Ruthenium oxide catalyst with high oxygen vacancy, preparation method, hydrogen production material and electrode thereof

Abstract

According to the preparation method of the high-oxygen-vacancy ruthenium oxide catalyst, the catalyst is nanoparticles, and the chemical formula of the catalyst is ZnxRu1-xO2 (x is more than or equal to 0 and less than or equal to 1); the preparation method adopts a dual regulation and control method, that is, metal Zn doping is performed on RuO2, polyvinylpyrrolidone (PVP) is added as a protective agent, and the doping content, the morphology and the crystallinity of the catalyst are regulated and controlled by adjusting factors such as the amount of a zinc source and the amount of macromolecules and adjusting the reaction time, the reaction temperature and the annealing temperature. The RuO2-based catalyst with high oxygen vacancy, high stability and high catalytic activity is rapidly and efficiently synthesized under the dual action of PVP and metal Zn doping. The method is easy to operate, raw materials are cheap and easy to obtain, batch preparation can be achieved, multi-step preparation treatment does not need to be conducted on a sample, Zn-Ru-O of a nano-particle structure exposes a large active surface area, stability is high, catalytic activity is high, and the method is green and free of pollution.

Description

Technical Field

[0001] The present invention belongs to the technical field of producing electrocatalytic oxygen evolution catalysts by nanotechnology and chemical methods and the field of catalytic materials, and particularly relates to a nanoparticle water electrolysis catalyst based on Zn-RuO2 modified by doping transition metals with PVP as a protective agent, a preparation method, a hydrogen production material and an electrode thereof. Background Art

[0002] Hydrogen energy is currently recognized as a clean, efficient and green energy source. It is a bridge connecting renewable energy and stable supply at the consumer end. As an effective hydrogen production technology, water electrolysis can be coupled with renewable energy power generation to provide a solution for hydrogen production. To realize the transition of water electrolysis hydrogen production technology from experiments to large-scale commercial applications, catalysts are one of the keys. Simplifying the synthesis path of water electrolysis catalysts, selecting suitable catalyst materials, and preparing electrochemical catalysts with high stability, high activity and low cost are the current hot spots and frontiers of research at home and abroad. Studies have shown that precious metals and their compound catalysts represented by Ir and Ru have good catalytic performance, but the scarcity and high cost of precious metals limit large-scale commercial applications.

[0003] In the process of hydrogen production by water electrolysis, proton exchange membrane electrolyzer has become a promising green hydrogen production technology due to its low operating temperature, high electrolysis efficiency and fast response speed. However, the oxygen evolution reaction (OER) on the anode side usually consumes more energy, which limits the efficiency of hydrogen production by water electrolysis. In recent years, in order to improve the catalytic performance of precious metals while reducing their costs, the literature Chem. Int. Ed. 2014, 53, 14016-14021 reported that ruthenium oxide (RuO2) is considered to be a promising catalyst and is expected to become a substitute for the precious metal catalyst I rO2. However, poor stability is the main problem hindering the development of RuO2-based catalysts. Therefore, solving the stability of RuO2 will be a huge challenge. In general, the poor stability of RuO2 mainly comes from two reasons, namely, the oxidation release of lattice oxygen and the leaching of surface Ru. The former is caused by the peroxidation of Ru to RuO4 and the participation of lattice oxygen in OER, while the latter is caused by the demetallization of surface Ru. Therefore, in order to achieve high stability, it is very desirable to improve the stability of lattice oxygen and surface Ru at the same time. The main methods to enhance the stability of RuO2 are metal doping, heterostructure, defect engineering and morphology control. The core of these methods is to adjust the surface atomic arrangement and the electronic structure of RuO2, and optimize the binding strength of OER intermediates (i.e. *OH, *O and *OOH).

