Preparation method and application of alkaline hydroxide palladium ruthenium-cerium oxide electrocatalyst with high activity and wide potential stability window

Abstract

The invention relates to a preparation method and application of an alkaline palladium ruthenium hydroxide-cerium oxide electrocatalyst with a high-activity and wide-potential stability window. According to the preparation method, the non-platinum carbon-loaded ruthenium-based alloy is successfully prepared by adopting a wet chemical reduction and annealing combined method, and uniform dispersion of metal nanoparticles is realized. The palladium ruthenium-cerium oxide electrocatalyst prepared by the invention is small in particle size, uniform in dispersity and relatively high in current density and mass ratio activity, the problem of inactivation caused by over-oxidation of the ruthenium-based electrocatalyst under relatively high potential is also greatly improved, and the palladium ruthenium-cerium oxide electrocatalyst is suitable for an oxidation reaction of hydrogen at an anode side of an alkaline fuel cell.

Description

Technical Field

[0001] The invention relates to a preparation method and application of a carbon-supported palladium ruthenium-cerium oxide electrocatalyst for alkaline hydrogen oxidation reaction, belonging to the field of alkaline fuel cell electrocatalyst materials. Background Art

[0002] Hydrogen fuel cells are one of the important application directions of clean and sustainable hydrogen energy. For alkaline fuel cells, the overall reaction is 2H2+O2→2H2O, where the hydrogen oxidation reaction (HOR) occurs on the anode side, and the reaction formula is 2H2+4OH - →4H2O+4e - On the cathode side, the oxygen reduction reaction (ORR) occurs, and the reaction formula is O2+4e - +2H2O→4OH - , ultimately realizing the conversion of the chemical energy of hydrogen and oxygen into electrical energy. In recent years, with the development of alkaline anion exchange membrane technology, alkaline fuel cells have attracted much attention because they can use electrocatalysts that do not contain platinum group metals (PGM) on the cathode ORR side, thereby significantly reducing the cost of fuel cells. However, the kinetics of anode HOR in alkaline media are about 2-3 orders of magnitude lower than in acidic media, resulting in the need to use a large amount of Pt on the anode side to maintain the high performance of alkaline fuel cells. Therefore, exploring efficient and low-cost electrocatalysts in alkaline media is crucial to promoting the commercial application of alkaline fuel cells.

[0003] In PGM, Ru has an electronic structure similar to that of Pt, a relatively economical cost (the cost of Ru is about 50% of that of Pt), and excellent adsorption capacity for OH* and H* at low anode potentials. Therefore, Ru-based electrocatalysts are considered to be potential alternatives to Pt. However, the activity of Ru-based electrocatalysts is insufficient. When the potential exceeds ~0.1V vs.RHE, stable Ru-O bonds are easily generated, thereby losing sites for hydrogen adsorption and causing deactivation. To this end, researchers have invested a lot of effort to improve the activity of Ru. Sun et al. (Advanced Materials, 2022, 35, 2208821) constructed an interface-rich Ru and RuO2 heterostructure, presenting the best adsorption sites for H* and OH*, thereby improving the performance of alkaline HOR. However, the current density of the electrocatalyst begins to decrease when the potential is higher than 0.1V vs.RHE, and the deactivation problem of the electrocatalyst at high potential has not been solved. Han et al. (Small, 2023, 20, 2307725) used a template method to synthesize ultrathin carbon-coated RuNi alloy nanoparticles (NiRu / C) using a metal-organic framework. The metal-organic framework structure can effectively inhibit the agglomeration of alloy particles, thereby improving the stability of the electrocatalyst at high potentials. However, the synthesis steps are complicated and easily lead to waste of raw materials.

