Low-iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst and preparation method thereof

Abstract

The invention belongs to the technical field of catalytic energy conversion, and particularly relates to a low-iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps: dissolving and mixing soluble ruthenium metal precursor salt and other metal precursor salt in ethylene glycol, and reducing metal ions to be in a low valence state by utilizing the reducibility of the ethylene glycol; adding a carbon carrier as a template, and controlling the particle size of metal particles; performing solvothermal reaction and pyrolysis oxidation to obtain a catalyst; wherein ruthenium is a base metal, and the doped metal comprises a transition metal and a platinum group noble metal. The preparation process disclosed by the invention considers both the catalytic efficiency and the synthesis cost of the catalyst and has high expansibility, and the material components have high selectivity. According to the prepared catalyst, reaction activity and stability of ruthenium in water oxidation reaction are effectively optimized through multi-element cooperative regulation, a new choice is provided for cost reduction and efficiency improvement of an electrolytic water anode catalyst, and the catalyst has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalytic energy conversion, and particularly relates to a low-iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst and a preparation method thereof. BACKGROUND

[0002] Under the background of the transformation of global energy structure to clean and low-carbon, hydrogen energy, as a clean and efficient secondary energy carrier, has important application value in the fields of renewable energy storage, transportation, industrial energy supply, etc. Proton exchange membrane water electrolysis technology has become a key technology for connecting renewable energy and hydrogen energy due to its advantages of high working current density, high hydrogen production purity, and fast dynamic response speed, and can effectively absorb the production fluctuation of fluctuating energy such as wind energy and solar energy.

[0003] However, the commercialization process of proton exchange membrane water electrolysis technology is limited by the high reaction barrier and harsh working conditions (acidic environment and high potential) of the anode oxygen evolution reaction. At present, the commonly used acidic oxygen evolution catalyst in industry is iridium (Ir) based catalyst, but its crustal reserves are extremely low (about 0.001 ppm) and the price is high, which seriously restricts the large-scale application. Although the oxygen evolution activity of ruthenium oxide (RuO2) catalyst is higher and the cost is lower than that of iridium-based catalyst, it is easy to be oxidized and dissolved under acidic and high potential conditions, and has poor stability, so it is difficult to be used in 1A / cm 2 for long-term operation under industrial-grade large current density. Therefore, the development of an acidic oxygen evolution catalyst with low cost, high activity and high stability has become a core requirement for promoting the commercialization of proton exchange membrane water electrolysis technology. SUMMARY

[0004] The purpose of the present application is to overcome the defects of high cost of iridium-based catalyst and insufficient stability of pure ruthenium oxide catalyst under acidic conditions in the prior art, and to provide a low-iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst and a preparation method thereof.

[0005] The preparation method of the low-iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst provided by the present application adopts the strategy of combining solvent (such as ethylene glycol) reduction method and carbon template method, and through subsequent thermal oxidation and acid washing treatment, a multi-metal oxide nanocatalyst with flexible and controllable composition and uniform mixing is synthesized; the specific preparation steps are as follows: (1) precursor pretreatment: dissolving a ruthenium metal precursor salt and other one or more metal M, N precursor salts in an organic solvent, and performing ice bath ultrasonic treatment to obtain a uniform transparent mixed metal salt solution; (2) carbon carrier dispersion: dispersing a high specific surface area carbon carrier material in an organic solvent by mechanical grinding to obtain a uniform carbon carrier slurry; (3) Solvothermal reduction reaction: the solution obtained in step (1) is mixed with the slurry obtained in step (2), and solvothermal reflux reaction is carried out at 160-200℃ for 3-5h, so that the metal ions are reduced and loaded on the surface of the carbon carrier; (4) Centrifugal washing and drying: after the reaction is completed, the product is centrifuged, repeatedly washed with a solvent to remove impurities, and then vacuum dried to obtain a metal / carbon composite precursor; (5) Thermal treatment oxidation: the dried powder is subjected to programmed temperature heat treatment in an air or oxygen atmosphere to completely remove the carbon template and completely oxidize the metal precursor to form the target composite metal oxide; (6) Acid washing purification: the product after heat treatment is immersed in a dilute acid solution for a long time under ultrasonic washing to remove soluble impurities generated during heat treatment, and after deionized water washing and drying, the final catalyst product is obtained.

