CN113422080B

CN113422080B - Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation

Info

Publication number: CN113422080B
Application number: CN202110642370.5A
Authority: CN
Inventors: 宋玉江; 柴春晓
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2021-06-09
Filing date: 2021-06-09
Publication date: 2022-04-08
Anticipated expiration: 2041-06-09
Also published as: CN113422080A

Abstract

The invention discloses a carbon-supported non-platinum palladium-ruthenium-tungsten nanoparticle catalyst for alkaline hydrogen oxidation reaction, and a preparation method and application thereof, and belongs to the technical field of electrocatalysts. According to the invention, the uniformly dispersed non-platinum palladium-ruthenium-tungsten electrocatalyst with uniform particle size is prepared by a simple and easy-to-operate water bath reaction without any surfactant, the electrocatalyst with non-platinum low noble metal loading (10-20 wt%) is finally obtained by washing the catalyst with a large amount of deionized water, and the prepared supported catalyst is a non-platinum palladium-ruthenium-tungsten nanoparticle crystal uniformly dispersed on the surface of a carbon carrier. The invention adjusts the performance of the catalyst and the high-potential oxidation resistance of the ruthenium by adding different metal precursor salts into the mixed system. The nano crystal particles obtained by the method are very small, have excellent size uniformity and dispersibility, have higher electrochemical activity specific surface area and intrinsic activity, and are suitable for the anode side hydrogen oxidation reaction of an alkaline fuel cell.

Description

Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation

Technical Field

The invention belongs to the technical field of non-platinum noble metal and non-noble metal alloy electro-catalysts, and relates to a preparation method and application of a carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electro-catalyst.

Background

Due to the advantages of environmental friendliness, sustainability and the like, the development of the hydrogen-oxygen fuel cell is receiving attention from all countries all over the world. For alkaline hydrogen-oxygen fuel cells the conducting ion is OH^-. The total reaction therein is (H)₂+1/2O₂→H₂O), oxygen reduction reaction occurs at the cathode side thereof (1/2O)₂+H₂O+2e^-→2OH^-) On the anode side, the oxidation reaction (H) of hydrogen₂+2OH^-→2H₂O+2e^-) And finally, the chemical energy in the hydrogen and oxygen fuels is converted into clean electric energy. In recent years, with the continuous improvement of the performance and stability of the alkaline membrane, the catalyst adopted in the cathode side oxygen reduction reaction process in the alkaline fuel cell is expected to completely use non-noble metal catalyst to replace expensive and scarce platinum catalyst, and the alkaline fuelThe battery overcomes the problem that the acid fuel battery is easy to corrode, so that the development of the alkaline fuel battery is expected to exceed that of the acid fuel battery, and the alkaline fuel battery becomes a new generation of energy conversion device with high efficiency and low cost. However, alkaline fuel cells also have certain problems on the anode hydrogen oxidation side: the reaction rate of the commercial platinum-carbon catalyst under an alkaline condition is 2-3 orders of magnitude slower than that of the commercial platinum-carbon catalyst under an acidic condition, and the cost of the catalyst is higher due to the fact that the catalyst is mostly concentrated on a platinum-based noble metal catalyst, so that the rapid commercialization of the alkaline fuel cell is restricted. Therefore, the development of a high-performance, low-cost alkaline fuel cell anode oxyhydrogen electrocatalyst, in particular, metal nanoparticles uniformly dispersed on a carbon support and the improvement of the electrochemical performance of the catalyst and the further reduction of the cost of the catalyst by modulating the electronic structure of a non-platinum noble metal with an inexpensive tungsten metal, has made the rapid commercialization of the alkaline fuel cell a research hotspot in this field.

In 2017, King et al dissolved a metal salt precursor in water, then added a carbon carrier to the solution, ultrasonically treated, impregnated, dried, and finally annealed at high temperature to obtain IrPdRu/C catalysts with different proportions, which use Ir and Pd which are more expensive than ruthenium and have higher content (20% -90%) to increase the cost of the catalysts (Journal of the American Chemical Society,2017,139: 6807-. In 2018, the rest of the raw materials are mixed by using n-hexane (20mL) and n-hexanol (10mL) as mixed solvents, cetyl trimethyl ammonium bromide as a surfactant and sodium borohydride as a reducing agent. H is to be₂IrCl₆And RuCl₃The IrRu alloy with the nanowire structure is obtained by reaction at 40 ℃, but the catalyst uses a surfactant in the preparation process, and the residual surfactant can cover certain active sites; although the performance is improved in the micro-polarization region compared with that of Ru/C catalyst, the catalyst is instantly deactivated and loses the catalytic activity in the high potential region (Journal of Materials Chemistry A,2018,6: 20374-.