[0004] Researchers have conducted extensive research on Ru. Although some progress has been made, the prepared Ru-based electrocatalysts cannot simultaneously solve the problems of low activity and poor stability at high potentials. Therefore, it is urgent to design and prepare Ru-based electrocatalysts with excellent comprehensive performance. Summary of the Invention

[0005] The purpose of the present invention is to address the deficiencies in the prior art and to provide a method for preparing and applying a palladium ruthenium-cerium oxide electrocatalyst having high activity and a wide potential stability window for hydrogen oxidation reaction on the anode side of an alkaline fuel cell.

[0006] The technical solution of the present invention is:

[0007] The present invention provides a method for preparing a carbon-supported palladium ruthenium-cerium oxide electrocatalyst for alkaline hydroxide with high activity and a wide potential stability window, the preparation method comprising the following steps:

[0008] (1) Dispersing the carbon support in a solvent and ultrasonicating for 10 to 30 minutes to obtain a uniform dispersion, then adding a ruthenium-containing metal salt, a palladium-containing metal salt, and a cerium-containing metal salt, and ultrasonicating again for 10 to 30 minutes to fully mix the various substances, and then adding additives and stirring to react, followed by washing and drying;

[0009] (2) The black solid powder obtained in step (1) is fully ground and placed in a tube furnace for annealing and pyrolysis, programmed temperature is used, and after cooling to room temperature, it is ground again to obtain a palladium ruthenium-cerium oxide electrocatalyst for alkaline hydrogen oxidation reaction.

[0010] The carbon carrier of the present invention is at least one of activated carbon, carbon black, carbon nanotubes, carbon nanofibers, porous carbon and graphene.

[0011] The solvent in step (1) of the present invention is at least one of water, ethanol, N,N-dimethylformamide, acetone, ethylene glycol, cyclohexane, and tert-butanol.

[0012] The palladium-containing metal salt described in the present invention is at least one of palladium chloride, palladium nitrate, palladium sulfate, potassium tetrachloropalladate, and palladium acetate; the ruthenium-containing metal salt is at least one of ruthenium trichloride, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, chlororuthenic acid, ammonium chlororuthenate, and ruthenium acetylacetonate; and the cerium-containing metal salt is at least one of cerium trichloride, cerium nitrate, cerium sulfate, cerium acetate, ammonium cerium acetate, and ammonium cerium sulfate.

[0013] The additive added during the reaction in step (1) of the present invention is at least one of citric acid, sodium citrate, formic acid, acetic acid, formaldehyde, acetaldehyde, ascorbic acid, sodium ascorbate, hydrazine hydrate, ethylenediamine, lithium borohydride, sodium borohydride, potassium borohydride, sodium hydroxide, and glucose.

[0014] In step (1) of the present invention, the concentration of the carbon carrier in the solvent is 1 to 10 mg / mL, preferably 1 to 5 mg / mL;

[0015] The concentration of the ruthenium-containing precursor metal salt in the solvent is 1 to 10 mg / mL, preferably 1 to 5 mg / mL;

[0016] The concentration of the palladium-containing precursor metal salt in the solvent is 0.1 to 5 mg / mL, preferably 0.1 to 3 mg / mL;

[0017] The concentration of the cerium-containing precursor metal salt in the solvent is 0.1 to 3 mg / mL, preferably 0.1 to 1 mg / mL;

[0018] The concentration of the additive in the solvent is 0.1 to 10 mg / mL, preferably 0.1 to 5 mg / mL.

[0019] The molar ratio of palladium to ruthenium in the present invention is 0.1 to 0.3:1, for example, 0.1:1, 0.2:1, or 0.3:1.

[0020] The reaction time in step (1) of the present invention is 0.5 to 8 hours, preferably 0.5 to 3 hours, the reaction temperature is 80 to 230° C., preferably 120 to 200° C., and the stirring rate is 50 to 800 rpm, preferably 100 to 600 rpm.

[0021] The washing in step (1) of the present invention is centrifugal washing, the number of centrifugal washings is 1 to 5 times, the rotation speed of the centrifugal washing is 5000 to 20000 rpm, preferably 5000 to 10000 rpm, and the centrifugal time of each time is 3 to 20 minutes, preferably 3 to 10 minutes. The solvent for the centrifugal washing is at least one of ethanol, acetone, or a mixed solvent of n-hexane and water, and the volume ratio of ethanol, acetone, or n-hexane to water is 1:1 to 6:1, preferably 2:1 to 5:1.

