阅读说明：本技术 一种碱性溶液析氢电催化剂NiVRu三元合金及其制备方法和应用 (Alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy and preparation method and application thereof ) 是由 商爱国 周敏 张秀云 薛玉雄 曾祥华 刘洋 曹荣幸 陈鹏辉 于 2020-12-21 设计创作，主要内容包括：本发明公开了一种碱性溶液析氢电催化剂NiVRu三元合金及其制备方法和应用,所述碱性溶液析氢电催化剂NiVRu三元合金主要成分为Ni,其中V元素的质量百分比含量为1-15％,Ru元素的质量百分比含量为1-15％,Ni元素的质量百分比含量为70-90％。本发明所述制备方法得到的碱性溶液析氢电催化剂NiVRu三元合金作为电极材料,不仅具有较好的碱性析氢性能,而且具有较低的贵金属钌含量,钌含量可以低至1％,同时表现出优良的电化学稳定性,展现了良好的碱性电解水析氢催化性能。本发明的制备方法简单、绿色环保、低成本,适合工业大规模生产。(The invention discloses an alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy and a preparation method and application thereof, wherein the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy mainly comprises Ni, wherein the mass percent of V element is 1-15%, the mass percent of Ru element is 1-15%, and the mass percent of Ni element is 70-90%. The alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy obtained by the preparation method is used as an electrode material, has good alkaline hydrogen evolution performance and low noble metal ruthenium content which can be as low as 1 percent, simultaneously shows excellent electrochemical stability and shows good alkaline electrolysis water hydrogen evolution catalytic performance. The preparation method is simple, environment-friendly, low in cost and suitable for industrial large-scale production.)

1. An alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy is characterized in that: the main component of the NiVRu ternary alloy of the alkaline solution hydrogen evolution electrocatalyst is Ni, wherein the mass percent content of the V element is 1-15%, the mass percent content of the Ru element is 1-15%, and the mass percent content of the Ni element is 70-90%.

2. The alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 1, characterized in that: the surface of the NiVRu ternary alloy contains Ni nano-particles as a substrate, and the V element and the Ru element are attached to the Ni nano-particle substrate to form a porous nano-sheet structure.

3. The alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 2, wherein: the particle size range of the Ni nano-particles is 0.01-10 mu m.

4. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to any one of claims 1 to 3, characterized by comprising the following steps:

1) dissolving water-soluble nickel salt and vanadium chloride in purified water, adding an alkaline solution, and stirring to obtain a green mixed solution;

2) pouring the green mixed solution obtained in the step 1) into a hydrothermal reaction kettle, then placing the hydrothermal reaction kettle into an air-blast drying oven, carrying out hydrothermal treatment, and cooling to obtain a reaction product;

3) centrifuging the reaction product obtained in the step 2), washing with purified water and ethanol, and drying to obtain light yellow powder;

4) dissolving the faint yellow powder obtained in the step 3) in purified water, adding ruthenium chloride, and stirring to obtain a mixed solution;

5) pouring the mixed solution obtained in the step 4) into a hydrothermal reaction kettle, carrying out hydrothermal treatment and cooling;

6) centrifuging the precipitate in the reaction kettle in the step 5), washing with purified water and ethanol, and vacuum-drying to obtain black powder;

7) calcining the black powder obtained in the step 6) by using a high-temperature gas phase reduction method to obtain the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy.

5. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 4, characterized in that: in the step 1), the nickel salt is one of nickel nitrate hexahydrate, nickel chloride and nickel sulfate, and the alkaline solution is one of urea or ammonium fluoride.

6. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 4, characterized in that: in the step 1), the molar ratio of the nickel salt to the vanadium chloride is 20:1-20: 5.

7. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 4, characterized in that: in the step 2), the hydrothermal condition is 90-150 ℃, and the hydrothermal time is 2-10 h. In the step 5), the hydrothermal condition is 90-150 ℃ and the hydrothermal time is 2-10 h.

8. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 4, characterized in that: the calcination temperature in the step 7) is 300-500 ℃, and the calcination time is 1-5 h.