[0004] Prior art, such as Chinese patent application (publication number: CN111628187 A, application number: CN202010375202.X) discloses a carbon-supported ruthenium oxide catalyst and its preparation method, and a one-step hydrothermal method is used to prepare a RuO2 / AC catalyst, which can be operated according to the following steps: dissolving ruthenium chloride hydrate in isopropanol, slowly adding activated carbon under ultrasonic conditions to obtain a uniform suspension, adding the obtained suspension to a hydrothermal reactor, and performing a hydrothermal reaction for 6 hours at a hydrothermal temperature of 160°C. The obtained product is centrifuged, washed with water and alcohol, and then dried under vacuum conditions to obtain a catalyst precursor, which is calcined, cooled, and ground to obtain a carbon-supported ruthenium oxide catalyst. The ruthenium oxide catalyst prepared by the invention uses carbon as a carrier, and the carbon-based material is easily dissolved under acidic and strongly oxidizing conditions, causing the catalyst to fall off. The Chinese patent application (patent number: CN118186469A, application number: CN202410167553.X) discloses a bismuth-doped ruthenium dioxide electrocatalyst and its preparation method and application, which can be prepared according to the following steps: ruthenium salt, bismuth salt, reducing agent, surfactant and a mixed solution of 1-octadecene and oleylamine are mixed, wherein the molar ratio of ruthenium salt to bismuth salt is 1:1-1:2, and the molar ratio of bismuth salt to reducing agent is 1:5-1:10, and the mixed solution is heated and stirred to obtain a mixed solution, and the mixed solution is washed and centrifuged with an organic solvent to obtain a solid precipitate, and a part of the impurities are roasted to obtain a precursor, and then mixed with an acidic solution and washed and dried again to obtain a bismuth-doped ruthenium dioxide electrocatalyst. The method used in this invention requires the use of a variety of organic substances such as reducing agents and surfactants, and the preparation process is cumbersome and energy-intensive. The document App l.Surf.Sci.2024,642,158613 reports a preparation method of glucose-assisted thermal decomposition synthesis of cerium-doped ruthenium dioxide electrocatalyst, the steps of which include: adding cerium salt and ruthenium salt to deionized water of glucose and urea and stirring, heating at 140°C for 5 hours to form porous foam, and then annealing in air at 500°C for 8 hours to obtain the catalyst sample Ce-RuO2. The prepared Ce-RuO2 catalyst has a conductivity of 10 mA cm -2 A 25-hour stability test was conducted at a current density of , and no obvious degradation occurred. The document Small 2024,20,2305889 reported a method of preparing molybdenum-doped mesoporous ruthenium dioxide spheres (Mo-RuO2) by impregnation and calcination. First, a mixed reaction of organic solvents such as phenol and formaldehyde was performed, and then mesoporous carbon spheres were obtained by carbonization at high temperature. After that, the precursors of Ru and Mo were infiltrated into the mesoporous carbon spheres, and then calcined in air at 500°C to obtain Mo-RuO2 catalysts. After 5000 CV tests, the current density of the catalyst sample was slightly attenuated, and a 20-hour stability test was carried out at 1.4V, and the current density was attenuated by 9%. This method uses toxic drugs such as phenol and formaldehyde in the preparation process, which is very dangerous, and the stability of the prepared catalyst samples is not high.

[0005] However, the above-mentioned prior art has a series of problems in the preparation process of ruthenium oxide-based catalysts, such as high energy consumption, complex preparation process, poor catalyst stability, and long periodicity, especially the prior art of publication number: CN118186469 A, whose preparation method is complicated and cumbersome, and requires the use of a variety of organic solvents such as reducing agents and surfactants. When preparing the precursor, it is necessary to use organic solvents for washing and centrifugation and then roasting treatment. The process has a long cycle, high energy consumption, and is not easy to operate, and the obtained catalyst performance is poor. In addition, although most of the prepared ruthenium-based catalysts have good catalytic activity, their stability is not high. They are usually inactivated after being maintained for dozens of hours in acidic electrolytes, and the experimental operation, precision, conditions, etc. are too high, and it is difficult to achieve large-scale commercial production. Therefore, how to further improve the stability of the catalyst on the basis of ensuring the activity of the ruthenium oxide catalyst, improve the efficiency of catalyst preparation, reduce the preparation cost, and optimize the electrode preparation process has become the key to the research of ruthenium oxide-based electrocatalysts. Summary of the invention

[0006] In order to solve the deficiencies in the prior art, the present invention discloses a ruthenium oxide catalyst using PVP as a protective agent and doping metal Zn to increase oxygen vacancies, and the technical scheme is as follows:

[0007] A high oxygen vacancy ruthenium oxide catalyst, a high oxygen vacancy ruthenium oxide catalyst nanoparticle prepared by using PVP as a protective agent and doping metal Zn, wherein the ruthenium oxide catalyst is a black solid oxide particle, and its chemical formula is Zn x Ru 1-x O2(0≤x≤1).