[0006] Further: In step (1), the ruthenium metal precursor salt is one of acetylacetone ruthenium, ruthenium trichloride, and ruthenium acetate; The metal M is one or more of Co, Mn, Sn, Ti, Nb, Ta, Cr, Mo, and W; the precursor salt of the metal M is one or more of hydrochloride, nitrate, sulfate, acetate, and perchlorate; The metal N is one of Ir, Pt, and Pd; the precursor salt of N is hydrochloride, and one or more of acetylacetone ruthenium, acetylacetone platinum, acetylacetone iridium, acetylacetone palladium, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum nitrate, potassium hexachloroplatinate, potassium tetrachloroplatinate, chloroiridic acid, and potassium hexachloroiridate; The organic solvent is one of ethylene glycol and glycerol.

[0007] In step (2), the carbon carrier material is one of Ketjen black, Vulcan XC-72, carbon nanotube, and graphene; the mechanical grinding adopts a three-roll mill, a ball mill, or a high-speed shear emulsifier. The organic solvent is one or more of ethanol, methanol, isopropanol, and acetone.

[0008] In step (4), the product is centrifuged at a speed of 8000-10000rpm for 30-40min, the supernatant is discarded, and the product is washed with ethanol and ultrapure water alternately for 3 times, and then dried in a vacuum oven at 60-70℃ for 10-12h to obtain a black powder.

[0009] In step (5), the heat treatment condition is: heating to 300-600℃ at a heating rate of 1-10℃ / min in air or pure oxygen atmosphere for 2-5h; preferably, the heat treatment condition is: heating to 450℃ at a heating rate of 2℃ / min in air atmosphere for 2h.

[0010] In step (6), the dilute acid is a hydrochloric acid, sulfuric acid or perchloric acid solution with a concentration of 0.5-1 mol / L, and the pickling time is 12-24 hours.

[0011] The low iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst prepared by the above preparation method has a chemical formula of Ru a M b N c O x , wherein M is a doped transition metal, N is a doped platinum group noble metal, a, b and c are respectively the mole fraction of each metal, 0.5

[0012] The application also provides the use of the low iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst in the anode of a proton exchange membrane water electrolysis device.

[0013] The application has the following beneficial effects: (1) Controllable cost and high utilization rate of noble metal: by using relatively low-cost ruthenium (Ru) as the main metal and doping a small amount of high-activity but expensive iridium (Ir) or other noble metals (Pt, Pd), the cost of the catalyst material is significantly reduced, and the utilization efficiency and intrinsic activity of noble metal atoms are greatly improved by using the surface segregation and electronic regulation effect of noble metals; (2) Multi-element synergy and significantly enhanced stability: the introduction of transition metal elements (M) into the RuO2 lattice effectively suppresses the peroxidation and dissolution loss of ruthenium active sites at high anode potentials by regulating the electronic structure of ruthenium and forming strong metal-oxygen bonds (M-O-Ru), thereby greatly improving the electrochemical stability of the catalyst in the acidic oxygen evolution reaction (OER); (3) Universal method and controllable structure and performance: the adopted ethylene glycol reduction-carbon template method is simple and has good repeatability, and the final composition of the catalyst can be accurately regulated by flexibly adjusting the proportion of the precursor salt. The carbon carrier effectively limits the sintering and growth of nanoparticles during the heat treatment process, ensuring that the obtained catalyst has uniform size, high specific surface area and porous structure characteristics, which is beneficial to reaction mass transfer and exposure of more active sites; (4) Excellent activity and broad application prospects: The catalyst prepared by this method exhibits excellent catalytic activity and extremely high stability in an acidic electrolyte, with the voltage maintained at 1.65 V and the voltage rise of less than 20 mV after continuous operation for 100 h, which can meet the requirements of long-term operation of anode catalysts for proton exchange membrane (PEM) water electrolysis under industrial-level high current density, and provide a new material solution for the commercialization of PEM water electrolysis technology. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 Ru 0.6 Co 0.35 Ir 0.05 O x Transmission electron microscope (TEM) image of the catalyst. The catalyst is shown as uniform nanoparticles with a diameter of about 10 nm, and the dispersion is good without obvious agglomeration.

[0015] Figure 2 Ru 0.6 Co 0.35 Ir 0.05 O x High-angle annular dark field scanning transmission electron microscope (HAADF-STEM) image and EDS element mapping image of the catalyst. The distribution of Ru, Co, and Ir elements is shown from left to right in the figure, and the four elements are uniformly distributed in the particles without obvious enrichment or depletion area.

