High-entropy alloy atomic layer catalyst, preparation method and application

Abstract

The present application relates to the technical field of fuel cells and water electrolysis, in particular to a high-entropy alloy atomic layer catalyst, a preparation method and application. The catalyst has a PGM@IGM-PGM-HEA core-shell nanocube structure, the core is a platinum group metal, the shell layer is a quinary alloy formed by 2-3 iron group metals and 2-3 platinum group metals, and the atomic ratio is 1-3:1. The preparation method includes two steps of seed preparation and IGM-PGM-HEA atomic layer growth. The catalyst is coated on a carbon-based, metal or metal oxide electrode substrate to form an electrode, which is used for hydrogen evolution reaction and hydrogen oxidation reaction. In the hydrogen evolution reaction, the activity does not decrease by more than 10% after 15000 cycles in a 0.5 mol / L sulfuric acid solution test; in the hydrogen oxidation reaction, the intrinsic activity does not decrease by more than 20% after 3000 cycles in a 0.1 mol / L KOH solution test. Compared with a commercial Pt / C catalyst, the catalyst has high catalytic activity, good stability, can effectively reduce the reaction activation energy, and has important application value.

Description

Technical Field

[0001] This invention relates to the fields of fuel cell and water electrolysis technology, and in particular to a high-entropy alloy atomic layer catalyst, its preparation method, and its application. Background Technology

[0002] Hydrogen energy, as a representative of clean energy, relies on high-performance catalysts for its efficient preparation (HER, hydrogen evolution reaction) and utilization (HOR, hydrogen oxidation reaction). Currently, platinum group metals (PGMs), such as Pt and Ru catalysts, while exhibiting excellent performance, are scarce and expensive. In recent years, high-entropy alloys (HEAs) have become a research hotspot due to their multi-element synergistic effect ("cocktail effect"). By combining PGMs with iron group metals (IGMs), which are abundant on Earth, such as Fe, Co, and Ni, not only can the amount of precious metals used be reduced, but the catalytic performance can also be optimized through electronic interactions between multiple elements. However, existing high-entropy alloy catalysts face numerous challenges: Regarding atomic arrangement control, the significant differences in crystal structures between platinum group metals and iron group metals make it extremely difficult to achieve specific atomic arrangements on nanocrystal surfaces, directly impacting the formation of active sites and the efficiency of catalytic reactions. In terms of component optimization, current technologies lack systematic research on the catalytic performance of multi-element combinations, failing to fully realize the potential of high-entropy alloys and hindering the selection of optimal element combinations and ratios. Furthermore, the synergistic mechanisms among multiple elements are currently unclear, and the interactions and active sites between them are unknown, limiting a deeper understanding and effective improvement of catalyst performance. Additionally, whether high-entropy alloys are thermodynamically stable or metastable remains to be verified, raising questions about their thermal stability. This could lead to changes in the catalyst's structure and performance during practical applications, affecting its lifespan and reliability.

[0003] In summary, developing a high-entropy alloy atomic layer catalyst with high catalytic reaction efficiency, reasonable alloy element ratio, and thermodynamic stability is an urgent problem to be solved. Summary of the Invention

[0004] To address the problems of existing technologies, this invention reports a high-entropy alloy atomic layer catalyst prepared by wet chemical synthesis, its preparation method, and its application. The specific technical solution is as follows:

[0005] A high-entropy alloy atomic layer catalyst has a core-shell structure, wherein the core is a platinum group metal and the shell is an alloy formed of iron group metals and platinum group metals, and its structural formula is PGM@IGM-PGM-HEA; the catalyst has a cubic shape and a {100} crystal facet PGM@IGM-PGM-HEA core-shell nanocubic structure.

[0006] Furthermore, the core is a platinum group metal, and the shell is a pentagonal alloy formed by 2-3 iron group metals and 2-3 platinum group metals, with a shell thickness of 1-5 nm.