Li Hao et al synthesizes PtPdCu ternary alloy catalyst with Pt, Pd and Cu salt precursor in the presence of surfactant through hydrothermal process, and uses it in electrocatalytic ethanol oxidation, and the preparation process is not only carried out with surfactant but also under dangerous hydrothermal conditions of high temperature and high pressure, and is not suitable for large-scale production (Li Hao; Pengle super, chat city university, application number: 201910059027.0).

In view of the above, there is no article or patent reporting that a non-platinum palladium ruthenium tungsten (palladium content is very low) catalyst is used as an alkaline hydrogen oxidation catalyst, and the article or patent is related to the reported alkaline hydrogen oxidation electrocatalyst; most of the synthesized catalysts are platinum-based metal catalysts with high cost or ruthenium-based electrocatalysts which are rapidly oxidized under high potential to lose electrochemical activity or the synthesis conditions of the catalysts are complicated and difficult to produce on a large scale. Therefore, the research on the hydrogen oxidation reaction suitable for the anode of the alkaline fuel cell has important application value.

Disclosure of Invention

The invention aims to provide a preparation method and application of a carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for anode hydrogen oxidation reaction of an alkaline fuel cell, aiming at the defects of the prior art.

In order to realize the purpose, the invention adopts the technical scheme that:

the invention provides a preparation method of a carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst, which comprises the following steps:

(1) dispersing a carbon carrier in a solvent, and performing ultrasonic treatment to obtain a uniform dispersion liquid; and then adding a palladium metal salt precursor, a ruthenium metal salt precursor and a tungsten metal salt precursor into the dispersion liquid, and performing ultrasonic homogenization again to completely dissolve the metal salt. Then stirring the system for 2-20 min at the temperature of 20-60 ℃, adding a reducing agent, and reacting for 1-5 h at the temperature of 20-60 ℃ under stirring to reduce metal from the precursor; and (4) carrying out suction filtration, washing, drying and grinding to obtain the carbon-supported non-platinum palladium ruthenium tungsten catalyst. The performance of the catalyst and the high-potential oxidation resistance of ruthenium are adjusted by adding different metal precursor salts into the mixed system.

(2) Reacting the catalyst obtained in the step (1) for 0.2-4 h at 100-600 ℃ in a reducing atmosphere to further reduce and alloy the metal, cooling to room temperature, and grinding again to finally obtain the alkaline carbon hydroxide-supported non-platinum palladium ruthenium tungsten alloy nanoparticle electrocatalyst;

the concentration of the palladium metal salt precursor, the ruthenium metal salt precursor and the tungsten metal salt precursor in a solvent is 0.1-20 mmol L^-1The mass ratio of the palladium metal salt precursor to the ruthenium metal salt precursor to the tungsten metal salt precursor is 1-51-40: 1-10; the molar ratio of the palladium metal salt to the ruthenium metal salt to the tungsten metal salt is 0.01-1: 0.01-1; the concentration of the reducing agent in the solvent is 1-30 mg mL^-1(ii) a The concentration of the carbon carrier in the solvent is 1-20 mg mL^-1。

In the above technical solution, further, the palladium metal salt precursor is one of palladium dichloride, palladium tetraammine dichloride, palladium acetylacetonate, potassium chloropalladate, sodium chloropalladate, ammonium chloropalladate, potassium chloropalladite, sodium chloropalladite, ammonium chloropalladite and chloropalladite; the ruthenium metal salt precursor is one of ruthenium trichloride, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, ammonium chlororuthenate and ruthenium acetylacetonate; the precursor of the tungsten metal salt is one of sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate, zinc tungstate and phosphotungstic acid.

In the above technical solution, further, the reducing agent is one, two or more of glucose, citric acid, ascorbic acid, sodium borohydride and potassium borohydride; the solvent is one or more than two of deionized water, ethanol and glycol.

In the above technical solution, further, the carbon carrier is one, two or more of carbon black, activated carbon, carbon fiber, carbon nanotube, and graphene.

