A surface engineering-activated hydrogen evolution electrocatalyst, its preparation method and application

Abstract

A hydrogen evolution electrocatalyst activated by surface engineering and its preparation method and application disclosed by the present invention. The preparation method includes the steps of: providing RTX powder; adding an organic acid and / or an organic acid salt to the RTX powder for the first surface engineering treatment, so that the organic acid and / or the organic acid salt undergoes a metal chelation reaction with the RTX powder to obtain a first product; adding an alkali solution to the first product for the second surface engineering treatment to obtain a hydrogen evolution electrocatalyst. By utilizing the strong chelating ability of organic acids and organic acid salts for lanthanide metals, the surface lanthanide elements of RTX particles are effectively etched, and then the strong scavenging ability of alkali solution for Si and Ge is used to remove Si and / or Ge on the surface of RTX, so that while the intermetallic electronide still maintains its original crystal structure and electronide characteristics, the surface is greatly optimized, and the specific surface area is increased by several times to hundreds of times, thereby obtaining a catalyst with ultra-high hydrogen evolution activity.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen evolution electrocatalysts, and particularly relates to a hydrogen evolution electrocatalyst activated by surface engineering, a preparation method thereof, and an application thereof. Background Art

[0002] Energy is one of the most important cornerstones for the development of modern society. However, as the main component of modern energy, fossil fuels are consumed at an increasing rate and are accompanied by serious industrial pollution, bringing a large number of economic and environmental problems to the current development. Therefore, in the long run, the development of renewable clean energy has become an urgent need for human society. As a gas with the highest energy mass density, hydrogen burns in air without producing any pollutants, so it is regarded as one of the most important green energy sources in future society. However, the traditional hydrogen production method, namely methane reforming, will produce a large amount of greenhouse gas carbon dioxide. Therefore, hydrogen production by electrolysis of water has attracted much attention in renewable energy engineering. However, the currently best-performing catalyst Pt is not suitable for large-scale application due to its high cost and poor stability. Therefore, the design and development of highly efficient and stable non-Pt hydrogen evolution electrocatalysts have become an urgent task at present.

[0003] Intermetallic electride RTX (R includes at least one of lanthanide elements; T includes at least one of transition metals such as Ni, Fe, Co, Mo, Mn, Cu, Ru, etc.; X includes at least one of Si, Ge) is a large class of intermetallic compounds with a tetragonal crystal structure (P4 / nm) pioneered by the team of Professor H. Hosono. It has attracted wide attention due to its relatively extremely low work function, high concentration of surface anion electrons, extremely strong thermal stability, stability in aqueous solution, and extremely large regulation space. Since electron anions usually have high activity and can be replaced by other anions, such as H-, combined with its low work function characteristics, it shows a unique activation ability for H, and the intermetallic electride can effectively fix the transition metal catalytic center in the compound. Therefore, RTX shows strong potential for electrocatalytic hydrogen evolution. However, as the key active center site T of the catalyst, the transition metal atoms are wrapped by the R layer and the X layer, and the catalytic activity of RTX is severely inhibited.

[0004] Meanwhile, high-temperature melting is the main method for producing intermetallic electrides in industry at present. Its main feature is to mix and heat metal blocks to a predetermined temperature, keep warm to reach phase equilibrium, then crush the sample evenly and repress it, and then perform high-temperature annealing to obtain a product with high crystallinity. For the intermetallic electride catalyst prepared by the above method, its specific surface area is usually small, and its catalytic activity has not been effectively developed.

[0005] Therefore, the prior art still needs to be improved and developed. Summary of the Invention

[0006] In view of the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a surface-engineered activated hydrogen evolution electrocatalyst, its preparation method and application, aiming to solve the problem that the specific surface area of intermetallic electronides prepared by existing methods is small and the catalytic activity cannot be effectively developed.