9. The method for preparing the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to claim 4, characterized in that: the gas environment in the high-temperature gas-phase reduction method of the step 7) is inert gas and H₂Mixed gas, wherein the inert gas is Ar or N₂One of (1), H₂The mass fraction is 5-30%.

10. Use of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy according to any one of claims 1 to 3 for the preparation of electrode materials.

Technical Field

The invention relates to a hydrogen evolution electrocatalyst and a preparation method and application thereof, in particular to a NiVRu ternary alloy of an alkaline solution hydrogen evolution electrocatalyst and a preparation method and application thereof.

Background

Because of the excessive dependence on fossil fuel, the increasing problems of energy crisis, environmental pollution and the like, energy conservation and environmental protection are the two most urgent challenges on the 21 st century sustainable development road. Hydrogen is expected to replace fossil fuels and is considered to be the most promising sustainable clean energy source today. The Hydrogen production by electrochemical water cracking is a simple and environment-friendly zero-carbon Hydrogen production process, and has recently attracted attention, and because the large-scale production of Hydrogen in the industry is mostly carried out in an alkaline environment at present, compared with an acidic solution, a Hydrogen Evolution Reaction (HER) in alkaline electrolyzed water shows relatively retarded dynamic characteristics, and becomes a key factor for restricting the improvement of the efficiency of electrolyzed water. Therefore, the development of efficient, stable, cost-effective water-splitting electrocatalysts is one of the most critical challenges.

The hydrogen produced by electrolyzing water is high in purity, pollution-free in production process, simple and convenient to operate and recyclable, and therefore the method is considered to have a wide application prospect. Generally, the electrolysis of water involves two reactions, the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER), the efficiency of which is mainly due to the activity of the catalyst. The performance of the catalyst is closely related to the environment of the solution, and currently, the method mainly uses the electrolyzed water in the alkaline environment, so that firstly, the efficiency of electrolyzing the water under the alkaline condition is higher, and secondly, non-noble metals are more likely to be utilized under the alkaline environment, and the cost of the catalyst is greatly reduced. Meanwhile, hydrogen evolution reaction under alkaline conditions is more difficult to occur than under acidic conditions, so that research on HER under alkaline conditions is more helpful for industrial application. However, the electrolysis of water requires a large supply of energy, according to Faraday's law, under standard conditionsPreparation of 1m³The theoretical amount of hydrogen used was 2.49kWh and the actual amount of hydrogen used was twice the theoretical amount. Therefore, the preparation of hydrogen evolution materials with high catalytic activity to reduce energy consumption is a very worthy subject to be researched. The hydrogen production by water electrolysis is an important means for realizing large-scale hydrogen production, but the existence of hydrogen evolution overpotential increases the tank pressure in the water electrolysis process, so that the energy consumption is increased; therefore, the development of high hydrogen evolution catalytic active electrode materials and the reduction of cathode hydrogen evolution overpotential are the most effective methods for reducing energy consumption.

For alkaline HER, the noble metal platinum (Pt) is widely used on the benchmark, being the most active catalyst for electrolysis of water. However, due to the scarcity and high cost of Pt, Pt is not suitable for large-scale industrial hydrogen production. Therefore, finding a noble metal to replace Pt to prepare a high efficiency catalyst remains a great challenge. Ruthenium (Ru) belongs to a noble metal family related to platinum, but its cost is only 4% of platinum, and it has a platinum-like hydrogen bond strength, and also exhibits excellent performance against dissociation of water and adsorption of OH. In recent years, people adopt a plurality of strategies to prepare high-efficiency ruthenium-based electro-catalysts, including crystal face regulation, heteroatom doping, multi-element alloy, interface defect engineering, electronic structure regulation and the like.