[0008] The present invention also discloses a method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies, wherein the ruthenium oxide catalyst is the above-mentioned ruthenium oxide catalyst with high oxygen vacancies, and the method is characterized by comprising the following steps:

[0009] Step 1: doping metal ratio;

[0010] Step 2: Add protective agent;

[0011] Step 3: Heat and stir in an oil bath;

[0012] Step 4: Sample oxidation preparation.

[0013] The present invention also discloses a material for catalyzing proton exchange membrane water electrolysis to produce hydrogen, which is characterized in that: the material adopts the above-mentioned ruthenium oxide catalyst with high oxygen vacancies, and the metal Zn-doped modified ruthenium oxide catalyst nanoparticles have abundant oxygen vacancies.

[0014] The present invention also discloses an electrode, which is characterized by: high oxygen vacancy ruthenium oxide catalyst nanoparticles prepared by using PVP as a protective agent and doping metal Zn, and a catalyst nanoparticle electrode obtained by the above-mentioned high oxygen vacancy ruthenium oxide catalyst nanoparticle preparation method.

[0015] Beneficial Effects

[0016] Compared with the existing metal-doped ruthenium oxide catalyst, the present invention is simple to operate and time-saving. The raw material is transition metal Zn, which is cheap and easily available. There is no need for multi-step preparation of samples, no very high working conditions, and no need for any surfactants or other organic chemicals. The materials and experimental equipment such as ethanol and PVP used in the preparation process are very common. The process includes easy-to-operate processes such as solution proportioning, oil bath heating, and high-temperature oxidation. It is simple and efficient, the reaction process is adjustable and controllable, and the cost is extremely low. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a SEM image of ruthenium oxide catalyst nanoparticles prepared in Example 1 of the present invention, in which oxygen vacancies are increased by a dual regulation method of oxygen vacancies, i.e., using PVP as a protective agent and doping metal Zn, wherein the magnification is 100,000.

[0018] Figure 2 The OER polarization curves are obtained by comparing the ruthenium oxide catalysts with different doping ratios (1:9, 2:8, 3:7) prepared by ultrasonic mixing for 20 minutes, adding 60 mg PVP, heating in an oil bath at 80°C for 6 hours, and high-temperature oxidation at 400°C for 3 hours with the pure ruthenium oxide catalyst and the commercial ruthenium oxide catalyst.

[0019] Figure 3 The CP curve is obtained by comparing the ruthenium oxide catalyst with a doping ratio of Zn:Ru=1:9 prepared by ultrasonic mixing for 20 minutes, adding 60 mg of PVP, heating in an oil bath at 80°C for 6 hours, and high-temperature oxidation at 400°C for 3 hours with a pure ruthenium oxide catalyst and a commercial ruthenium oxide catalyst. DETAILED DESCRIPTION

[0020] The present invention also discloses a method for preparing ruthenium oxide catalyst nanoparticles using PVP as a protective agent and doping metal Zn to increase oxygen vacancies, comprising the following steps:

[0021] Step 1: Doping metal ratio

[0022] During the whole experiment, the total molar amount of metal was controlled to be 0.25 mmol. First, while maintaining the experimental environment as an inert gas Ar gas, 0-0.075 mmol ZnCl 2 and 0.175-0.25 mmol RuCl 3 were added as Zn source and Ru source to a glass vial containing 10 mL of ethanol, respectively. The glass vial was placed under ultrasonic conditions for 20 minutes to fully dissolve the raw materials added therein and mix them evenly. A reddish-brown solution 1 was observed. The parameter is set to 0.25 mmol here in order to minimize the loss of the drug in the experiment. The purpose of the experiment is to control the performance by controlling the ratio of doped metals (i.e., Zn:Ru). Therefore, as long as the metal molar ratio is guaranteed, the total amount can be set arbitrarily.

[0023] Step 2: Add protective agent

[0024] In order to improve the catalytic activity and stability of the catalyst, increase the crystallinity and prevent particle agglomeration, the parameters were optimized through experiments. In the process of solution proportioning, PVP is often used as a protective agent to prevent too little PVP from failing to act as a bonding and stabilizing agent, and excessive PVP may completely cover the catalyst material to ensure that the final material has better performance. Therefore, in the process of adding PVP, 20-100 mg of PVP is weighed with an electronic balance and added directly to solution 1. Solution 1 will change from reddish brown to light yellow suspension 2. It was finally found that adding 60 mg of PVP had the best effect, so in the preparation process, it was finally determined to weigh 60 mg of PVP as a protective agent.