[0007] The technical solution of the present invention is as follows:

[0008] A preparation method of a surface-engineered activated hydrogen evolution electrocatalyst, comprising the steps of:

[0009] Providing RTX powder, wherein R comprises at least one of lanthanide elements; T comprises at least one of Ni, Fe, Co, Mo, Mn, Cu, Ru; X comprises at least one of Si, Ge;

[0010] Adding an organic acid and / or an organic acid salt to the RTX powder for the first surface engineering treatment, so that the organic acid and / or the organic acid salt undergoes a metal chelation reaction with the RTX powder to obtain a first product;

[0011] Adding an alkali solution to the first product for the second surface engineering treatment to obtain a surface-engineered activated hydrogen evolution electrocatalyst.

[0012] In the preparation method of the surface-engineered activated hydrogen evolution electrocatalyst, the concentration of the organic acid and / or the organic acid salt is less than 5M.

[0013] In the preparation method of the surface-engineered activated hydrogen evolution electrocatalyst, the organic acid is selected from at least one of acetylpyruvic acid, hexafluoroacetylpyruvic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid; the organic acid salt is selected from at least one of the salts corresponding to acetylpyruvic acid, hexafluoroacetylpyruvic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid.

[0014] In the preparation method of the surface-engineered activated hydrogen evolution electrocatalyst, the pH of the alkali solution is greater than 13 and the concentration is greater than 1M.

[0015] In the preparation method of the surface-engineered activated hydrogen evolution electrocatalyst, the alkali solution is selected from at least one of potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution, rubidium hydroxide solution, cesium hydroxide solution.

[0016] In the preparation method of the surface-engineered activated hydrogen evolution electrocatalyst, the preparation method of the RTX powder comprises the steps of:

[0017] Mix the elemental particles or bulk materials of R, T, and X in proportion and then perform repeated melting and cooling to form a bulk material;

[0018] Grind the bulk material into powder and press it into a mixed block under the protection of an inert gas;

[0019] Anneal the mixed block to obtain the purified intermetallic electronide RTX;

[0020] Grind the intermetallic electronide RTX into powder to obtain RTX powder;

[0021] R includes at least one of the lanthanide elements; T includes at least one of Ni, Fe, Co, Mo, Mn, Cu, and Ru; X includes at least one of Si and Ge.

[0022] In the preparation method of the surface engineering activated hydrogen evolution electrocatalyst, the step of grinding the bulk material into powder includes: subjecting the bulk material to ball milling under the protection of an inert gas or manually grinding it in a glove box environment;

[0023] The step of grinding the intermetallic electronide RTX into powder includes: subjecting the intermetallic electronide RTX to ball milling under the protection of an inert gas or manually grinding it in a glove box environment.

[0024] In the preparation method of the surface engineering activated hydrogen evolution electrocatalyst, after the first surface engineering treatment, centrifugation and washing treatments are further included to obtain a first product;

[0025] After the second surface process treatment, centrifugation, washing, and drying are further included to obtain the surface engineering activated intermetallic electronide hydrogen evolution electrocatalyst;

[0026] The reagent used for the washing is selected from at least one of deionized water and ethanol; the drying is vacuum drying.

[0027] A surface engineering activated hydrogen evolution electrocatalyst is prepared by using the preparation method of the surface engineering activated hydrogen evolution electrocatalyst.

[0028] An application of a surface engineering activated hydrogen evolution electrocatalyst, wherein the surface engineering activated hydrogen evolution electrocatalyst is used for hydrogen production by electrolyzing water.