Among the non-noble metals, metallic nickel is the most typical hydrogen evolution electrocatalyst material in alkaline electrolysis water. And the alkaline HER catalytic activity of the nickel-based material can be improved by introducing foreign atoms or other active ingredients to perform electronic regulation or concerted catalysis on nickel. Such as MoNi₄，Pt NWs/SL-Ni(OH)₂,MoS₂-NiS₂And the like show that the heterogeneous structure catalyst can greatly improve the alkaline hydrogen evolution performance. Studies have shown that the enhancement of catalyst performance is closely related to the nature of the foreign atom or active ingredient. Exploring new catalysts may facilitate understanding of the structure or component activity relationships and catalyst performance. Group VB metals, particularly vanadium-based materials (e.g., oxides, vanadates, carbides, etc.), while abundant in earth resources and emerging as water-splitting catalysts, have been rarely studied relative to molybdenum and tungsten-based materials. Recently, Wang et al demonstrated that V can be a potent HER active ingredient. IdentificationHere we expect that the V material could be a new candidate material that synergistically promotes HER catalytic activity of the NiRu alloy. However, how to precisely regulate and control the electronic structure of the nickel-based material to prepare the low-ruthenium and high-efficiency alkaline hydrogen evolution electrocatalyst is still a challenge.

Disclosure of Invention

The purpose of the invention is as follows: the first purpose of the invention is to provide a NiVRu ternary alloy of an alkaline solution hydrogen evolution electrocatalyst.

The second purpose of the invention is to provide a preparation method of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy.

The third purpose of the invention is to provide the application of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy in the preparation of electrode materials.

The technical scheme is as follows: the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy comprises, by mass, 1-15% of a V element, 1-15% of a Ru element and 70-90% of a Ni element.

Further, the surface of the NiVRu ternary alloy contains Ni nanoparticles as a substrate, and the V element and the Ru element are attached to the Ni nanoparticle substrate to form a porous nano flaky structure.

Further, the particle size of the Ni nanoparticles ranges from 0.01 to 10 μm.

The invention relates to a preparation method of an alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy, which comprises the following steps:

1) dissolving water-soluble nickel salt and vanadium chloride in purified water, adding an alkaline solution, and stirring to obtain a green mixed solution;

2) pouring the green mixed solution obtained in the step 1) into a hydrothermal reaction kettle, then placing the hydrothermal reaction kettle into an air-blast drying oven, carrying out hydrothermal treatment, and cooling to obtain a reaction product;

3) centrifuging the reaction product obtained in the step 2), washing with purified water and ethanol, and drying to obtain light yellow powder;

4) dissolving the faint yellow powder obtained in the step 3) in purified water, adding ruthenium chloride, and stirring to obtain a mixed solution;

5) pouring the mixed solution obtained in the step 4) into a hydrothermal reaction kettle, carrying out hydrothermal treatment and cooling;

6) centrifuging the precipitate in the reaction kettle in the step 5), washing with purified water and ethanol, and vacuum-drying to obtain black powder;

7) calcining the black powder obtained in the step 6) by using a high-temperature gas phase reduction method to obtain the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy.

Further, in step 1), the nickel salt is one of nickel nitrate hexahydrate, nickel chloride and nickel sulfate, and the alkaline solution is one of urea or ammonium fluoride.

Further, in the step 1), the molar ratio of the nickel salt to the vanadium chloride is 20:1-20: 5.

Further, in the step 2), the hydrothermal condition is 90-150 ℃, and the hydrothermal time is 2-10 h. In the step 5), the hydrothermal condition is 90-150 ℃ and the hydrothermal time is 2-10 h.

Further, the calcination temperature in the step 7) is 300-.

Further, the gas atmosphere in the high-temperature gas-phase reduction method of the step 7) is inert gas and H₂Mixed gas, wherein the inert gas is Ar or N₂One of (1), H₂The mass fraction is 5-30%.

The invention relates to an application of an alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy in preparation of an electrode material.

Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared by a hydrothermal method and a high-temperature gas-phase reduction method has low noble metal ruthenium content which can be as low as 1%. The alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy is used as an electrode material, and when the current density is 10mA/cm²When the catalyst is used, the overpotential of alkaline hydrogen evolution is as low as 10mV, and the catalyst has more excellent alkaline hydrogen evolution performance and good electrochemical stability than commercial Pt/C, and shows good catalytic performance of alkaline electrolyzed water hydrogen evolution. And bookThe preparation method of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy is simple, short in flow, green, environment-friendly, low in cost and suitable for industrial large-scale production.