In the technical scheme, furthermore, the ultrasonic time in the step (1) is 0.2-1.5 h; the stirring speed in the step (1) is 500-900 rpm.

In the technical scheme, further, the stirring speed in the step (1) is 600-800 rpm.

In the above technical scheme, further, when the reaction temperature in the step (1) is higher than room temperature, after the reaction is finished, the reaction product is cooled to room temperature, and then the reaction product is subjected to suction filtration, washing, drying and grinding to obtain the carbon-supported non-platinum palladium-ruthenium-tungsten catalyst.

In the above technical solution, further, the suction filtration and washing in the step (1) specifically comprises the following steps: slowly pouring the suspension into a Buchner funnel with reduced pressure suction filtration, pumping out the filtrate, and washing the filter cake with 200-700 mL of deionized water until the sample is neutral.

In the technical scheme, furthermore, the drying time in the step (1) is 5-10 hours, and the drying temperature is 50-70 ℃.

In the technical scheme, the reducing atmosphere is one or more of hydrogen and a hydrogen-argon mixed gas, and when the reducing atmosphere is the hydrogen-argon mixed gas, the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1-5: 99-95.

The invention provides a metal nanoparticle electrocatalyst with uniformly dispersed carbon-supported non-platinum palladium-ruthenium-tungsten and uniform particle size, which is prepared by the preparation method, wherein the loading amount of palladium-ruthenium-tungsten metal on carbon in the carbon-supported non-platinum low-noble palladium-ruthenium-tungsten nanoparticle catalyst is 10-20 wt%.

According to the supported electrocatalyst prepared by the invention, the non-platinum palladium-ruthenium-tungsten metal spherical nano particles are uniformly dispersed on the carbon carrier, the particle diameter is about 2-3 nm, and the obtained nano crystal particles are very small and have excellent size uniformity and dispersibility.

In a third aspect, the invention provides the use of a carbon-supported non-platinum palladium ruthenium tungsten metal nanoparticle electrocatalyst for the hydrogen oxidation reaction of an alkaline fuel cell anode.

Compared with the prior art, the invention has the following advantages:

the method has the advantages that no surfactant is needed, the adsorption-reduction method is used for simply and quickly preparing the carbon-supported non-platinum metal nanoparticle electrocatalyst with uniform particle size, the preparation process is simple and easy to implement, the water bath reaction is realized, the batch production is easy, the simple physical adsorption method is adopted to uniformly disperse the metal nanoparticles on the carbon carrier, and the dispersion of the metal spherical nanoparticles is improved by controlling the carbonization temperature and the reduction atmosphere; the non-noble metal tungsten and a very small amount of palladium are introduced into a research object, the non-noble metal tungsten and the very small amount of palladium are used for modulating the electronic structure of ruthenium, other active sites and high-potential oxidation resistance are increased, and the prepared carbon-supported non-platinum palladium-ruthenium-tungsten metal nano-particle electrocatalyst with uniform particle size has high electrocatalytic activity, specific surface area and intrinsic activity, and is suitable for the anode hydrogen oxidation reaction of an alkaline fuel cell.

Drawings

FIG. 1 is a Transmission Electron Microscope (TEM) photograph of a sample prepared in example 1.

FIG. 2 is a graph of the particle size distribution of a sample prepared in example 1;

FIG. 3 is a thermogravimetric analysis (TG) curve of a sample prepared in example 1;

FIG. 4 is an X-ray diffraction (XRD) profile of a sample prepared in example 1;

FIG. 5 is a plot of the alkaline hydroxide micropolarization area of samples prepared in example 1 fitted to commercial platinum/carbon (20 wt%, Johnson Matthey) and comparative example 1 ruthenium/carbon and comparative example 2 palladium/carbon electrocatalysts prepared under the same conditions;

FIG. 6 is a TEM photograph of a sample prepared in example 2.

FIG. 7 is a graph of the particle size distribution of a sample prepared in example 2;

FIG. 8 is a TG curve of a sample prepared in example 2;

FIG. 9 is an X-ray diffraction (XRD) profile of a sample prepared in example 2;

FIG. 10 is a plot of the alkaline hydroxide micropolarization area of samples prepared in example 2 fitted to commercial platinum/carbon (20 wt%, Johnson Matthey) and comparative example 1 ruthenium/carbon and comparative example 2 palladium/carbon electrocatalysts prepared under the same conditions.