[0029] Beneficial effects: The present invention provides a surface-engineered activated hydrogen evolution electrocatalyst, its preparation method and application. The preparation method includes the steps of: providing RTX powder, where R includes at least one of lanthanide elements; T includes at least one of Ni, Fe, Co, Mo, Mn, Cu, Ru; X includes at least one of Si, Ge; adding an organic acid solution and / or an organic acid salt solution to the RTX powder for the first surface engineering treatment, so that the organic acid and / or the organic acid salt undergo a metal chelation reaction with the RTX powder to obtain a first product; adding an alkali solution to the first product for the second surface engineering treatment to obtain a hydrogen evolution electrocatalyst. By utilizing the strong chelating ability of the organic acid and / or the organic acid salt for lanthanide metals, the present invention effectively etches the surface lanthanide elements of the RTX particles, and then uses an alkali solution with a strong scavenging ability for Si and Ge to remove Si and / or Ge on the surface of RTX. While the intermetallic electron compound still maintains its original crystal structure and electron compound characteristics, the surface is greatly optimized and the specific surface area is increased by several times to hundreds of times, thereby obtaining a catalyst with ultra-high hydrogen evolution activity. Description of the Drawings

[0030] Figure 1 Schematic diagram of selective etching by surface engineering using CeRuSi as a model in Example 1 of the present invention;

[0031] Figure 2 Graph of the change in surface element ratio after selective etching by surface engineering using CeRuSi as a model in Example 1 of the present invention;

[0032] Figure 3 Graph of the change in crystal structure characterized by XRD during the process of selective etching by surface engineering using CeRuSi as a model in Example 1 of the present invention;

[0033] Figure 4 Graph of the change in electrocatalytic hydrogen evolution activity of CeRuSi after surface etching in Example 1 of the present invention. Detailed Embodiments

[0034] The present invention provides a surface-engineered activated hydrogen evolution electrocatalyst, its preparation method and application. To make the purpose, technical solution and effects of the present invention clearer and more definite, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0035] In the embodiments and the claims, unless otherwise specifically defined in the text for articles, the words "a", "an", "the", and "said" may also include plural forms. If there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only for descriptive purposes and should not be construed as indicating or implying their relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features.

[0036] It should be further understood that the term "comprising" used in the specification of the present invention means the presence of the described features, integers, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or their groups. The phrase "and / or" used herein includes all or any unit and all combinations of one or more of the associated listed items.

[0037] Those skilled in the art of the present technology can understand that, unless otherwise defined, all terms (including technical terms and scientific terms) used herein have the same meaning as the general understanding of those of ordinary skill in the art to which the present invention pertains. It should also be understood that terms such as those defined in a general dictionary should be understood to have a meaning consistent with the meaning in the context of the prior art, and will not be interpreted with an idealized or overly formal meaning unless specifically defined as here.

[0038] Intermetallic electronides exist in the form of RTX (R includes at least one of the lanthanide elements; T includes at least one of transition metals such as Ni, Fe, Co, Mo, Mn, Cu, Ru; X includes at least one of Si, Ge), and are often prepared by methods of metal smelting and annealing purification. However, the directly obtained intermetallic electronides have too small a specific surface area and too few exposed active sites, resulting in too low catalytic hydrogen evolution performance.

[0039] Based on this, the present invention provides a preparation method of a surface-engineered activated hydrogen evolution electrocatalyst, including the steps:

[0040] Step S10: Provide RTX powder, where R includes at least one of the lanthanide elements; T includes at least one of Ni, Fe, Co, Mo, Mn, Cu, Ru; X includes at least one of Si, Ge;

[0041] Step S20, first surface engineering selective etching of RTX powder: Add organic acid and / or organic acid salt to the RTX powder for the first surface engineering treatment, so that the organic acid and / or organic acid salt undergoes a metal chelation reaction with the RTX powder to obtain a first product;

[0042] Step S30: Second surface engineering selective etching of the first product: Add an alkali solution to the first product for second surface engineering treatment to obtain an intermetallic electronide hydrogen evolution electrocatalyst with surface engineering activation.

[0043] In this embodiment, the surface of the sample particles is activated by selective chemical etching. After activation, the surface of the material is optimized and modified, but the bulk phase still retains the structural characteristics of the intermetallic electronide, and its electrocatalytic hydrogen evolution performance has been greatly improved, with a catalytic efficiency comparable to that of noble metal Pt in alkaline electrolytes. That is, by using the method of surface engineering activation to treat the metal electronide powder, not only is the process simple, but also an intermetallic electronide RTX with small particle size, high specific surface area, highly activated surface, and the bulk phase retaining the characteristics of the electronide can be obtained; moreover, the chemical structure of the intermetallic electronide is stable, the surface structure is greatly optimized and stabilized, and it has excellent electrocatalytic hydrogen evolution activity.