Drawings

FIG. 1 is a low-magnification TEM picture of an alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 1;

FIG. 2 is a high-power TEM picture of an alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 1;

FIG. 3 is a low power TEM picture of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 2;

FIG. 4 is a high-power TEM picture of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 2;

FIG. 5 is a low power TEM picture of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 3;

FIG. 6 is a high-power TEM picture of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 3;

FIG. 7 is an XRD picture of the ternary alloy NiVRu of the alkaline solution hydrogen evolution electrocatalyst prepared in example 1-example 3;

FIG. 8 is a graph showing the performance of alkaline hydrogen evolution reaction of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 1-example 3;

FIG. 9 is a graph showing the cycle stability of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy alkaline hydrogen evolution reaction prepared in example 1.

Detailed Description

The technical scheme of the invention is further explained by combining the attached drawings.

Example 1

(1) 2.7mmol nickel nitrate hexahydrate (Ni (NO) was weighed₃)₂·6H₂O), 0.3mmol of vanadium chloride (VCl)₃) Dissolving in 60mL purified water, adding 15mmol urea (CH)₄N₂O), stirred for 15 minutes to prepare a green mixed solution.

(2) Pouring the green mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an air-blowing drying oven, reacting for 4 hours under the hydrothermal condition of 120 ℃, and turning off the air-blowing drying oven to cool the reaction kettle to room temperature;

(3) centrifuging the product obtained in the reaction kettle, washing twice with a purified water solvent, washing twice with an ethanol solvent, and drying in a vacuum drying oven to obtain light yellow powder;

(4) weighing 20mg of the yellow powder obtained in step (3) and dissolving it in 25mL of a purified aqueous solution, 0.5mg of RuCl was added₃Stirring to obtain a mixed solution;

(5) pouring the mixed solution obtained in the step (4) into a hydrothermal reaction kettle, reacting for 4 hours under the hydrothermal condition of 120 ℃, and naturally cooling the reaction kettle to room temperature;

(6) centrifuging the precipitate in the reaction kettle in the step (5), washing twice with a purified water solvent, washing twice with an ethanol solvent, and vacuum-drying to obtain black powder;

(7) putting the black powder obtained in the step (6) into a muffle furnace in a gas environment Ar and H₂The mass percentage of (1) is 95%: in the content of 5 percent, the temperature is raised to 400 ℃ at the heating rate of 10 ℃/min, the calcination is carried out for 2h, and the obtained black powder is the prepared alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy after the tubular furnace is cooled to the room temperature.

The wavelength and intensity of the characteristic X-Ray of the element emitted from the sample in example 1 were analyzed by EDX (Energy Dispersive X-Ray Spectroscopy), and the content of the element in the sample was determined from the intensities of the spectral lines of the different elements. Specific data are shown in table 1 below.

TABLE 1 alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy content of each element

As can be seen from the table, the main component of the NiVRu ternary alloy of the prepared alkaline solution hydrogen evolution electrocatalyst is Ni, wherein the mass percent content of the V element is 15%, the mass percent content of the Ru element is 1%, and the mass percent content of the Ni element is 84%. Wherein the NiVRu ternary alloy is a nano structure consisting of porous nano sheets, and the particle size of Ni nano particles is 0.01-2 μm.

Example 2

(1) Weighing 8mmol of nickel chloride (NiCl)₂) 0.4mmol of vanadium chloride is dissolved in 60mL of purified water, 18mmol of urea is added, and the mixture is stirred for 15 minutes to prepare a green mixed solution.

(2) Pouring the green mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an air-blowing drying oven, reacting for 2 hours under the hydrothermal condition of 150 ℃, and turning off the air-blowing drying oven to cool the reaction kettle to room temperature;

(3) centrifuging the product obtained in the reaction kettle, washing twice with a purified water solvent, washing twice with an ethanol solvent, and drying in a vacuum drying oven to obtain light yellow powder;

(4) 10mg of the yellow powder obtained in step (3) was weighed and dissolved in 50mL of a purified aqueous solution, and 1.0mg of RuCl was added₃Stirring to obtain a mixed solution;