[0007] Furthermore, the iron group metal is two or three of Fe, Co, and Ni, and the platinum group metal is two or three of Ru, Rh, Pd, Os, Ir, and Pt.

[0008] Furthermore, in the shell, the atomic ratio of platinum group metals to iron group metals is 1-3:1.

[0009] A method for preparing a high-entropy alloy atomic layer catalyst is characterized by comprising two key steps: seed preparation and IGM-PGM-HEA atomic layer growth.

[0010] Furthermore, the preparation method of the high-entropy alloy atomic layer catalyst using Pd as the core is as follows:

[0011] Preparation of S1 and Pd cubic seeds: Add 0.01-0.1g of ascorbic acid, 0.1-1g of polyvinylpyrrolidone, and 0.1-1g of KBr to 20-100mL of deionized water and stir until homogeneous. Heat to 80-120℃, then add 1-5mL of Na2PdCl4 aqueous solution with a concentration of 0.05-0.2mol / L for reaction at 80-120℃ for 3-5h with a stirring rate of 500-800r / min to obtain the reaction product. Wash the reaction product with deionized water 3-5 times, and then ultrasonically disperse it in 10-50mL of oleylamine solvent to obtain a solution containing Pd cubic seeds.

[0012] S2, IGM-PGM-HEA atomic layer growth: Mix 5-20 mL of the solution containing Pd cubic seeds described in S1 with 10-50 mL of 1-octadecene until homogeneous. Preheat at 110℃ for 10-60 min, then at 200℃ for 10-60 min. Then add dropwise to 5-20 mL of metal salt precursor solution at a rate of 0.8-2 mL / h. Stir at 300-500 r / min. After the reaction is complete, wash and centrifuge 3-5 times. After drying, the high-entropy alloy atomic layer catalyst is obtained.

[0013] Furthermore, the preparation method of the high-entropy alloy atomic layer catalyst using Pd as the core is as follows:

[0014] Preparation of S1 and Pd octahedral seeds:

[0015] S1-1, Preparation of Pd nanocubes: In a flask, add 60-100 mg of ascorbic acid, 100-200 mg of polyvinylpyrrolidone, and 300-500 mg of KBr to 20-30 mL of deionized water, stir until homogeneous, heat at 80-120℃ for 5-20 min, then quickly inject 3-5 mL of Na2PdCl4 aqueous solution with a concentration of 15-30 g / L, and magnetically stir under sealed conditions for 3-5 h at a temperature of 80-120℃ and a stirring rate of 300-500 r / min. After stirring, allow to cool naturally to room temperature, then centrifuge and wash with deionized water 3-5 times. Sonicate the washed Pd nanocubes in 1-5 mL of formaldehyde solvent with a concentration of 0.1-0.5 mol / L to obtain a Pd nanocube solution.

[0016] S1-2. Add the Pd nanocube solution described in S1-1 and 0.5-5g of polyvinylpyrrolidone to 50-100mL of deionized water, then add 1-5mL of Na2PdCl4 solution with a concentration of 0.05-0.2mol / L to react at a temperature of 80-120℃ for 3-5h with a stirring rate of 500-800r / min to obtain the reaction product. Wash the reaction product with deionized water 3-5 times, and then ultrasonically disperse it in 10-50mL of oleylamine solvent to obtain a solution containing Pd octahedral seeds.

[0017] S2, IGM-PGM-HEA atomic layer growth: Mix 5-20 mL of the solution containing Pd octahedral seeds described in S1 with 10-50 mL of 1-octadecene until homogeneous. Preheat at 110℃ for 10-60 min, then at 200℃ for 10-60 min. Then add dropwise to 5-20 mL of metal salt precursor solution at a rate of 0.8-2 mL / h. Stir at 300-500 r / min. After the reaction is complete, wash and centrifuge 3-5 times. After drying, the high-entropy alloy atomic layer catalyst is obtained.

[0018] Furthermore, the precursor solution is an aqueous solution of a mixture of soluble salts of iron group metals and platinum group metals, wherein the concentration of each metal ion is 2×10⁻⁵-8×10⁻⁵ mol / L.