[0025] Step 3: Oil bath heating and stirring

[0026] Add a PTFE stirring magnet of appropriate size to the light yellow suspension 2 prepared in step 2, keep the rotation speed at 500 rpm, seal the glass vial and place it in an oil bath, control the oil bath temperature and reaction time. After the reaction is completed, open the lid of the glass vial and continue to heat evenly under the original conditions, the purpose of which is to evaporate all the ethanol solvent, and finally obtain a light yellow block solid.

[0027] Since the temperature and time of heating in the oil bath have a great influence on the subsequent formation of nanoparticles, if the temperature is too low, the time required is too long and the performance of the formed solid material is poor, while if the temperature is too high, the internal structure of the solid material will be destroyed. Therefore, in this method, the oil bath temperature is adjusted to 40-80°C and the heating time is 4-12 hours. It was finally found that the oil bath temperature was 80°C and the heating time was 6 hours, so 80°C and 6 hours were finally determined as the oil bath temperature and time in the preparation process.

[0028] Step 4: Sample oxidation preparation

[0029] During the annealing process, the annealing temperature has a great influence on the microstructure and crystallinity of the material. If the temperature is too low, the sample material has a low crystallinity and an amorphous structure; if the temperature is too high, the sample particles are easily covered and agglomerated, resulting in insufficient exposure of the catalytic active sites and poor performance. The yellow block solid obtained in step 3 is properly ground and then transferred to a crucible porcelain boat. The temperature is increased to 250-450°C at a heating rate of 5°C / min in a tubular furnace in an air atmosphere and kept warm for 1-5 hours. Finally, it is naturally cooled to 25°C to obtain a black oxide solid powder. It was finally found that the annealing temperature was 400°C and the annealing time was 3 hours, so 400°C and 3 hours were finally determined as the annealing temperature and time during the preparation process.

[0030] The present invention is a method for preparing ruthenium oxide catalyst nanoparticles by doping metal Zn with PVP as a protective agent to increase oxygen vacancies. The present invention is different from the current ruthenium dioxide-based catalyst preparation method in that the present invention does not use a surfactant and then a multi-step preparation method, but adopts a sol-gel method and adds PVP as a protective agent. By controlling the metal ratio added at the beginning, Zn salt and Ru salt are uniformly mixed in ethanol. With the proportion of doping elements, protective agent content, oil bath temperature and time, oxidation process, etc. as the main influencing factors, Zn-Ru-O catalyst nanoparticles prepared by the sol-gel method can be directly used for catalytic anode oxygen evolution reaction. This method is not only simple to operate, short in preparation cycle, and can be mass-produced, but also the material finally obtained can enhance catalytic performance and stability and reduce the amount of precious metal catalysts.

[0031] Compared with the existing metal-doped ruthenium oxide catalyst, the present invention is simple to operate, and the raw materials are transition metals, which are cheap and easy to obtain. There is no need to perform multi-step preparation processing on the sample, and very high working conditions are not required. No surfactants or other organic chemicals are required. The materials and experimental equipment such as ethanol and PVP used in the preparation process are very common. The process includes easy-to-operate processes such as solution proportioning, oil bath heating, and high-temperature oxidation. It is simple and efficient, the reaction process is adjustable and controllable, and the cost is extremely low.

[0032] The preparation method proposed in the present invention is not limited to the Zn-Ru-O bimetallic catalyst, and other transition metal elements can also be used to prepare binary (Nd-Ru-O, Ta-Ru-O) or even multi-element transition metal oxides (such as Ni-Co-Ru-O). The prepared products can not only be directly used to prepare proton exchange membrane water electrolysis catalytic reaction electrodes, but also can be used to prepare other fields such as alkaline water electrolysis catalytic reaction electrodes, fuel cell cathode and anode catalyst integrated electrodes, solid oxide water electrolysis catalytic reaction electrodes and coated structure nanomaterials.