[0022] The drying in step (1) of the present invention is carried out by placing the product in an oven for drying at a temperature of 50 to 100° C., preferably 50 to 80° C., and for a drying time of 3 to 16 hours, preferably 6 to 12 hours.

[0023] The grinding time for each time in step (2) of the present invention is 3 to 20 minutes, preferably 5 to 15 minutes.

[0024] The pyrolysis conditions in step (2) of the present invention are: a programmed heating rate of 1 to 10°C / min, preferably 3 to 10°C / min, a pyrolysis temperature of 100 to 800°C, preferably 100 to 600°C, a pyrolysis time of 0.5 to 5h, preferably 0.5 to 3h, and an atmosphere of argon, a hydrogen-argon mixture (the volume ratio of H2 to Ar is 1:99 to 10:90), or air.

[0025] The present invention provides a carbon-supported palladium ruthenium-cerium oxide electrocatalyst with high activity and a wide potential stability window for alkaline hydroxide prepared by the above-mentioned preparation method. The mass specific activity reaches 300 to 1000 A / g, and the electrocatalyst can still maintain good stability at a potential of 0.3 to 0.8 V vs. RHE. The size of the electrocatalyst can be controlled. The metal particles of the palladium ruthenium-cerium oxide nanoparticle electrocatalyst are uniformly loaded on the surface of the carbon support, have uniform size, and have an average particle size of 3 to 6 nm; the metal loading is 10 to 60 wt%, preferably 20 to 40 wt%.

[0026] The present invention provides the use of the carbon-supported palladium ruthenium-cerium oxide electrocatalyst in the hydrogen oxidation reaction on the anode side of an alkaline fuel cell.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] The present invention successfully prepared a non-platinum carbon-supported ruthenium-based alloy by combining wet chemical reduction and annealing, achieving a uniform distribution of metal nanoparticles. The synthesis method is simple and easy to implement, with high reproducibility. The metal nanoparticles of this electrocatalyst are small and uniform in size, with high current density and mass specific activity, outperforming commercial Pt / C electrocatalysts and effectively reducing costs. In addition, the oxidation problem of Ru-based electrocatalysts at high potentials is greatly improved, providing new ideas for the synthesis of hydrogen oxidation electrocatalysts and promoting the further development of alkaline fuel cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is the X-ray diffraction (XRD) spectrum of the sample prepared in Example 1.

[0030] Figure 2 This is a transmission electron microscope (TEM) image of the sample prepared in Example 1.

[0031] Figure 3 It is a statistical chart of particle size analysis of the samples prepared in Example 1.

[0032] Figure 4 It is the thermogravimetric analysis (TGA) curve of the sample prepared in Example 1.

[0033] Figure 5 These are the linear scan (LSV) graphs of the sample prepared in Example 1 and commercial Pt / C with a mass fraction of 20%, the sample prepared in Comparative Example 1, and the sample prepared in Comparative Example 2.

[0034] Figure 6 It is the Tafel plot of the sample prepared in Example 1 and commercial Pt / C with a mass fraction of 20%, the sample prepared in Comparative Example 1, and the sample prepared in Comparative Example 2.

[0035] Figure 7 It is the linear fitting curve of the Buter-Volmer equation in the micropolarization region of -5 to 5 mV for the sample prepared in Example 1 and commercial Pt / C with a mass fraction of 20%, the sample prepared in Comparative Example 1, and the sample prepared in Comparative Example 2.

[0036] Figure 8 The mass specific activities are those of the sample prepared in Example 1 and 20% mass fraction of commercial Pt / C, the sample prepared in Comparative Example 1, and the sample prepared in Comparative Example 2.