[0019] Furthermore, the soluble salts of platinum group metals are soluble salts of iron (Fe), cobalt (Co), and nickel (Ni), while the soluble salts of platinum group elements are soluble salts of platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), and ruthenium (Ru).

[0020] The present invention also provides an electrode coated with a high-entropy alloy atomic layer catalyst, wherein the electrode is obtained by coating the high-entropy alloy atomic layer catalyst onto an electrode substrate and then drying it.

[0021] Furthermore, the electrode substrate can be any one of carbon-based materials, metallic materials, or metal oxide materials.

[0022] This invention also provides a method for using a high-entropy alloy atomic layer catalyst to catalyze the hydrogen evolution reaction. The electrode coated with the high-entropy alloy atomic layer catalyst is applied to the electrochemical catalysis of the hydrogen evolution reaction. Electrochemical testing is performed using a three-electrode system with a 0.5 mol / L sulfuric acid solution as the electrolyte. Specifically, the electrode coated with the high-entropy alloy atomic layer catalyst is used as the working electrode, an Ag / AgCl electrode as the reference electrode, and a Pt electrode as the auxiliary electrode. The activity of the high-entropy alloy atomic layer catalyst decreases by no more than 10% after 15,000 cycles.

[0023] This invention also provides a method for using a high-entropy alloy atomic layer catalyst in a hydrogenation reaction. The electrode coated with the high-entropy alloy atomic layer catalyst is applied to the electrochemical catalysis of the hydrogenation reaction. Electrochemical testing is performed using a three-electrode system with a 0.1 mol / L KOH solution as the electrolyte. Specifically, the electrode coated with the high-entropy alloy atomic layer catalyst is used as the working electrode, an Hg / HgO electrode as the reference electrode, and a Pt electrode as the auxiliary electrode. The intrinsic activity of the high-entropy alloy atomic layer catalyst decreases by no more than 20% after 3000 cycles.

[0024] Beneficial effects of the present invention

[0025] 1. Unique Structure Enhances Catalytic Activity: The high-entropy alloy atomic layer catalyst of this invention possesses a PGM@IGM-PGM-HEA core-shell nanocube structure. The core is a platinum group metal, and the shell is a pentagonal alloy composed of various iron group metals and platinum group metals. This structure unexpectedly leverages the synergistic effect of each element. The platinum group metal, as the core, provides the basic active sites for the catalytic reaction. The multi-element alloy structure of the shell optimizes the electron cloud distribution on the catalyst surface through the "cocktail effect." The electronegativity differences between different metal atoms cause electron transfer between atoms, thereby changing the adsorption energy of reactants on the catalyst surface. Taking the Pd@PtRuFeCoNi atomic layer catalyst as an example, when the Pd@PtRuFeCoNi atomic layer catalyst is formed, the "cocktail effect" begins to take effect. Due to the different electronegativity of Pt, Ru, Fe, Co, and Ni atoms in the shell, electrons transfer between atoms, increasing the electronegativity of the atoms. The highly reactive Pt and Ru attract some electrons from Fe, Co, and Ni. For example, some electrons from Fe atoms flow to Pt and Ru, making the electron cloud more dispersed and uniform, no longer confined to the vicinity of a single atom. Simultaneously, the new chemical bonds and lattice structure formed by alloying further alter the electron cloud distribution, making electrons more delocalized throughout the shell region. While the Pd core is relatively stable, it also interacts with the shell atoms, fine-tuning the overall electron cloud distribution of the core and shell, enhancing the synergistic electronic effect of the entire catalyst system. In HOR, the optimized electron cloud distribution promotes the oxidation reaction of hydrogen molecules, allowing them to more effectively transfer electrons to the catalyst, thus improving the efficiency of the catalytic reaction. Therefore, the Pd@PtRuFeCoNi atomic layer catalyst, with its "cocktail effect" optimized electron cloud distribution, exhibits excellent catalytic activity in HER and HOR reactions.

