preparing the iridium-modified ruthenium-based transition metal-doped oxide catalyst according to claim 1, characterized in that, In step B, the calcination temperature is 800-1000℃ and the calcination time is 1-2h.

3. The method for preparing the iridium-modified ruthenium-based transition metal-doped oxide catalyst according to claim 1, characterized in that, In step D, the iridium precursor is chloroiridium acid, with a mass percentage of 2%-10%.

4. An iridium-modified ruthenium-based transition metal doped oxide catalyst, prepared by the method for preparing an iridium-modified ruthenium-based transition metal doped oxide catalyst according to any one of claims 1 to 3.

5. The application of the iridium-modified ruthenium-based transition metal doped oxide catalyst of claim 4 in electrode catalysis, including its use as a catalyst material for oxygen evolution in acidic environments during proton exchange membrane water electrolysis.

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