[0037] Figure 9 This is a linear scan (LSV) diagram of the sample prepared in Example 1 over a larger potential range (<0.8 V vs. RHE).

[0038] Figure 10 It is a linear scan (LSV) comparison diagram of the sample prepared in Example 1 and the sample prepared in Example 2. DETAILED DESCRIPTION

[0039] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0040] In the following examples, commercial platinum / carbon (20 wt %) electrocatalyst was purchased from Shanghai Hesen Electric Co., Ltd.

[0041] In the electrochemical performance tests of the electrocatalysts in the following examples, freshly prepared 0.1M KOH solution was used, and the temperature of the reaction system was ensured to be always at 25° C. by circulating water.

[0042] Example 1

[0043] Disperse 40 mg of Vulcan XC-72 in 20 mL of ethylene glycol and sonicate for 10 minutes to obtain a uniform dispersion. Then, add 26.9 mg of ruthenium trichloride, 8.5 mg of potassium tetrachloropalladate, and 2.8 mg of cerium nitrate hexahydrate. Sonicate again for 30 minutes to thoroughly mix the ingredients. Then, add 40 mg of sodium hydroxide and transfer the mixture to an oil bath. The mixture is heated from room temperature to 180°C and reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, wash the mixture three times with a 3:1 volume ratio of ethanol to water at 10,000 rpm for 10 minutes each wash. Then put it into a vacuum oven for drying, the time is set to 12 hours, the temperature is set to 60 ° C, the black solid powder obtained by drying is ground for 10 minutes, and then placed in a tube furnace for annealing and pyrolysis. The temperature is programmed to increase at a rate of 5 ° C / min under an argon atmosphere. After reaching 300 ° C, it is kept warm for 2 hours. After cooling to room temperature, it is ground again for 10 minutes to obtain Pd for alkaline hydrogen oxidation reaction. 0.2 Ru1-CeO2 / C electrocatalyst, denoted as PdRu-CeO2 / C.

[0044] like Figure 1 As shown in the XRD spectrum of PdRu-CeO2 / C electrocatalyst, diffraction peaks of Ru and RuO2 appeared, and the diffraction peak of Ru at 44° showed a slight negative shift, indicating that there was an alloy structure.

[0045] like Figure 2 The TEM images show that the metal nanoparticles of PdRu-CeO2 / C electrocatalyst are evenly distributed on the carbon support and the particle size is uniform.

[0046] like Figure 3 Particle size analysis statistics show that the metal nanoparticles of PdRu-CeO2 / C electrocatalyst are small in size, with an average particle size of 4.7nm.

[0047] like Figure 4The TGA curve of PdRu-CeO2 / C electrocatalyst showed that the metal loading was 24.5 wt%.

[0048] like Figure 5 The LSV curve shows that the current density of the PdRu-CeO2 / C electrocatalyst increases fastest around 0V vs. RHE, indicating that its reaction kinetics is the fastest, which is better than the commercial Pt / C electrocatalyst, the Ru / C electrocatalyst of Comparative Example 1, and the Pd / C electrocatalyst of Comparative Example 2.

[0049] like Figure 6 The Tafel slope curve shows that PdRu-CeO2 / C has the highest mass specific activity, which is better than the commercial Pt / C electrocatalyst, the Ru / C electrocatalyst of Comparative Example 1 and the Pd / C electrocatalyst of Comparative Example 2.

[0050] like Figure 7 The linear fitting curve of the Buter-Volmer equation in the -5 to 5 mV micropolarization region shows that the PdRu-CeO2 / C electrocatalyst has the highest HOR activity, which is better than the commercial Pt / C electrocatalyst, the Ru / C electrocatalyst of Comparative Example 1, and the Pd / C electrocatalyst of Comparative Example 2.