[0026] 2. Precise control of atomic arrangement enhances catalytic selectivity: The technical solution employs a specific wet chemical synthesis method to precisely control the atomic arrangement, forming a structure with {100} crystal planes. This precise control is crucial in catalytic reactions. The presence of {100} crystal planes ensures an ordered atomic arrangement on the catalyst surface, with atoms of different elements distributed uniformly and regularly on the crystal planes. During catalytic reactions, reactants can interact more precisely with specific atoms or combinations of atoms, thereby improving the selectivity of the catalytic reaction. Taking the HER reaction as an example, the specific atomic arrangement makes it easier for hydrogen atoms to adsorb and react at specific positions on the catalyst surface, reducing unnecessary side reactions and improving the efficiency and purity of hydrogen generation, thus ensuring efficient hydrogen production.

[0027] 3. Excellent stability extends catalyst lifespan: The catalyst of this invention exhibits excellent stability in HER and HOR reactions. For example, in the HER test, the catalytic activity decreased by no more than 10% after 15,000 cycles, and in the HOR test, the catalytic activity decreased by no more than 20% after 3,000 cycles. This is attributed to its core-shell structure and the synergistic effect between elements. The core-shell structure provides a stable framework for the catalyst. The internal platinum group metal core ensures the basic catalytic performance of the catalyst, while the external alloy shell enhances the structural stability through inter-element interactions. During the reaction, the iron group metals and platinum group metals in the shell cooperate with each other, inhibiting atomic migration and aggregation, and reducing structural changes in the catalyst. At the same time, this structure also enhances the catalyst's tolerance to the reaction environment. For example, it can maintain stable catalytic activity in acidic (0.5 mol / L H2SO4 electrolyte in HER) and alkaline (0.1 mol / L KOH solution in HOR) environments, greatly extending the catalyst's lifespan, reducing usage costs, and improving its feasibility in practical applications. Detailed Implementation

[0028] To better explain the present invention, exemplary embodiments of the invention will be described in more detail below. While exemplary embodiments of the invention are shown below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments described herein. Rather, these embodiments are provided to enable a clearer and more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art.

[0029] Example 1: Preparation of Pd@PtRuFeCoNi atomic layer catalyst

[0030] S1, Pd cubic seed preparation

[0031] 60 mg of ascorbic acid, 105 mg of polyvinylpyrrolidone, and 300 mg of KBr were dissolved in 8 mL of water and stirred until homogeneous. The mixture was heated at 80 °C for 10 min, and then 3 mL of a 19 g / L Na₂PdCl₄ aqueous solution was rapidly injected in one go. The mixture was then magnetically stirred for 3 h under sealed conditions at 80 °C and a stirring rate of 300 r / min. After stirring, the mixture was allowed to cool naturally to room temperature to obtain Pd nanocubes. The Pd nanocubes were washed three times with deionized water and then ultrasonically dispersed in 10 mL of oleylamine to obtain a Pd cubic seed solution.

[0032] S2, PtRuFeCoNi atomic layer growth

[0033] 10 mL of the Pd cubic seed solution described in S1 was mixed thoroughly with 20 mL of 1-octadecene. The mixture was preheated at 110 °C for 30 min, then at 200 °C for 30 min. Afterward, 10 mL of a metal salt precursor solution was added dropwise at a rate of 0.8 mL / h. The precursor solution was a mixture of H₂PtCl₆·6H₂O, RuCl₃·xH₂O, Ni(C₅H₇O₂)₂, Co(C₅H₇O₂)₂, and Fe(C₅H₇O₂)₃, wherein the concentration of each metal ion was 4.2 × 10⁻⁶. -5 The catalyst was prepared by stirring at 300 r / min with a concentration of mol / L, washing and centrifuging three times after the reaction was completed, and then drying to obtain the Pd@PtRuFeCoNi atomic layer catalyst.