[0016] Figure 3 Ru 0.6 Co 0.35 Ir 0.05 O x X-ray diffraction (XRD) pattern of the catalyst. The horizontal coordinate is 2θ (°), and the vertical coordinate is the diffraction intensity (a.u.). The curve is the XRD spectrum of the catalyst, and the dashed line is the characteristic peak of the standard PDF card of ruthenium oxide. The peak positions are consistent, and the catalyst diffraction peak half-width is wider, indicating smaller grain size.

[0017] Figure 4 Ru 0.6 Co 0.35 Ir 0.05 O x X-ray photoelectron spectroscopy (XPS) pattern of the catalyst. In a, the horizontal coordinate is the binding energy (eV), and the vertical coordinate is the count rate (counts / s), which shows the existence of Ru, Co, Ir, and O element characteristic peaks. In b, the high-resolution spectrum of Ru is shown, the horizontal coordinate is the binding energy (eV), and the vertical coordinate is the count rate (counts / s), which shows the Ru3p 3 / 2 and Ru3p 1 / 2 characteristic peaks, and there is Ru3+ Ru 4+ Valence state distribution.

[0018] Figure 5 Ru 0.6 Co 0.35 Ir 0.05 O x Figure 1 is a comparison chart of electrochemical polarization curves of the catalyst and pure ruthenium oxide catalyst. The horizontal coordinate is overpotential (mV), and the vertical coordinate is current density (mA / cm 2 ); curve 1 is the Ru 0.6 Co 0.35 Ir 0.05 O x catalyst, and curve 2 is the pure ruthenium oxide catalyst; it can be seen that the overpotential of the catalyst is 200 mV at a current density of 10 mA / cm 2 , which is much lower than the 300 mV of the pure ruthenium oxide.

[0019] Figure 6 Ru 0.6 Co 0.35 Ir 0.05 O x Figure 2 is a voltage-time stability curve of the catalyst at a current density of 1 A / cm 2 ; the horizontal coordinate is time (h), and the vertical coordinate is working voltage (V); the curve shows that the catalyst works continuously at a voltage of 1.65 V for 250 h, the voltage slowly rises, and the final attenuation is less than 20 mV, and the stability is excellent.

[0020] Figure 7 Ru 0.6 Co 0.35 Ir 0.05 O x Figure 3 is a current-voltage curve of a membrane electrode prepared by the catalyst; the horizontal coordinate is current density (A / cm 2 ), and the vertical coordinate is working voltage (V); the curve shows that when the current density reaches 1 A / cm 2 , the corresponding working voltage of the membrane electrode is 1.65 V, which meets the requirements of industrial applications. DETAILED DESCRIPTION

[0021] The application will be further described below by specific examples in conjunction with the accompanying drawings. In the examples, the specific conditions not specified are carried out according to the conventional conditions or the conditions recommended by the manufacturer; and the reagents or instruments not specified by the manufacturer are all conventional products that can be purchased on the market.

[0022] Example 1. Ru 0.6 Co 0.35 Ir 0.05 O xPreparation of the catalyst (1) Precursor pretreatment: 0.6 mmol of ruthenium acetylacetonate (Ru(acac)3, mass 214.41 mg), 0.05 mmol of iridium acetylacetonate (Ir(acac)3, mass 24.48 mg), and 0.35 mmol of cobalt acetylacetonate (Co(acac)3, mass 124.69 mg) were weighed and added to 30 mL of ethylene glycol (analytical pure) in an ice bath (0-5°C), and ultrasonic treatment was performed at a power of 300 W for 45 min until the solid was completely dissolved, to obtain a light yellow transparent reagent A.

[0023] (2) Carbon carrier treatment: 100 mg of Ketjen black (KB-300) was weighed and added to 30 mL of ethylene glycol, and then transferred to a three-roll ball mill (the grinding medium was Φ5 mm zirconia balls, and the ball-to-material ratio was 10:1), and the rotation speed was set to 300 rpm for grinding for 12 h, to obtain a black and uniform slurry-shaped reagent B.

[0024] (3) Reaction: reagent A and reagent B were transferred to a 100 mL glass pressure-resistant reaction bottle, and a magnetic stirrer was added, and stirring was performed at a speed of 500 rpm on a magnetic stirrer, and the pressure-resistant reaction bottle was placed in an oil bath, and the temperature was increased to 160°C, and reflux reaction was maintained for 3 h.