[0051] like Figure 8 The bar chart shows that the mass specific activity of the PdRu-CeO2 / C electrocatalyst reaches 781.7 A / g, which is better than the commercial Pt / C electrocatalyst (329.7 A / g), the Ru / C electrocatalyst of Comparative Example 1 (193.5 A / g) and the Pd / C electrocatalyst of Comparative Example 2 (16.2 A / g), which are 2.5 times, 3.9 times and 48.3 times higher than those of the commercial Pt / C electrocatalyst (329.7 A / g), the Ru / C electrocatalyst of Comparative Example 1 (193.5 A / g) and the Pd / C electrocatalyst of Comparative Example 2 (16.2 A / g), respectively.

[0052] like Figure 9 The LSV curves in a larger range (<0.8V vs.RHE) show that the stability of the PdRu-CeO2 / C electrocatalyst at high potentials is greatly enhanced, and the current density begins to decrease when the potential is higher than 0.67V vs.RHE, which is much better than that of the Ru / C electrocatalyst at 0.1V vs.RHE ( Figure 5 ).

[0053] Example 2

[0054] Disperse 40 mg of Vulcan XC-72 in 20 mL of ethylene glycol and sonicate for 10 minutes to obtain a uniform dispersion. Then, add 26.9 mg of ruthenium trichloride, 8.5 mg of potassium tetrachloropalladate, and 2.8 mg of cerium nitrate hexahydrate. Sonicate again for 30 minutes to thoroughly mix the ingredients. Then, add 40 mg of sodium hydroxide and transfer the mixture to an oil bath. The mixture is heated from room temperature to 180°C and reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, wash the mixture three times with a 3:1 volume ratio of ethanol to water at 10,000 rpm for 10 minutes each wash. Then put it into a vacuum oven for drying, the time is set to 12 hours, the temperature is set to 60 ° C, the black solid powder obtained by drying is ground for 10 minutes, and then placed in a tube furnace for annealing and pyrolysis. The temperature is programmed to increase at a rate of 5 ° C / min under an argon atmosphere. After reaching 400 ° C, it is kept warm for 2 hours, cooled to room temperature, and ground again for 10 minutes to obtain Pd for alkaline hydrogen oxidation reaction. 0.2 Ru1-CeO2 / C-400 electrocatalyst, denoted as PdRu-CeO2 / C-400.

[0055] like Figure 10 The LSV curves show that in the entire potential range, the performance of the electrocatalyst annealed at 300°C is better than that annealed at 400°C, indicating that the appropriate annealing temperature plays a vital role in the rational construction of the electrocatalyst.

[0056] Example 3

[0057] Disperse 40 mg of Vulcan XC-72 in 20 mL of ethylene glycol and sonicate for 10 minutes to obtain a uniform dispersion. Then, add 26.9 mg of ruthenium trichloride, 4.2 mg of potassium tetrachloropalladate, and 2.8 mg of cerium nitrate hexahydrate. Sonicate again for 30 minutes to thoroughly mix the ingredients. Then, add 40 mg of sodium hydroxide and transfer the mixture to an oil bath. The mixture is heated from room temperature to 180°C and reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, wash the mixture three times with a 3:1 (volume ratio) mixture of ethanol and water at 10,000 rpm for 10 minutes each wash. Then put it into a vacuum oven for drying, the time is set to 12 hours, the temperature is set to 60 ° C, the black solid powder obtained by drying is ground for 10 minutes, and then placed in a tube furnace for annealing and pyrolysis. The temperature is programmed to increase at a rate of 5 ° C / min under an argon atmosphere. After reaching 300 ° C, it is kept warm for 2 hours. After cooling to room temperature, it is ground again for 10 minutes to obtain Pd for alkaline hydrogen oxidation reaction. 0.1 Ru1-CeO2 / C electrocatalyst.