(5) pouring the mixed solution obtained in the step (4) into a hydrothermal reaction kettle, reacting for 10 hours under the hydrothermal condition of 90 ℃, and naturally cooling the reaction kettle to room temperature;

(6) centrifuging the precipitate in the reaction kettle in the step (5), washing twice with a purified water solvent, washing twice with an ethanol solvent, and vacuum-drying to obtain black powder;

(7) putting the black powder obtained in the step (6) into a muffle furnace in a gas environment Ar and H₂The mass percentage is 85%: in 15 percent, the temperature is raised to 300 ℃ at the heating rate of 10 ℃/min, the calcination is carried out for 5 hours, and the obtained black powder is the prepared alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy after the tubular furnace is cooled to the room temperature.

The wavelength and intensity of the element characteristic X-Ray emitted by the sample in example 2 were analyzed by EDX (Energy Dispersive X-Ray Spectroscopy), and the obtained alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy had a main component of Ni, in which the mass percentage content of V element was 1%, the mass percentage content of Ru element was 9%, and the mass percentage content of Ni element was 90%. Wherein the NiVRu ternary alloy is a nano structure consisting of porous nano sheets, and the particle size of Ni nano particles is 0.01-3 μm.

Example 3

(1) Weighing 12mmol of nickel sulfate and 3mmol of vanadium chloride, dissolving in 80mL of purified water, adding 150mmol of urea, and stirring for 15 minutes to obtain a green mixed solution.

(2) Pouring the green mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an air-blowing drying oven, reacting for 10 hours under the hydrothermal condition of 90 ℃, and turning off the air-blowing drying oven to cool the reaction kettle to room temperature;

(3) centrifuging the product obtained in the reaction kettle, washing twice with a purified water solvent, washing twice with an ethanol solvent, and drying in a vacuum drying oven to obtain light yellow powder;

(4) weighing 20mg of the yellow powder obtained in step (3) and dissolving it in 25mL of a purified aqueous solution, 2.0mg of RuCl was added₃Stirring to obtain a mixed solution;

(5) pouring the mixed solution obtained in the step (4) into a hydrothermal reaction kettle, reacting for 2 hours under the hydrothermal condition of 150 ℃, and naturally cooling the reaction kettle to room temperature;

(6) centrifuging the precipitate in the reaction kettle in the step (5), washing twice with a purified water solvent, washing twice with an ethanol solvent, and vacuum-drying to obtain black powder;

(7) putting the black powder obtained in the step (6) into a muffle furnace in a gas environment N₂And H₂The mass percentage is 70%: and in the concentration of 30%, heating to 500 ℃ at a heating rate of 10 ℃/min, calcining for 1h, and cooling the tubular furnace to room temperature to obtain black powder which is the prepared alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy.

The wavelength and intensity of the element characteristic X-Ray emitted by the sample in example 3 were analyzed by EDX (Energy Dispersive X-Ray Spectroscopy), and the obtained alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy had a main component of Ni, in which the mass percentage content of V element was 15%, the mass percentage content of Ru element was 15%, and the mass percentage content of Ni element was 70%. Wherein the NiVRu ternary alloy is a nano structure consisting of porous nano sheets, and the particle size of Ni nano particles is 0.01-10 μm.

A small amount of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in the embodiment 1 to the embodiment 3 is taken and dispersed in alcohol solution, and is dripped on a silicon wafer to be dried, a transmission electron microscope shows a TEM image, and the finer structure of the material can be analyzed and observed from the atomic level of a sample through the TEM image. As shown in fig. 1 to 6, the flower-like porous nanosheet crystal structure of the NiVRu ternary alloy can be seen, and the porous structure can increase the active specific surface area, thereby improving the hydrogen evolution performance. The lattice fringes in fig. 2, 4 and 6 have slight differences because the Ni lattice undergoes different degrees of fine distortion after the nickel base is doped with V and Ru in different contents, but the crystal structure of the Ni-based ternary alloy is not changed.