[0025] (4) Centrifugation and washing: after the reaction was completed, the mixture was cooled to room temperature, transferred to a 50 mL centrifuge tube, centrifuged at a speed of 10,000 rpm for 30 min, and the supernatant was discarded; 20 mL of ethanol was added, ultrasonic dispersion was performed for 5 min, and then the same condition was used for centrifugation for 30 min, and the supernatant was discarded; after repeating the ethanol washing for 3 times, 20 mL of ultrapure water was used for washing for 3 times under the same condition, and finally the obtained black solid was placed in a 60°C vacuum oven for drying for 12 h.

[0026] (5) Heat treatment to remove the carbon carrier: the dried black solid was ground in a jade mortar for 10 min to be fluffy, and then transferred to a 5 mL alumina magnetic boat; the magnetic boat was placed in a tube furnace, and air was introduced (flow rate 50 mL / min), and the temperature was increased to 450°C at a rate of 2°C / min, and maintained for 2 h; after the heat preservation was completed, the temperature was naturally cooled to room temperature, to obtain a black powder.

[0027] (6) Acid washing: the black powder was transferred to a 100 mL beaker, 50 mL of 1 mol / L dilute hydrochloric acid was added, and ultrasonic acid washing was performed for 24 h in an ultrasonic cleaning instrument; after the acid washing was completed, the powder was washed with ultrapure water until the pH of the filtrate was 7, and the powder was placed in a 60°C vacuum oven for drying for 12 h, to obtain Ru 0.6 Co 0.35 Ir0.05 O x catalyst.

[0028] Performance test: in 0.5mol / L H2SO4 solution, three-electrode system test: overpotential is 210mV at 10mA / cm2current density; prepare it into a membrane electrode (catalyst loading 1mg / cm2), assemble into a single cell electrolytic cell, continuously run for 100h at 1A / cm2current density, voltage 1.65V, excellent stability. 2 2 2

[0029] Example 2. Ru 0.9 Co 0.05 Ir 0.05 O x Preparation of catalyst (1) Precursor pretreatment: weigh 0.9mmol of ruthenium acetylacetonate (Ru (acac)3, mass 321.62mg), 0.05mmol of iridium acetylacetonate (Ir (acac)3, mass 24.48mg), 0.05mmol of cobalt acetylacetonate (Co (acac)3, mass 17.81mg), add to 30mL of ethylene glycol, ice bath ultrasonic for 60min until completely dissolved, to obtain a light yellow transparent reagent A.

[0030] (2) Carbon carrier treatment: weigh 100mg of XC-72 carbon black, add to 30mL of ethylene glycol, three-roll ball mill for 12h (rotation speed 350rpm), to obtain reagent B.

[0031] (3) Reaction: mix reagent A and reagent B in a 100ml glass pressure-resistant reaction bottle, stir at 500rpm, reflux at 160℃ in an oil bath for 3h.

[0032] (4) Centrifugation and washing: as in Example 1, wash with ethanol, ultrapure water each for 3 times, 60℃ vacuum drying for 12h.

[0033] (5) Carbon carrier removal by heat treatment: as in Example 1, 450℃ for 2h in a tube furnace under air atmosphere.

[0034] (6) Acid washing: add 50mL of 0.5mol / L dilute sulfuric acid, ultrasonic acid washing for 24h, dry after washing to neutral, to obtain Ru 0.9 Co 0.05 Ir 0.05 O x catalyst.

[0035] Example 3. Ru 0.6 Mn​​​0.35 Ir 0.05 O x Preparation of catalyst (1) Precursor pretreatment: 0.6 mmol of ruthenium acetylacetonate (Ru(acac)3, mass 214.41 mg), 0.05 mmol of iridium acetylacetonate (Ir(acac)3, mass 24.48 mg), and 0.35 mmol of manganese acetylacetonate (Mn(acac)3, mass 124.35 mg) were weighed into 30 mL of ethylene glycol, and ultrasonic treatment was performed in an ice bath for 40 min until complete dissolution to obtain a light red transparent reagent A.

[0036] (2) Carbon carrier treatment: 100 mg of Ketjen black was weighed into 30 mL of ethylene glycol, and three-roll ball milling was performed for 12 h (rotation speed 350 rpm) to obtain reagent B.

[0037] (3) Reaction: reagent A and reagent B were mixed in a pressure-resistant reaction bottle, and stirring was performed at 500 rpm, and reflux reaction was performed at 160°C in an oil bath for 3 h.

[0038] (4) Centrifugation and washing: the same as in Example 1, and washing was performed with ethanol and ultrapure water alternately, and vacuum drying was performed at 60°C for 12 h.