Detailed Description

The invention is further illustrated but is not in any way limited by the following specific examples. Platinum/carbon (20 wt%, Johnson Matthey) in the following examples was obtained commercially.

Example 1

Dispersing 40mg of VXC-72 carbon black in deionized water (5mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then, 4.74mL of a ruthenium trichloride solution (20mmoL), potassium chloropalladite (1.55mg), and sodium tungstate dihydrate (1.56mg) were added to the dispersion, and the mixture was subjected to ultrasonic treatment for 30min to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at 20 ℃ and 800 rpm. 43.0mg (10mg/mL) of sodium borohydride solution is then added, followed by stirring at 800rpm for 2 h. Then, the solid and the liquid are separated by a decompression suction filtration funnel, and then a large amount of deionized water is used for washing until the black solid filter cake is neutral. The black solid was then dried in an oven at 65 ℃ for 8 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; after the temperature is reduced to room temperature, the mixture is ground again to finally obtain the carbon-supported Pd with uniform particle size_0.05Ru_0.9W_0.05Metal nanoparticle electrocatalysts.

As shown in FIG. 1, TEM results showed that the obtained product was carbon-supported Pd having uniform particle size_0.05Ru_0.9W_0.05A nanoparticle electrocatalyst.

As shown in FIG. 2, the particle size statistics show that Pd is_0.05Ru_0.9W_0.05The particle size of the/C nanoparticles was approximately 2.7 nm.

TG determination of Pd in the resulting product as in FIG. 3_0.05Ru_0.9W_0.05The metal loading of/C was 13 wt%.

FIG. 4 is an X-ray diffraction (XRD) pattern of the sample prepared in example 1, from which Pd is known_0.05Ru_0.9W_0.05An alloy structure is formed.

Pd prepared as in FIG. 5_0.05Ru_0.9W_0.05Basic Hydrogen Oxidation Activity of/C electrocatalyst (460A g)_PdRuW ^-1) Superior to commercial platinum/carbon (343A g)_Pt ^-1) And Ru/C (160A g) prepared in comparative example 1_Ru ^-1) The specific mass activity was 1.34 and 2.88 times that of platinum/carbon and ruthenium/carbon, respectively.

Example 2

Dispersing 40mg of VXC-72 carbon black in deionized water (5mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then, 4.65mL of a ruthenium trichloride solution (20mmoL), potassium chloropalladite (0.76mg), and sodium tungstate dihydrate (2.30mg) were added to the dispersion, and the mixture was subjected to ultrasonic treatment for 30 minutes to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at 20 ℃ and 800 rpm. 42.3mg (10mg/mL) of sodium borohydride solution is then added, followed by stirring at 800rpm for 2 h. Then, the solid and liquid were separated with a vacuum filtration funnel and washed with a large amount of deionized water until the black solid became neutral. The black solid was then dried in an oven at 65 ℃ for 8 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; after the temperature is reduced to room temperature, the mixture is ground again to finally obtain the carbon-supported Pd with uniform particle size_0.025Ru_0.9W_0.075a/C metal nanoparticle electrocatalyst.

As shown in FIG. 6, TEM showed that the obtained product was carbon-supported Pd having uniform particle size_0.025Ru_0.9W_0.075A nanoparticle electrocatalyst.

As shown in FIG. 7, the particle size statistics of Pd_0.025Ru_0.9W_0.075The particle size of the nanoparticles was approximately 2.25 nm.

TG determination of Pd in the resulting product, as in FIG. 8_0.025Ru_0.9W_0.075The metal loading of (a) is 16 wt%.

As shown in fig. 9, XRD demonstrated that Pd was synthesized_0.025Ru_0.9W_0.075An alloy is formed.