[0044] Specifically, the purpose of adding an organic acid and / or an organic acid salt to the RTX powder is to effectively etch the lanthanide elements on the surface of the RTX particles by using the strong chelating ability of the organic acid and / or the organic acid salt with the lanthanide elements; then, a suitable base is used to effectively remove Si and / or Ge on the surface of the RTX particles, so that the surface of the RTX particles is greatly optimized and the specific surface area is increased by several times to hundreds of times, thereby obtaining a catalyst with ultra-high hydrogen evolution activity.

[0045] In some embodiments, the concentration of the organic acid and / or the organic acid salt is less than 5M; an excessive amount of the organic acid and / or the organic acid salt is added to the RTX powder, and the strong metal chelating ability of the organic acid and / or the organic acid salt is used to effectively etch the lanthanide elements on the surface of the RTX particles to achieve the first surface engineering treatment.

[0046] Specifically, adding an organic acid and / or an organic acid salt to the RTX powder can be: adding an organic acid to the RTX powder, adding an organic acid salt to the RTX powder, or adding a mixture of an organic acid and an organic acid salt to the RTX powder.

[0047] In a preferred embodiment, after adding an excessive amount of the organic acid and / or the organic acid salt to the RTX powder, any one of the auxiliary methods such as standing, ultrasonic treatment, and stirring is used for treatment for 3 - 5h, which can limitedly etch the lanthanide elements on the surface of the RTX particles, improve the effect of selective chemical etching, and achieve the purpose of activating the surface of the RTX particles, so that the surface of the material after activation is optimized and modified, but the bulk phase still retains the structural characteristics of the intermetallic electronide. After the treatment is completed, the solid at the bottom is obtained by centrifugation, and the product is repeatedly washed with deionized water and ethanol to obtain the first product.

[0048] In some embodiments, the organic acid is selected from at least one of acetylpyruvic acid, hexafluoroacetylpyruvic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid; the organic acid salt is selected from at least one of the salts corresponding to acetylpyruvic acid, hexafluoroacetylpyruvic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid; by using the chelating ability of the organic acid / organic acid salt to lanthanide metals, etching of the lanthanide metals on the surface of RTX particles is achieved.

[0049] In some embodiments, the pH of the alkali solution is greater than 13 and the concentration is greater than 1 M; the alkali solution with a pH greater than 13 has strong alkalinity and can effectively remove Si and / or Ge on the surface of RTX particles, improving the hydrogen evolution catalytic activity of the intermetallic electron compound RTX.

[0050] In some embodiments, the alkali solution is selected from at least one of potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution, rubidium hydroxide solution, cesium hydroxide; the alkali solution uses water as a solvent.

[0051] In a preferred embodiment, after adding the alkali solution to the first product, it is treated by any one of standing, ultrasonic treatment, stirring, etc. for 2.5 h - 5 h, so that Si and / or Ge on the surface of the RTX particles can be effectively removed, improving the catalytic efficiency of the surface-engineered activated intermetallic electron compound hydrogen evolution electrocatalyst.

[0052] In some embodiments, in step S10, the intermetallic electron compound RTX is purified by metal melting combined with high-temperature annealing, and then ground to obtain RTX powder; the preparation method of the RTX powder includes the steps:

[0053] Step S11: The elemental particles or blocks of R, T, and X are mixed in proportion and then repeatedly melted, and a block is formed after cooling;

[0054] Step S12: Grind the block into powder and press it into a mixed block under inert gas protection;

[0055] Step S13: Anneal the mixed block (anneal at not less than 1000 degrees Celsius for more than one week) to obtain the purified intermetallic electron compound RTX;

[0056] Step S14: Grind the intermetallic electron compound RTX into powder to obtain RTX powder; wherein, R includes at least one of lanthanide elements; T includes at least one of transition metals such as Ni, Fe, Co, Mo, Mn, Cu, Ru; X includes at least one of Si, Ge.