[0039] (5) Carbon carrier removal by heat treatment: the same as in Example 1, and heat treatment was performed at 450°C in a muffle furnace under air atmosphere for 2 h.

[0040] (6) Acid washing: 50 mL of 1 mol / L perchloric acid was added, and ultrasonic acid washing was performed for 24 h, and the catalyst was dried after washing to neutral to obtain Ru 0.6 Mn 0.35 Ir 0.05 O x catalyst.

[0041] The modified ruthenium-based acidic oxygen evolution catalyst Ru 0.6 Co 0.35 Ir 0.05 O x obtained in Example 1 was observed by transmission electron microscopy (TEM), and it was found that it was a uniform nanoparticle with a diameter of about 10 nm, and the particle had good dispersibility and no obvious agglomeration. The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image showed that the particle had a uniform brightness distribution, indicating that the element distribution was uniform. The energy dispersive X-ray spectroscopy (EDS) element mapping clearly showed the uniform distribution of Ru, Co, Ir, and O elements in the particle, and through EDS semi-quantitative analysis, the molar ratio of Ru, Co, and Ir was about 0.6:0.35:0.05, which was consistent with the expected feed ratio.

[0042] The modified ruthenium-based acidic oxygen evolution catalyst Ru prepared in Example 1 was subjected to modification. 0.6 Co 0.35 Ir 0.05 O x X-ray diffraction (XRD) analysis revealed that the diffraction peaks of this catalyst perfectly matched the characteristic peak positions of the ruthenium oxide standard PDF card (e.g., JCPDS No. 40-1290), indicating that its main crystal structure is the ruthenium oxide phase. Compared to the standard card, the half-width at half-maximum (WHM) of the diffraction peaks of this catalyst was significantly increased. Calculations based on the Scherrer equation showed that its grain size was small, consistent with the approximately 10 nm particle size observed by TEM. Furthermore, the absence of impurity diffraction peaks indicated high catalyst purity. X-ray photoelectron spectroscopy (XPS) analysis clearly detected the characteristic peaks of Ru, Co, Ir, and O in the full spectrum, with no other impurity element peaks, further confirming the catalyst purity. The high-resolution XPS spectrum of Ru showed Ru 3p at 280.1 eV and 284.3 eV. 3 / 2 and Ru3p 1 / 2 The characteristic peaks, and the presence of Ru 3+ With Ru 4+ The splitting of the characteristic peaks indicates that Ru exists in the form of multivalent oxides, and this valence distribution is beneficial to improving the oxygen evolution reaction activity.

[0043] The oxygen evolution performance of the catalyst was tested in a 0.5 mol / L sulfuric acid solution using a three-electrode system (working electrode: glassy carbon electrode with catalyst supported; counter electrode: platinum wire; reference electrode: mercury / mercuric sulfate electrode). Electrochemical polarization curves showed that the modified ruthenium-based acidic oxygen evolution catalyst Ru prepared in Example 1 exhibited good oxygen evolution performance. 0.6 Co 0.35 Ir 0.05 O x Catalyst at 10 mA / cm 2 The oxygen evolution overpotential at current density is only 200 mV, which is far superior to that of pure ruthenium oxide catalyst (10 mA / cm²). 2 An overpotential of approximately 300 mV indicates a significant enhancement in oxygen evolution activity. Electron impedance spectroscopy results show that the charge transfer resistance of this nanocatalyst is lower than that of the commercial RuO2 catalyst, indicating a faster electron transfer rate and further reflecting higher oxygen evolution catalytic activity. The same catalytic activity evaluation was performed on Examples 2 and 3 at 10 mA / cm². 2 The oxygen evolution overpotentials at the current densities were 210 mV and 230 mV, respectively, showing good catalytic activity and demonstrating the good universality of the doping preparation scheme.

[0044] The modified ruthenium-based acidic oxygen evolution catalyst Ru 0.6 Co 0.35 Ir 0.05 O x 1A / cm 2 Voltage-time stability test at industrial level high current density, which was prepared into membrane electrode (catalyst loading 1 mg / cm 2 , proton exchange membrane is Nafion 115), assembled into a single cell test system, and its current-voltage curve showed that the corresponding working voltage of the membrane electrode was 1.65 V at a current density of 1 A / cm 2 , meeting the voltage requirement of industrial level proton exchange membrane water electrolysis device and having practical application potential. Working continuously at 1.65 V for 250 h, the voltage decay was less than 20 mV, and the stability was excellent. The same industrial water electrolysis test was carried out on the same embodiment cases 2 and 3, which could also work stably at a current density of 1 A / cm 2 for more than 100 h with a decay of less than 50 mV, also showing industrialization potential, proving that the catalyst synthesized by the method can achieve the large current long time working ability required by industrial water electrolysis test.