[0034] Example 2: Preparation of Pd@PtRhFeCoNi atomic layer catalyst

[0035] Preparation of S1 and Pd octahedral seeds:

[0036] S1-1. Preparation of Pd nanocubes: In a flask, 60 mg of ascorbic acid, 105 mg of polyvinylpyrrolidone, and 300 mg of KBr were added to 8 mL of deionized water and stirred until homogeneous. The mixture was heated at 80 °C for 10 min, and then 3 mL of a 19 g / L Na2PdCl4 aqueous solution was rapidly injected. The mixture was then magnetically stirred for 3 h under sealed conditions at 80 °C and a stirring rate of 300 r / min. After stirring, the mixture was allowed to cool naturally to room temperature, then centrifuged and washed three times with deionized water. The washed Pd nanocubes were ultrasonically dispersed in 1 mL of a 0.1 mol / L formaldehyde solvent to obtain a Pd nanocube solution.

[0037] S1-2. Add the Pd nanocube solution described in S1-1 and 0.5g of polyvinylpyrrolidone to 50mL of deionized water, then add 1mL of 0.05mol / L Na2PdCl4 solution to react at 80℃ for 3h with a stirring rate of 500r / min to obtain the reaction product. Wash the reaction product three times with deionized water, and then ultrasonically disperse it in 10mL of oleylamine solvent to obtain the Pd octahedral seed solution.

[0038] S2, PtRhFeCoNi atomic layer growth

[0039] 10 mL of the Pd octahedral seed solution described in S1 was mixed thoroughly with 10 mL of 1-octadecene. The mixture was preheated at 110 °C for 10 min, then at 200 °C for 10 min. Afterward, 5 mL of a metal salt precursor solution was added dropwise at a rate of 1 mL / h. The precursor solution was a mixture of H₂PtCl₆·6H₂O, RhCl₃·xH₂O, Ni(C₅H₇O₂)₂, Co(C₅H₇O₂)₂, and Fe(C₅H₇O₂)₃, wherein the concentration of each metal ion was 4.2 × 10⁻⁶. -5 The catalyst was prepared by stirring at 350 r / min with a concentration of mol / L, washing and centrifuging three times after the reaction was completed, and drying to obtain the Pd@PtRhFeCoNi atomic layer catalyst.

[0040] Example 3: Preparation of Pd@IrRuFeCoNi atomic layer catalyst

[0041] S1, Pd cubic seed preparation

[0042] 60 mg of ascorbic acid, 105 mg of polyvinylpyrrolidone, and 300 mg of KBr were dissolved in 8 mL of water and stirred until homogeneous. The mixture was heated at 80 °C for 10 min, and then 3 mL of a 19 g / L Na₂PdCl₄ aqueous solution was rapidly injected in one go. The mixture was then magnetically stirred for 3 h under sealed conditions at 80 °C and a stirring rate of 300 r / min. After stirring, the mixture was allowed to cool naturally to room temperature to obtain Pd nanocubes. The Pd nanocubes were washed three times with deionized water and then ultrasonically dispersed in 15 mL of oleylamine to obtain a Pd cubic seed solution.

[0043] S2, IrRuFeCoNi atomic layer growth

[0044] 15 mL of the Pd cubic seed solution described in S1 was mixed thoroughly with 30 mL of 1-octadecene. The mixture was preheated at 110 °C for 50 min, then at 200 °C for 50 min. Afterward, 15 mL of a metal salt precursor solution was added dropwise at a rate of 1.5 mL / h. The precursor solution was a mixture of IrCl3·xH2O, RuCl3·xH2O, Ni(C5H7O2)2, Co(C5H7O2)2, and Fe(C5H7O2)3, wherein the concentration of each metal ion was 4.2 × 10⁻⁶. -5 The catalyst was prepared by stirring at 400 r / min with a concentration of mol / L, washing and centrifuging three times after the reaction was completed, and then drying to obtain the Pd@IrRuFeCoNi atomic layer catalyst.