[0058] Example 4

[0059] Disperse 40 mg of Vulcan XC-72 in 20 mL of ethylene glycol and sonicate for 10 minutes to obtain a uniform dispersion. Then, add 26.9 mg of ruthenium trichloride, 12.7 mg of potassium tetrachloropalladate, and 2.8 mg of cerium nitrate hexahydrate. Sonicate again for 30 minutes to thoroughly mix the ingredients. Then, add 40 mg of sodium hydroxide and transfer the mixture to an oil bath. The mixture is heated from room temperature to 180°C and reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, wash the mixture three times with a 3:1 (volume ratio) mixture of ethanol and water at 10,000 rpm for 10 minutes each wash. Then put it into a vacuum oven for drying, the time is set to 12 hours, the temperature is set to 60 ° C, the black solid powder obtained by drying is ground for 10 minutes, and then placed in a tube furnace for annealing and pyrolysis. The temperature is programmed to increase at a rate of 5 ° C / min under an argon atmosphere. After reaching 300 ° C, it is kept warm for 2 hours. After cooling to room temperature, it is ground again for 10 minutes to obtain Pd for alkaline hydrogen oxidation reaction. 0.3 Ru1-CeO2 / C electrocatalyst.

[0060] The mass specific activities of the above-mentioned Example 1, Example 3, Example 4 and commercial Pt / C electrocatalysts are shown in Table 1.

[0061] Table 1

[0062] electrocatalysts Mass specific activity (A / g) Example 1 <![CDATA[Pd 0.2 Ru1-CeO2 / C]]> 781.7 Example 3 <![CDATA[Pd 0.1 Ru1-CeO2 / C]]> 595.7 Example 4 <![CDATA[Pd 0.3 Ru1-CeO2 / C]]> 527.1 Business Pt / C 315.6

[0063] The mass specific activity of the electrocatalyst material and the content of doped palladium show a volcano-shaped curve relationship that first increases and then decreases. The appropriate amount of Pd component is more effective in regulating the electronic structure of Ru, accelerating the reaction kinetics and enhancing the catalytic activity.

[0064] Comparative Example 1

[0065] 40 mg of Vulcan XC-72 was dispersed in 20 mL of ethylene glycol and sonicated for 10 minutes to obtain a uniform dispersion. 26.9 mg of ruthenium trichloride was then added and sonicated again for 30 minutes. After thorough mixing, 40 mg of sodium hydroxide was added and the mixture was transferred to an oil bath for reaction. The mixture was heated from room temperature to 180°C and then reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, the mixture was centrifuged and washed three times with a 3:1 ethanol / water mixture at 10,000 rpm, each wash lasting 10 minutes. The mixture was then dried in a vacuum oven at 60°C for 12 hours. The resulting black solid powder was ground for 10 minutes and then annealed and pyrolyzed in a tube furnace. A temperature program was used, increasing the temperature at a rate of 5°C / min under an argon atmosphere to 300°C, holding for 2 hours, cooling to room temperature, and then grinding again for 10 minutes to obtain the Ru / C electrocatalyst for alkaline hydrogen oxidation.

[0066] Comparative Example 2

[0067] 40 mg of Vulcan XC-72 was dispersed in 20 mL of ethylene glycol and sonicated for 10 minutes to obtain a uniform dispersion. 42.1 mg of potassium tetrachloropalladate was then added and sonicated again for 30 minutes. After thorough mixing, 40 mg of sodium hydroxide was added and the mixture was transferred to an oil bath for reaction. The mixture was heated from room temperature to 180°C and then reacted for 3 hours at a rotor speed of 600 rpm. After completion of the reaction, the mixture was centrifuged and washed three times with a 3:1 ethanol / water mixture at 10,000 rpm, each wash lasting 10 minutes. The mixture was then dried in a vacuum oven for 12 hours at 60°C. The resulting black solid powder was ground for 10 minutes and then annealed and pyrolyzed in a tube furnace. A temperature program was used, increasing the temperature at a rate of 5°C / min under an argon atmosphere to 300°C, holding for 2 hours, cooling to room temperature, and then grinding again for 10 minutes to obtain the Pd / C electrocatalyst for alkaline hydrogen oxidation.