Claims

1. A method for preparing a low iridium-doped ruthenium oxide-based acidic oxygen evolution catalyst, characterized by, The strategy of combining solvent reduction method with carbon template method is adopted, and the multi-metal oxide nanocatalyst with flexible and controllable components and uniform mixture is synthesized through subsequent thermal oxidation and acid washing treatment; the specific steps are as follows: (1) precursor pretreatment: dissolving the ruthenium metal precursor salt and other metal M, N precursor salts in an organic solvent, and obtaining a uniform transparent mixed metal salt solution through ice bath ultrasonic treatment; (2) carbon carrier dispersion: dispersing the high specific surface area carbon carrier material in the organic solvent by mechanical grinding to obtain a uniform carbon carrier slurry; (3) solvent thermal reduction reaction: mixing the solution obtained in step (1) with the slurry obtained in step (2), and performing solvent thermal reflux reaction at 160-200℃ for 3-5 hours to reduce the metal ions and load them on the surface of the carbon carrier; (4) centrifugal washing and drying: after the reaction is completed, the product is centrifuged, and the supernatant is discarded; the product is washed repeatedly with ethanol and ultrapure water to remove impurities, and then vacuum dried to obtain a metal / carbon composite precursor; (5) thermal treatment oxidation: drying the powder in an air or oxygen atmosphere and performing programmed temperature thermal treatment to completely remove the carbon template and completely oxidize the metal precursor to form the target composite metal oxide; (6) acid washing purification: immersing the product after thermal treatment in a dilute acid solution for a long time under ultrasonic immersion to remove soluble impurities generated during the thermal treatment process; after deionized water washing and drying, the final catalyst product is obtained.

2. The production method according to claim 1, characterized by, In step (1): The ruthenium metal precursor salt is one of ruthenium acetylacetone, ruthenium trichloride and ruthenium acetate; The metal M is one or more of Co, Mn, Sn, Ti, Nb, Ta, Cr, Mo and W; the precursor salt of the metal M is one or more of hydrochloride, nitrate, sulfate and acetate; The metal N is one of Ir, Pt and Pd; the precursor salt of N is hydrochloride, and one or more of ruthenium acetylacetone, platinum acetylacetone, iridium acetylacetone, palladium acetylacetone, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum nitrate, potassium hexachloroplatinate, potassium tetrachloroplatinate, chloroiridic acid and potassium hexachloroiridate; The organic solvent is one of ethylene glycol and glycerol.

3. The preparation method according to claim 1, characterized in that, In step (2): The carbon carrier material is one of Ketjen black, Vulcan XC-72, carbon nanotube and graphene; The mechanical grinding adopts three-roll mill, ball mill or high-speed shear emulsifier; The organic solvent is one or more of ethanol, methanol, isopropanol and acetone.

4. The preparation method according to claim 1, characterized in that, In step (4), the product is centrifuged at a speed of 8000-10000rpm for 30-40min, the supernatant is discarded, and the product is washed with ethanol and ultrapure water alternately for 3 times, and then dried in a vacuum oven at 60-70℃ for 10-12h to obtain a black powder.

5. The preparation method according to claim 1, characterized in that, In step (5), the thermal treatment conditions are as follows: heating to 300-600℃ at a heating rate of 1-10℃ / min in an air or pure oxygen atmosphere and holding for 2-5h.

6. The method of claim 1, wherein, In step (6), the dilute acid is a hydrochloric acid, sulfuric acid or perchloric acid solution with a concentration of 0.5-1 mol / L, and the pickling time is 12-24 hours.

7. The production method according to one of claims 1 to 6, characterized in that, The chemical formula of the catalyst is Ru a M b N c O x , wherein M is a doped transition metal, N is a doped platinum group noble metal, a, b, and c are molar fractions of each metal, 0.5 < a < 0.95, 0.05 < b < 0.4, 0 < c < 0.1, and a + b + c = 1, and 0 < x < 2.

8. A low iridium doped ruthenium oxide-based acidic oxygen evolution catalyst obtainable by the preparation method of any one of claims 1 to 7.

9. Use of a low iridium doped ruthenium oxide-based acidic oxygen evolution catalyst according to claim 8 in the anode of a proton exchange membrane electrolyzer water splitting device.

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