[0045] Hydrogen evolution reaction test

[0046] A three-electrode system was used, with the electrode coated with the atomic layer catalyst prepared in Examples 1-3 as the working electrode, the Ag / AgCl electrode as the reference electrode, and the Pt electrode as the auxiliary electrode. The test was carried out in 0.5 mol / L H2SO4 electrolyte. The test potential range was (-0.1)-0.1 V relative to the reversible hydrogen electrode, and the scan rate was 5 mV / s. The test results are shown in Table 1.

[0047] Hydroxylation reaction test

[0048] A three-electrode system was used, with the electrode coated with the atomic layer catalyst prepared in Examples 1-3 as the working electrode, the Hg / HgO electrode as the reference electrode, and the Pt electrode as the auxiliary electrode. The test was conducted in a 0.1 mol / L KOH electrolyte, with a geometric current density of -10 mA·cm⁻¹. -2 The test potential was increased from 0 to 0.2V, and the scan rate was 10mV / s. The test results are shown in Table 2.

[0049] Comparative Example

[0050] The working electrode was coated with a commercial Pt / C catalyst (Microvent), the reference electrode was Ag / AgCl, and the auxiliary electrode was Pt. The hydrogen evolution reaction was tested under the same conditions as in the example, and the test results are shown in Table 1; the hydrogen oxidation reaction was tested, and the test results are shown in Table 2.

[0051] Table 1. Test results of hydrogen evolution reaction in the examples and comparative examples.

[0052]

[0053] As shown in Table 1, the PGM@IGM-PGM-HEA atomic layer catalyst of the present invention can effectively reduce the activation energy of the HER reaction and promote hydrogen generation compared with commercial Pt / C catalysts, enabling the reaction to proceed at a lower additional voltage and demonstrating good catalytic activity. In particular, the Pd@PtRuFeCoNi atomic layer catalyst, due to its specific composition and ratio, can fully exert the "cocktail effect" to optimize the performance of the catalyst. As a result, the Pd@PtRuFeCoNi atomic layer catalyst can maintain relatively stable catalytic activity and good durability during long-term HER reactions.

[0054] Table 2. Test results of hydrogenation reaction in the examples and comparative examples.

[0055]

[0056] As shown in Table 2, the PGM@IGM-PGM-HEA atomic layer catalyst of the present invention can effectively reduce the reaction resistance and promote the hydrogenation reaction compared with commercial Pt / C catalysts. In particular, the Pd@PtRuFeCoNi atomic layer catalyst, with its unique composition and ratio, exhibits high catalytic activity in the HOR reaction and can efficiently catalyze the hydrogenation reaction. Furthermore, the Pd@PtRuFeCoNi atomic layer catalyst also has excellent stability in the HOR reaction and can maintain high catalytic activity after multiple cycles.

[0057] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any modifications or equivalent changes made based on the technical essence of the present invention shall still fall within the scope of protection claimed by the present invention.

Claims

1. A high-entropy alloy atomic layer catalyst, characterized in that, The catalyst has a core-shell structure, with the core being a platinum group metal and the shell being an alloy of iron group metals and platinum group metals. Its structural formula is PGM@IGM-PGM-HEA. The catalyst has a cubic shape and a {100} crystal facet PGM@IGM-PGM-HEA core-shell nanocube structure. The core is a platinum group metal; the shell is a pentagonal alloy formed of 2-3 iron group metals and 2-3 platinum group metals; In the shell, the atomic ratio of platinum group metals to iron group metals is 1-3:

1.

2. The high-entropy alloy atomic layer catalyst according to claim 1, characterized in that, The iron group metals are two or three of Fe, Co, and Ni, and the platinum group metals are two or three of Ru, Rh, Pd, Os, Ir, and Pt, with a shell thickness of 1-5 nm.