[0068] Anyone skilled in the art will be able to utilize the above-disclosed technical content to make many possible changes and modifications to the technical solution of the present invention, or to modify it into equivalent embodiments with equivalent changes, without departing from the scope of the technical solution of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention that do not depart from the content of the technical solution of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing an alkaline hydrogenated palladium ruthenium-cerium oxide electrocatalyst with high activity and a wide potential stability window, characterized in that: The following steps are involved: (1) dispersing the carbon support in a solvent, ultrasonicating for 1 to 30 minutes to obtain a uniform dispersion, then adding a ruthenium-containing metal salt, a palladium-containing metal salt, and a cerium-containing metal salt, ultrasonicating again for 1 to 30 minutes, fully mixing, and then adding additives to react, followed by washing and drying to obtain a black solid powder; (2) Grinding the black solid powder obtained in step (1) and placing it in a tube furnace for pyrolysis, cooling it to room temperature, and then grinding it again to obtain a palladium ruthenium-cerium oxide electrocatalyst for the hydrogen oxidation reaction on the anode side of an alkaline fuel cell.

2. The preparation method according to claim 1, characterized in that The carbon carrier is at least one of activated carbon, carbon black, carbon nanotubes, carbon nanofibers, porous carbon, and graphene; and the solvent is at least one of water, ethanol, N,N-dimethylformamide, acetone, ethylene glycol, cyclohexane, and tert-butanol.

3. The preparation method according to claim 1, characterized in that The palladium-containing metal salt is at least one of palladium chloride, palladium nitrate, palladium sulfate, potassium tetrachloropalladate, and palladium acetate; the ruthenium-containing metal salt is at least one of ruthenium trichloride, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, chlororuthenic acid, ammonium chlororuthenate, and ruthenium acetylacetonate; the cerium-containing metal salt is at least one of cerium trichloride, cerium nitrate, cerium sulfate, cerium acetate, ammonium cerium acetate, and ammonium cerium sulfate.

4. The preparation method according to claim 1, characterized in that The additive is at least one of citric acid, sodium citrate, formic acid, acetic acid, formaldehyde, acetaldehyde, ascorbic acid, sodium ascorbate, hydrazine hydrate, ethylenediamine, lithium borohydride, sodium borohydride, potassium borohydride, sodium hydroxide, and glucose.

5. The preparation method according to claim 1, characterized in that In the step (1), the concentration of the carbon carrier in the solvent is 1 to 10 mg / mL; The concentration of the ruthenium-containing precursor metal salt in the solvent is 1 to 10 mg / mL; The concentration of the palladium-containing precursor metal salt in the solvent is 0.1 to 5 mg / mL; The concentration of the cerium-containing precursor metal salt in the solvent is 0.1 to 3 mg / mL; The concentration of the additive in the solvent is 0.1 to 10 mg / mL.

6. The preparation method according to claim 1, characterized in that In the step (1), the reaction time is 0.5 to 8 hours, the reaction temperature is 80 to 230° C., and the stirring rate is 50 to 800 rpm.

7. The preparation method according to claim 1, characterized in that The washing in step (1) is centrifugal washing; the drying temperature in step (1) is 50 to 90° C. and the drying time is 3 to 16 hours; The pyrolysis conditions in the step (2) are as follows: a heating rate of 1 to 10°C / min, a pyrolysis temperature of 100 to 800°C, a pyrolysis time of 0.5 to 5h, and an atmosphere of argon, a hydrogen-argon mixture, or air; and the grinding time for each grinding in the step (2) is 3 to 20min.

8. A palladium ruthenium-cerium oxide electrocatalyst for alkaline hydrogenation having high activity and a wide potential stability window, prepared by the preparation method according to any one of claims 1 to 7.

9. The palladium ruthenium-cerium oxide electrocatalyst according to claim 8, characterized in that The metal loading is 10 to 60 wt%.

10. Use of the palladium ruthenium-cerium oxide electrocatalyst according to claim 8 or 9 in the oxidation reaction of hydrogen on the anode side of an alkaline fuel cell.

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