[0033] Embodiment 1:

[0034] Under Ar gas conditions, 0.025 mmol ZnCl2 and 0.225 mmol RuCl3 raw materials were added to a glass vial containing 10 mL ethanol. The glass vial was placed under ultrasonic conditions for 20 minutes to fully dissolve the raw materials added therein and mix them evenly. After a reddish-brown liquid was observed, 60 mg polyvinyl pyrrolidone (PVP) was added, and the solution became a light yellow suspension. Then, a PTFE stirring magnet of appropriate size was added at a speed of 500 rpm, and the glass vial was sealed and placed in an oil bath pot and heated at 80 ° C for 6 hours. After the reaction was complete, the bottle cap was opened, and all ethanol was evaporated at 80 ° C to obtain a light yellow block solid. The block solid was properly ground and transferred to a crucible porcelain boat. The temperature was raised to 400 ° C in a tube furnace at a heating rate of 5 ° C / min in an air atmosphere, and annealed for 3 hours. Finally, it was naturally cooled to 25 ° C to obtain a black powder solid.

[0035] See attached Figure 1 As shown, this figure is a SEM image directly observed from the catalyst particles prepared in Example 1, where the magnification is 100,000.

[0036] Embodiment 2:

[0037] Under Ar gas conditions, 0, 0.05, 0.075 mmol ZnCl2 and 0.25, 0.2, 0.175 mmol RuCl3 raw materials were added to a glass vial containing 10 mL ethanol. The glass vial was placed under ultrasonic conditions for 20 minutes to fully dissolve the raw materials added therein and mix them evenly. After a reddish-brown liquid was observed, 60 mg polyvinyl pyrrolidone (PVP) was added, and the solution became a light yellow suspension. Then, a PTFE stirring magnet of appropriate size was added at a speed of 500 rpm, and the glass vial was sealed and placed in an oil bath pot and heated at 80 ° C for 6 hours. After the reaction was complete, the bottle cap was opened, and all ethanol was evaporated at 80 ° C to obtain a light yellow block solid. The block solid was properly ground and transferred to a crucible porcelain boat. The tube furnace was heated to 400 ° C at a heating rate of 5 ° C / min in an air atmosphere, and annealed for 3 hours. Finally, it was naturally cooled to 25 ° C to obtain a black powder solid.

[0038] The results are shown in the attached Figure 2As shown. This Example 2 shows the OER polarization curves of different doping ratios of Zn:Ru=1:9, 2:8, 3:7 and pure RuO2 and commercial RuO2 catalysts. It can be seen from the figure that different Zn doping contents have a significant effect on the catalytic performance of the catalyst. Too much Zn salt added may result in too little Ru content or too low crystallinity of the final sample, affecting the catalytic performance, while too little Zn salt added may result in Zn atoms not being easily doped into the RuO2 lattice and failing to achieve the design purpose of doping. Under the same electrolysis voltage, the sample prepared when the ruthenium oxide catalyst doping ratio is Zn:Ru=1:9 has the largest current density, the content of Zn salt doping in ruthenium oxide is optimal, and the OER catalytic performance exhibited is the best.

[0039] Embodiment 3:

[0040] Under Ar gas conditions, 0.25 mmol RuCl3 raw materials were added to a glass vial containing 10 mL ethanol. The glass vial was placed under ultrasonic conditions for 20 minutes to fully dissolve the raw materials added therein and mix them evenly. After a reddish-brown liquid was observed, 60 mg polyvinyl pyrrolidone (PVP) was added and the solution turned light yellow. Then, a PTFE stirring magnet of appropriate size was added at a speed of 500 rpm, and the glass vial was sealed and placed in an oil bath pot and heated at 80 ° C for 6 hours. After the reaction was complete, the bottle cap was opened and all ethanol was evaporated at 80 ° C to obtain a light yellow block solid. The block solid was properly ground and transferred to a crucible porcelain boat. The tube furnace was heated to 400 ° C at a heating rate of 5 ° C / min in an air atmosphere, and annealed for 3 hours. Finally, it was naturally cooled to 25 ° C to obtain a black ruthenium oxide powder solid.

[0041] See attached Figure 3 As shown, Example 3 is a preparation process of pure RuO2 without adding zinc salt, and the CP curve is tested under the same conditions as Example 1 and Example 2. It can be seen from the figure that the stability of the catalyst after adding transition metal Zn doping is obviously better than that of pure RuO2 and commercial RuO2, which is due to the fact that the addition of Zn adjusts the electronic structure of RuO2, increases more oxygen vacancies, and optimizes the adsorption energy of oxygen intermediates.