The diffraction of the basic solution hydrogen evolution electrocatalyst NiVRu ternary alloy surface crystal structure obtained in example 1 to example 3 by X-ray was measured by using X-ray diffractometer model Shimadzu XRD-7000 of the university of yangzhou test center with λ 0.154056nm and scanning speed of 2 °/min. According to the bragg formula: 2d sin θ ═ n λ, the lattice spacing was measured, and the samples were analyzed on a nanometer scale for characteristics such as phase, structure, and crystal plane orientation. As shown in fig. 7, it can be seen that the crystal structure of the sample prepared by us has three distinct peak positions, corresponding to the peak of Ni, and the overall structure of the sample shows a metallic nickel structure, while no other distinct peaks appear, suggesting the existence of the NiVRu ternary alloy.

And (3) testing the performance of the NiVRu ternary alloy of the alkaline solution hydrogen evolution electrocatalyst:

(1) the performance test of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in example 1 to example 3 was completed by a three-electrode test system, which mainly included a working electrode, a reference electrode, and a counter electrode. Wherein the working electrode and the counter electrode form a complete circuit loop, and the reference electrode is used as a reference for measuring and applying the working electrode. The glassy carbon electrode on which the sample material was dropped was used as a working electrode, a silver/silver chloride electrode (Ag/AgCl) as a reference electrode, and a 1.5cm x 1.5cm platinum sheet electrode as a counter electrode. For the present, the experimental studies are carried out under the standard reversible hydrogen electrode voltage (RHE), so the voltage in the test needs to be converted, and the conversion formula is as follows:

E_(vs.RHE)＝E_(vs.Ag/AgCl)+E⁰ _(AgCl)+0.0591*pH

wherein E is⁰ _AgClValue of (3) is 0.197V, pH of 1M KOH is 14, E_(vs.RHE)Voltage to the reversible hydrogen electrode, E_(vs.Ag/AgCl)And represents the voltage of a silver/silver chloride reference electrode, V represents the abbreviation of voltage volt, and pH represents the value of pH value. The specific data are shown in Table 2.

TABLE 2 RHE voltage values for examples 1-3

Name (R)	E(vs.Ag/AgCl)(V)	E(vs.RHE)(V)
			Example 1	-1.0144	0.010
Example 2	-0.9934	0.031
			Example 3	-1.0024	0.022

(2) Sample preparation of working electrode:

weighing 4.8mg of the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy prepared in the example 1, weighing 1.2mg of acetylene black, dissolving the acetylene black in 300L of an alcohol solution with the concentration of 95%, adding 30L of a Nafion solution with the concentration of 5%, mixing to obtain a mixed solution, performing ultrasonic dispersion on the obtained mixed solution for 20min by using a high-power ultrasonic machine, adding 300L of purified water, and continuing to perform ultrasonic dispersion for 20min to obtain a final test sample mixed solution. Example 2 and example 3 samples were prepared as above.

Example 1-example 3 the alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy samples prepared in example 1 have HER performance in alkaline environment:

as shown in fig. 8, it can be found that: the sample prepared in example 1 has the best performance of alkaline hydrogen evolution, and the current density is 10mA/cm²When the catalyst is used, the over-alkaline hydrogen evolution potential is as low as 10mV, which is far lower than that of commercial Pt/C, and the current density of the Pt/C catalyst is 10mA/cm²When the voltage is higher than the predetermined value, the overpotential is 40 mV. The samples prepared in examples 2 and 3 had a current density of 10mA/cm²When the alkaline hydrogen evolution overpotential is higher than the alkaline hydrogen evolution overpotential, the alkaline hydrogen evolution overpotential is 31mV and 22mV respectively.

The alkaline solution hydrogen evolution electrocatalyst NiVRu ternary alloy alkaline hydrogen evolution reaction has the following cycle stability:

as shown in fig. 9, it can be found that: after a constant current stability test for 12 hours, the voltage of the NiVRu ternary alloy of the hydrogen evolution electrocatalyst for the alkaline solution prepared in example 1 is basically unchanged, the Pt/C voltage is obviously changed, and the voltage value is reduced by more than 50mV, which shows that the NiVRu ternary alloy of the hydrogen evolution electrocatalyst for the alkaline solution prepared in example 1 has excellent reaction stability of hydrogen evolution by alkaline electrolysis.