Pd prepared as in FIG. 10_0.025Ru_0.9W_0.075Basic hydrogen oxidation activity of/C electrocatalyst (303A g)_PdRuW ^-1) Can be used with commercial platinum/carbon (343A g)_Pt ^-1) Is comparable with and far superior to Ru/C (160A g) prepared in comparative example 1_Ru ^-1)。

Example 3

Dispersing 40mg of VXC-72 carbon black in deionized water (10mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then 4.75mL of trichlorination was addedRuthenium solution (20mmoL), potassium chloropalladite (0.77mg), and sodium tungstate dihydrate (1.57mg) were added to the dispersion, and ultrasonic treatment was further performed for 30min to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at the temperature of 60 ℃ and the speed of 800 rpm. 43.1mg (10mg/mL) of sodium borohydride solution is then added, followed by stirring at 800rpm for 2 h. After cooling to room temperature, the solid and liquid were separated with a vacuum filtration funnel and washed with a large amount of deionized water until the black solid became neutral. The black solid was then dried in an oven at 60 ℃ for 9 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; and after the temperature is reduced to room temperature, grinding again to finally obtain the palladium-ruthenium-tungsten metal nano-particle electrocatalyst with uniform carbon-supported particle size.

Example 4

Dispersing 40mg of EC-600 carbon black in deionized water (10mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then, 4.74mL of a ruthenium trichloride solution (20mmoL), potassium chloropalladite (1.55mg), and sodium tungstate dihydrate (1.56mg) were added to the dispersion, and the mixture was subjected to ultrasonic treatment for 30min to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at 20 ℃ and 800 rpm. 43.0mg (10mg/mL) of glucose solution was then added, followed by stirring at 800rpm for 2 h. Then, the solid and liquid were separated with a vacuum filtration funnel and washed with a large amount of deionized water until the black solid became neutral. The black solid was then dried in an oven at 60 ℃ for 7 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) atmosphere in a tube furnace, and carbonizing for 1h at 300 ℃; and after the temperature is reduced to room temperature, grinding again to finally obtain the palladium-ruthenium-tungsten metal nano-particle electrocatalyst with uniform carbon-supported particle size.

Comparative example 1

Dispersing 40mg of VXC-72 black carbon in deionized water (5mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then 4.95mL of ruthenium trichloride solution (20mmoL) was added to the dispersion, and the mixture was further sonicated for 30min to completely dissolve the metal salt. And (3) placing the system in a water bath, and keeping the temperature at 20 ℃ and the speed at 800rpm for 2-5 min. Then 44.9 is addedmg (10mg/mL) of sodium borohydride solution, followed by 2h at 800 rpm. Then, the solid and liquid were separated with a vacuum filtration funnel and washed with a large amount of deionized water until the black solid became neutral. The black solid was then dried in an oven at 65 ℃ for 8 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; and after the temperature is reduced to room temperature, grinding again to finally obtain the ruthenium metal nano-particle (ruthenium/carbon) electrocatalyst with uniform carbon-supported particle size. But its catalytic performance for alkaline hydrogen oxidation is poor (160A g)_Ru ^-1)。

Comparative example 2

Dispersing 40mg of VXC-72 black carbon in deionized water (5mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then 30.68mg of potassium chloropalladite is added into the dispersion, and ultrasonic treatment is carried out for 30min to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at 20 ℃ and 800 rpm. 42.7mg (10mg/mL) of sodium borohydride solution are then added, followed by 2h at a stirring rate of 800 rpm. Then, the solid and liquid are separated by a decompression suction filter funnel, and then a large amount of ionized water is used for washing until the black solid becomes neutral. The black solid was then dried in an oven at 65 ℃ for 7 hours, ground, and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; and after the temperature is reduced to room temperature, grinding again to finally obtain the palladium metal nano-particle (palladium/carbon) electrocatalyst with uniform carbon-supported particle size. But its catalytic performance for alkaline hydrogen oxidation is poor (18A g)_Pd ^-1)。

Comparative example 3

Dispersing 40mg of VXC-72 black carbon in deionized water (5mL), and performing ultrasonic treatment for 30min to obtain uniformly dispersed carbon dispersion liquid; then, 4.69mL of a ruthenium trichloride solution (20mmoL) and potassium chloropalladite (1.63mg) were added to the dispersion, and the mixture was subjected to ultrasonic treatment for 30 minutes to completely dissolve the metal salt. And (3) placing the system in a water bath, and stirring for 2-5 min at 20 ℃ and 800 rpm. 44.8mg (10mg/mL) of sodium borohydride solution are then added, followed by stirring at 800rpm for 2 h. Then, the solid is first filtered by a vacuum filter funnelAnd the liquid was separated and washed with a large amount of deionized water until the black solid became neutral. Then the black solid is dried in an oven at 65 ℃, ground and mixed with hydrogen and argon (V)_Hydrogen:V_{Argon gas}5:95) in a tube furnace at 450 ℃ for 2 h; and after the temperature is reduced to room temperature, grinding again to finally obtain the palladium-ruthenium metal nano-particle electrocatalyst with uniform carbon-supported particle size. But its catalytic performance for alkaline hydrogen oxidation is not ideal (233A g)_PdRu ^-1)。

The performance of the commercial platinum on carbon, catalysts of examples 1, 2 and comparative examples 1, 2 described above is shown in table 1.