[0057] In this embodiment, a surface-engineered activated intermetallic hydride hydrogen evolution electrocatalyst is prepared by combining the method of metal melting and high-temperature purification with the surface engineering activation method. Without changing the crystal structure of the intermetallic hydride, the product has a high surface area, an activated surface, excellent performance, simple preparation, and is conducive to large-scale production.

[0058] In some embodiments, the step of grinding the block into powder includes: subjecting the block to ball milling under inert gas protection or manually grinding it in a glove box environment; the step of grinding the intermetallic hydride RTX into powder includes: subjecting the intermetallic hydride RTX to ball milling under inert gas protection or manually grinding it in a glove box environment. Grinding the block and the intermetallic hydride RTX into fine powder by ball milling under inert gas protection or manually grinding in a glove box environment can avoid oxidation and obtain powder without obvious particle feeling.

[0059] Specifically, the elemental particles or bulk materials of R, T, and X are mixed in a metal melting furnace in appropriate proportions and repeatedly melted to form a uniform block; after cooling, the block is taken out and manually ground or ball milled under the protection of an inert gas (such as Ar, He, etc.) in a glove box to form a uniform powder (without obvious particle feeling). Then, the powder is pressed into a block under inert gas protection; the mixed block is wrapped with a clean metal Mo sheet or placed in a small stainless steel crucible, placed in a quartz tube with appropriate length and thickness, evacuated or filled with an inert gas, sealed at both ends, and then annealed in a high-temperature heating device such as a box furnace or a tube furnace at an appropriate annealing temperature for more than one week to obtain a purified intermetallic hydride RTX.

[0060] In some embodiments, the inert gas is selected from at least one of nitrogen, argon, and helium; to ensure that the preparation process of the surface-engineered activated intermetallic hydride hydrogen evolution electrocatalyst is not oxidized and affect the catalytic performance.

[0061] In some embodiments, after the first surface engineering treatment, centrifugation and washing treatments are further included to obtain a first product; after the second surface process treatment, centrifugation, washing, and drying are further included to obtain a surface-engineered activated intermetallic hydride hydrogen evolution electrocatalyst; the reagent used for washing is selected from at least one of deionized water and ethanol; the drying is vacuum drying. Preferably, deionized water and ethanol are used to wash repeatedly to wash away the organic acid and / or organic acid salt and alkali solution to obtain a pure product.

[0062] In some embodiments, after the step S30, storage of the hydrogen evolution electrocatalyst is further included; the hydrogen evolution electrocatalyst is stored in an environment protected by an inert gas, such as a glove box.

[0063] In addition, the present invention also provides a hydrogen evolution electrocatalyst of surface-engineered activated intermetallic electronide, which is prepared by the preparation method of the hydrogen evolution electrocatalyst of surface-engineered activated intermetallic electronide.

[0064] In this embodiment, the catalytic activity measurement requirements of the hydrogen evolution electrocatalyst are as follows: the hydrogen evolution electrocatalyst is configured into an ink with a concentration between 0.1 mg / ml and 10 mg / ml, and then is loaded on the working electrode substrate by means of manual deposition, coating, etc. The working electrode substrate includes but is not limited to one of glassy carbon, nickel foam, copper foam, carbon paper, and carbon cloth. The electrolytes used in the test include but are not limited to solutions such as KOH and NaOH with different concentrations; the counter electrode includes but is not limited to carbon rods, nickel foam, etc.; the reference electrode includes but is not limited to Ag / AgCl reference electrode, saturated calomel electrode, mercury oxide electrode, etc.; the test method generally adopts a three-electrode system or a two-electrode system; the measuring tool generally has a cyclic voltammetry, linear sweep voltammetry, constant current or constant voltage test module.