3. A method for preparing the high-entropy alloy atomic layer catalyst according to claim 1, characterized in that, It consists of the following steps: Preparation of S1 and Pd octahedral seeds: S1-1, Preparation of Pd nanocubes: In a flask, add 0.01-0.1 g of ascorbic acid, 0.1-1 g of polyvinylpyrrolidone, and 0.1-1 g of KBr to 5-15 mL of deionized water, stir until homogeneous, heat at 80-120℃ for 5-20 min, then quickly inject 3-5 mL of Na2PdCl4 aqueous solution with a concentration of 15-30 g / L, and magnetically stir under sealed conditions for 3-5 h at a temperature of 80-120℃ and a stirring rate of 300-500 r / min. After stirring, allow to cool naturally to room temperature, then centrifuge and wash with deionized water 3-5 times. Sonicate the washed Pd nanocubes in 1-5 mL of formaldehyde solvent with a concentration of 0.1-0.5 mol / L to obtain a solution containing Pd nanocubes. S1-2. Add the solution containing Pd nanocubes described in S1-1 and 0.5-5g of polyvinylpyrrolidone to 50-100mL of deionized water, then add 1-5mL of Na2PdCl4 solution with a concentration of 0.05-0.2mol / L for reaction at a temperature of 80-120℃ for 3-5h and a stirring rate of 500-800r / min to obtain the reaction product. Wash the reaction product with deionized water 3-5 times, and then ultrasonically disperse it in 10-50mL of oleylamine solvent to obtain a solution containing Pd octahedral seeds. S2, IGM-PGM-HEA atomic layer growth: Mix 5-20 mL of the solution containing Pd octahedral seeds described in S1 with 10-50 mL of 1-octadecene until homogeneous. Preheat at 110-130℃ for 10-60 min, then at 200℃ for 10-60 min. Then add dropwise to 5-20 mL of the metal salt precursor solution at a rate of 0.8-2 mL / h. Stir at a rate of 300-500 r / min. After the reaction is complete, wash and centrifuge 3-5 times. After drying, the high-entropy alloy atomic layer catalyst is obtained.

4. The preparation method according to claim 3, characterized in that, The precursor solution is an aqueous solution of a mixture of soluble salts of iron group metals and platinum group metals, wherein the concentration of each metal ion is 2 × 10⁻⁶. -5 -8×10 -5 mol / L.

5. An electrode coated with a high-entropy alloy atomic layer catalyst, characterized in that, The high-entropy alloy atomic layer catalyst of claim 1 is coated onto an electrode substrate and dried to obtain the electrode coated with the high-entropy alloy atomic layer catalyst, wherein the electrode substrate is any one of carbon-based material, metal material, or metal oxide material.

6. A high-entropy alloy atomic layer catalyst for catalyzing the hydrogen evolution reaction, characterized in that, The electrode coated with the high-entropy alloy atomic layer catalyst as described in claim 5 was applied to the electrochemical catalysis of the hydrogen evolution reaction. Electrochemical tests were conducted using a three-electrode system with a 0.5 mol / L sulfuric acid solution as the electrolyte. Specifically, the electrode coated with the high-entropy alloy atomic layer catalyst was used as the working electrode, the Ag / AgCl electrode as the reference electrode, and the Pt electrode as the auxiliary electrode. The activity of the high-entropy alloy atomic layer catalyst decreased by no more than 10% after 15,000 cycles.

7. A method for using a high-entropy alloy atomic layer catalyst in a hydrogenation reaction, characterized in that, The electrode coated with the high-entropy alloy atomic layer catalyst as described in claim 5 was applied to the electrochemical catalysis of the hydrogenation reaction. Electrochemical tests were performed using a three-electrode system with a 0.1 mol / L KOH solution as the electrolyte. Specifically, the electrode coated with the high-entropy alloy atomic layer catalyst was used as the working electrode, the Hg / HgO electrode as the reference electrode, and the Pt electrode as the auxiliary electrode. The intrinsic activity of the high-entropy alloy atomic layer catalyst decreased by no more than 20% after 3000 cycles.

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