[0042] The double oxygen vacancy control method of Example 1 is to use PVP as a protective agent and dope metal Zn nanoparticle structure ruthenium oxide based catalyst, and its SEM image magnified 100000 times is as follows Figure 1 The LSV graphs and CP curves of the different catalysts prepared in Example 2 and Example 3 under the electrode system are shown in FIG. Figure 2 , Figure 3As shown. The catalyst was prepared by the dual oxygen vacancy regulation method, PVP was added as a protective agent, and transition metal Zn was added as a dopant, so that ruthenium oxide was uniformly grown into a Ru-O-Zn nanoparticle catalyst, which has good OER catalytic performance. It can not only prevent the excessive oxidation of Ru and enhance the stability of the catalyst, but also expose more active sites and enhance the activity of the catalyst. The process is easy to control and has strong repeatability.

[0043] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the principles and scope of the present invention. These changes and improvements fall within the scope of the present invention to be protected. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A ruthenium oxide catalyst with high oxygen vacancies, a ruthenium oxide catalyst with high oxygen vacancies prepared by using PVP as a protective agent and doping with metal Zn, Its characteristics are: The ruthenium oxide catalyst is a black solid oxide particle, and its chemical formula is Zn x Ru 1-x O 2 , 0≤x≤1.

2. A method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies, wherein the ruthenium oxide catalyst is the ruthenium oxide catalyst with high oxygen vacancies according to claim 1, Its characteristics are: The following steps are involved: Step 1: doping metal ratio; Step 2: Add protective agent; Step 3: Heat and stir in oil bath; Step 4: Sample oxidation preparation.

3. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 2, Its characteristics are: The step 1 further comprises the following steps: under argon conditions, adding Zn and Ru salts in a molar ratio of 1:9 into a glass vial containing an ethanol solution, and then ultrasonically mixing to disperse the metal precursor particles in the solvent, RuCl 3 Dissolved in ethanol to turn the solution into reddish brown, forming metal precursor solution 1.

4. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 3, Its characteristics are: The step 2 further comprises the following steps: using an electronic balance to weigh a certain mass of polyvinyl pyrrolidone PVP as a protective agent and directly adding it to the solution 1; the PVP is dissolved in the ethanol solution so that the solution 1 changes from reddish brown to light yellow, thereby forming a suspension 2.

5. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 2, Its characteristics are: The step 3 further includes the following steps: adding a PTFE stirring magnet at a certain rotation speed, and sealing the glass bottle and placing it in an oil bath pot, and simultaneously performing oil bath heating and magnetic stirring at a certain temperature; after the oil bath heating reaction for a period of time, opening the lid of the glass bottle and taking out the PTFE stirring magnet; heating under the original temperature conditions until all the solvent is evaporated, and finally obtaining a light yellow block solid.

6. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 5, Its characteristics are: The step 4 further comprises the following steps: grinding the light yellow block solid appropriately in an agate mortar to form a light yellow powder and transferring it to a crucible porcelain boat; annealing it in a tubular furnace for a certain period of time under an air atmosphere, and the heating rate of the tubular furnace is 5°C / min; finally, cooling it naturally to 25°C to obtain a black powder solid.

7. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 2, Its characteristics are: The amount of zinc salt is 0-0.075 mmol, the amount of ruthenium salt is 0.175-0.25 mmol, the content of polyvinyl pyrrolidone PVP is 20-100 mg, the oil bath temperature is 40-80° C., and the oil bath time is 4-12 hours.

8. The method for preparing ruthenium oxide catalyst nanoparticles with high oxygen vacancies according to claim 6, Its characteristics are: The annealing temperature is 250-450°C, and the annealing time is 1-5 hours.

9. Materials used for catalytic proton exchange membrane water electrolysis to produce hydrogen, Its characteristics are: The material adopts the ruthenium oxide catalyst with high oxygen vacancies as described in claim 1, and the ruthenium oxide catalyst nanoparticles modified by doping metal Zn have abundant oxygen vacancies.

10. An electrode, Its characteristics are: High oxygen vacancy ruthenium oxide catalyst nanoparticles prepared by using PVP as a protective agent and doping with metal Zn, and a catalyst nanoparticle electrode obtained by the preparation method of high oxygen vacancy ruthenium oxide catalyst nanoparticles according to any one of claims 2-8.

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