[0065] Meanwhile, the present invention also provides an application of the surface-engineered activated hydrogen evolution electrocatalyst, and the surface-engineered activated hydrogen evolution electrocatalyst is used for hydrogen production by electrolyzing water.

[0066] The following further gives examples to illustrate the present invention in detail. It should be understood that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the protection scope of the present invention.

[0067] Example 1

[0068] Weigh 2.8 g of metallic cerium lumps, 2.02 g of ruthenium, and 0.56 g of silicon, mix them evenly and put them into a metal melting furnace. Under Ar atmosphere, melt them multiple times until CeRuSi forms a uniform elliptical bulk material. After cooling, take out the bulk material, manually break it and grind it into a uniform powder (without obvious particle feeling) in a glove box environment. Take an appropriate amount of powder and press it into a block with a diameter of about 6 mm and a height of 5 mm in the glove box. The sample after re-pressing is wrapped with a clean metal Mo sheet and placed in a quartz tube with one end sealed and one end open, with a length of 20 cm and a thickness of 1.5 mm. The quartz tube is evacuated, and a high-temperature hydrogen-oxygen flame is used for sealing to ensure vacuum, and then annealed in a box furnace at 1000 °C for 10 days to obtain a purified sample.

[0069] After annealing, the sample was manually ground into a uniform powder (without obvious granularity) in a glove box environment. 500 mg of the obtained sample powder was weighed and placed in a 50 mL plastic centrifuge tube with scale, and then 50 mL of a disodium ethylenediaminetetraacetate solution with a concentration of 1 mol / L was added. After stirring evenly, it was left standing for 3 h. The sample after treatment was centrifuged to obtain the bottom solid, and the product was washed 6 times repeatedly with deionized water and ethanol.

[0070] The washed sample was dried in vacuum ( Figures 1-3 showing the changes in the surface and bulk phase after treatment). An appropriate amount of the above-obtained powder sample was weighed and placed in a 50 mL plastic centrifuge tube with scale, and then 50 mL of a potassium hydroxide solution with a concentration of 1 mol / L was added. Then, after stirring evenly, it was left standing for 3 h. The sample after treatment was centrifuged to obtain the bottom solid, and the product was washed 6 times repeatedly with deionized water and ethanol. The washed sample was dried in vacuum to prepare a hydrogen evolution electrocatalyst, and then it was stored in a glove box.

[0071] Its electrocatalytic hydrogen evolution activity was measured in a 150 ml glass five-necked electrolytic cell. The hydrogen evolution electrocatalyst was configured with an appropriate amount of Nafion, water and ethanol into an ink with a concentration of 5 mg / ml, and 10 μl was dropped on a rotating glassy carbon electrode with a diameter of 5 mm. After drying at room temperature, it became a working electrode. The reference electrode was a calibrated calomel electrode, and the counter electrode was a carbon rod with a diameter of 5 mm and a length of 15 cm. The electrolyte was 1M KOH solution. Combining with a PINE rotating disk electrode device and a Chenhua electrochemical workstation (CH760E) for electrocatalytic hydrogen evolution testing, its performance was as follows Figure 4 shown, the overpotential decreased from 152 mV to 28 mV, greatly reducing the hydrogen evolution energy consumption.

[0072] In summary, the present invention provides an intermetallic electronide hydrogen evolution electrocatalyst activated by surface engineering and a preparation method thereof. The preparation method includes the steps of: grinding the intermetallic electronide RTX into powder to obtain RTX powder; adding an organic acid and / or an organic acid salt to the RTX powder for the first surface engineering treatment, and then obtaining a first product through centrifugation and washing; adding an alkali solution to the first product for the second surface engineering treatment, and then obtaining a hydrogen evolution electrocatalyst through centrifugation, washing and drying. By utilizing the strong chelating ability of the organic acid and / or the organic acid salt for lanthanide metals, the surface lanthanide elements of RTX particles are etched limitedly, and then by using the strong scavenging ability of the alkali solution for Si and Ge, Si and / or Ge on the surface of RTX are scavenged, so that while the intermetallic electronide still maintains the original crystal structure and electronide characteristics, the surface is greatly optimized and the specific surface area is increased by several times to hundreds of times, thereby obtaining a catalyst with ultra-high hydrogen evolution activity.