TABLE 1

	Catalyst and process for preparing same	j_0,m(A g^-1)
			Commerce	Pt/C	343
Comparative example 1	Ru/C	160
			Comparative example 2	Pd/C	18
Example 1	Pd_0.05Ru_0.9W_0.05/C	460
			Example 3	Pd_0.025Ru_0.9W_0.075/C	303

It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims

1. A method of making a carbon-supported, non-platinum, palladium ruthenium tungsten alloy nanoparticle electrocatalyst, comprising the steps of:

(1) dispersing a carbon carrier in a solvent, and performing ultrasonic treatment to obtain a uniform dispersion liquid; then adding a palladium metal salt precursor, a ruthenium metal salt precursor and a tungsten metal salt precursor into the solution, and performing ultrasonic homogenization; stirring the system for 2-20 min at the temperature of 20-60 ℃, adding a reducing agent, and reacting for 1-5 h at the temperature of 20-60 ℃ under stirring; carrying out suction filtration, washing, drying and grinding to obtain a carbon-supported non-platinum palladium ruthenium tungsten catalyst;

(2) reacting the catalyst obtained in the step (1) in a reducing atmosphere at 100-600 ℃ for 0.2-4 h, cooling to room temperature, and grinding again to finally obtain the non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for the alkaline carbon hydroxide loading;

the concentration of the palladium metal salt precursor, the ruthenium metal salt precursor and the tungsten metal salt precursor in a solvent is 0.1-20 mmol L^-1Precursor of palladium metal salt, precursor of ruthenium metal salt, precursor of tungsten metal saltThe mass ratio of the substances is 1-5: 1-40: 1-5;

the concentration of the reducing agent in the solvent is 1-30 mg mL^-1；

The concentration of the carbon carrier in the solvent is 1-20 mg mL^-1。

2. The method according to claim 1, wherein the palladium metal salt precursor is one of palladium dichloride, tetraamminepalladium dichloride, palladium acetylacetonate, potassium chloropalladate, sodium chloropalladate, ammonium chloropalladate and chloropalladite; the ruthenium metal salt precursor is one of ruthenium trichloride, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, ammonium chlororuthenate and ruthenium acetylacetonate; the precursor of the tungsten metal salt is one of sodium tungstate, calcium tungstate, cobalt tungstate, ferrous tungstate, ammonium tungstate, zinc tungstate and phosphotungstic acid.

3. The preparation method according to claim 1, wherein the reducing agent is one or more of glucose, citric acid, ascorbic acid, sodium borohydride and potassium borohydride; the solvent is one or more than two of deionized water, ethanol and glycol.

4. The preparation method according to claim 1, wherein the ultrasonic time in the step (1) is 0.2-1.5 h; the stirring speed in the step (1) is 500-900 rpm.

5. The method according to claim 1, wherein the carbon support is one or more of carbon black, activated carbon, carbon fiber, carbon nanotube, and graphene.

6. The preparation method according to claim 1, wherein the drying time in the step (1) is 5-10 h, and the drying temperature is 50-70 ℃.

7. The preparation method according to claim 1, wherein the reducing atmosphere in the step (2) is one or more of hydrogen and a mixed hydrogen-argon gas, wherein the volume ratio of hydrogen to argon in the mixed hydrogen-argon gas is 1-5: 99-95.

8. The carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst prepared by the preparation method according to any one of claims 1 to 7.

9. The carbon-supported non-platinum palladium ruthenium tungsten alloy nanoparticle electrocatalyst according to claim 8, wherein the loading of palladium ruthenium tungsten metal on carbon is 10 to 20 wt%.

10. Use of the carbon-supported non-platinum palladium ruthenium tungsten alloy nanoparticle electrocatalyst according to claim 8 or 9 in hydrogen oxidation reactions on the anode side of alkaline fuel cells.