[0073] It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or modifications can be made according to the above description, and all such improvements and modifications shall fall within the protection scope of the appended claims of the present invention.

Claims

1. A preparation method of a surface engineering activated hydrogen evolution electrocatalyst, characterized in that, Including the steps: Providing RTX powder, wherein R includes at least one of lanthanide elements; T is Ru; X is Si; Adding an organic acid and / or an organic acid salt to the RTX powder for the first surface engineering treatment, such that the organic acid and / or the organic acid salt undergoes a metal chelation reaction with the RTX powder, etching the surface lanthanide elements of the RTX particles to obtain a first product; Adding an alkali solution to the first product for the second surface engineering treatment to remove Si on the surface of the RTX particles, obtaining a surface engineering-activated hydrogen evolution electrocatalyst.

2. The preparation method of the surface engineering activated hydrogen evolution electrocatalyst according to claim 1, wherein, The concentration of the organic acid and / or the organic acid salt is less than 5M.

3. The preparation method of the surface-engineered activated hydrogen evolution electrocatalyst according to claim 1, characterized in that, The organic acid is selected from at least one of acetylacetone, hexafluoroacetylacetone, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid; the organic acid salt is selected from at least one of the salts corresponding to acetylacetone, hexafluoroacetylacetone, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, citric acid, tartaric acid, gluconic acid.

4. The preparation method of the surface-engineered activated hydrogen evolution electrocatalyst according to claim 1, characterized in that, The pH of the alkali solution is greater than 13 and the concentration is greater than 1M.

5. The preparation method of the surface-engineered activated hydrogen evolution electrocatalyst according to claim 4, wherein The alkali solution is selected from at least one of potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution, rubidium hydroxide solution, cesium hydroxide solution.

6. The preparation method of the surface-engineered activated hydrogen evolution electrocatalyst according to claim 1, characterized in that, The preparation method of the RTX powder includes the steps: Mixing R, T, and X elemental particles or blocks in proportion and then performing repeated melting, and forming a block after cooling; Grinding the block into powder and pressing the powder into a mixed block under inert gas protection; Performing annealing treatment on the mixed block to obtain a purified intermetallic electron compound RTX; Grinding the intermetallic electron compound RTX into powder to obtain RTX powder; R includes at least one of lanthanide elements; T is Ru; X is Si.

7. The preparation method of the surface engineering-activated hydrogen evolution electrocatalyst according to claim 6, characterized in that, The step of grinding the block into powder includes: performing ball milling on the block under inert gas protection or performing manual grinding in a glove box environment; The step of grinding the intermetallic electron compound RTX into powder includes: performing ball milling on the intermetallic electron compound RTX under inert gas protection or performing manual grinding in a glove box environment.

8. The preparation method of the surface-engineered activated hydrogen evolution electrocatalyst according to claim 1, characterized in that, After the first surface engineering treatment, centrifugation and washing treatments are further included to obtain a first product; After the second surface process treatment, centrifugation, washing, and drying are further included to obtain a surface engineering-activated intermetallic electron compound hydrogen evolution electrocatalyst; The reagent used for washing is selected from at least one of deionized water and ethanol; the drying is vacuum drying.

9. A surface engineering-activated hydrogen evolution electrocatalyst, characterized in that, Prepared by using the preparation method of the surface engineering-activated hydrogen evolution electrocatalyst according to any one of claims 1-8.

10. Use of a surface-engineered activated hydrogen evolution electrocatalyst as described in claim 9, characterized in that, The surface engineering-activated hydrogen evolution electrocatalyst is used for hydrogen production by electrolyzing water.

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