阅读说明：本技术 WP2/Cu3P复合纳米结构催化剂在电解水产氢方面的应用 (WP2/Cu3Application of P composite nano-structure catalyst in aspect of hydrogen production by electrolyzing water ) 是由 王艳 陈衍涛 于 2019-11-14 设计创作，主要内容包括：WP-2/Cu-3P复合纳米结构催化剂在电解水产氢方面的应用,属于纳米材料与电化学催化领域。该复合材料由以下方法制备得到：(1)泡沫铜(Cu)预处理；(2)前驱体合成；(3)磷化实验。本发明我们利用水热合成与高温磷化的方法制备了泡沫铜网上原位生长WP-2纳米线材料作为析氢反应电极材料,并由于磷化深度的影响构成了具有WP-2/Cu-3P复合纳米结构催化剂的三维电极材料。由此,有效催化剂负载增加和电荷输运动力学增强使得该材料的催化活性显著增强,具有优异的电化学析氢性能。(WP 2 /Cu 3 An application of P composite nano-structure catalyst in the aspect of hydrogen production by electrolyzing water belongs to the field of nano materials and electrochemical catalysis. The composite material is prepared by the following method: (1) pretreating foamed copper (Cu); (2) synthesizing a precursor; (3) and (4) carrying out a phosphorization experiment. The invention prepares WP growing in situ on a foamy copper net by using a hydrothermal synthesis and high-temperature phosphorization method 2 The nanowire material is used as a hydrogen evolution reaction electrode material,and has WP due to the influence of the depth of phosphorization 2 /Cu 3 A three-dimensional electrode material of the P composite nano-structure catalyst. Therefore, the catalyst has obviously enhanced catalytic activity due to the increase of effective catalyst load and the enhancement of charge transport kinetics, and has excellent electrochemical hydrogen evolution performance.)

1. WP (total crown of heavy metals)₂/Cu₃The preparation method of the P composite nanostructure hydrogen production catalyst by electrolysis is characterized by comprising the following steps:

(1) copper (Cu) foam pretreatment

The pure copper net is cleaned before use, and the method comprises the following steps: soaking in acetone for 10 minutes and performing ultrasonic treatment for 5 minutes, then washing with deionized water, soaking in 2M/L hydrochloric acid for 30 minutes, washing with deionized water, and finally washing with ethanol for multiple times and storing for later use;

(2) synthesis of precursor

The oxide precursor is synthesized by a hydrothermal method: dissolving a certain amount of metal salt into deionized water, stirring vigorously, adjusting the pH of the solution by using 2M/L hydrochloric acid, adding a certain amount of oxalic acid and ammonium sulfate, adding water, diluting, mixing uniformly, putting into two copper nets (the thickness is 1.6mm), finally putting a polytetrafluoroethylene small bottle filled with the solution and the copper nets into a stainless steel autoclave, carrying out a hydrothermal process in an oven, taking out the two copper nets in the autoclave after the hydrothermal process is finished, repeatedly washing the two copper nets with deionized water and ethanol for multiple times, and putting into a drying box for drying;

(3) phosphating experiment

Taking out the dried two pieces of copper mesh loaded with the oxide precursor, placing the two pieces of copper mesh in a quartz boat, placing the two pieces of copper mesh in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio, placing the two pieces of sodium hypophosphite in the quartz boat, placing the two pieces of sodium hypophosphite in the upper half area of the gas flow direction, and heating for phosphorization.

2. WP according to claim 1₂/Cu₃The preparation method of the P composite nano-structure catalyst for producing hydrogen by electrolyzing water is characterized by comprising the following steps: the substrate of the material in the step (1) is foam copper.

3. WP according to claim 1₂/Cu₃The preparation method of the P composite nano-structure catalyst for producing hydrogen by electrolyzing water is characterized by comprising the following steps: the oxide precursor in the step (2) is one or more of tungsten oxide, molybdenum oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide and manganese oxide.

4. WP according to claim 1₂/Cu₃The preparation method of the P composite nano-structure catalyst for producing hydrogen by electrolyzing water is characterized by comprising the following steps: the molar ratio of the oxide precursor to the sodium hypophosphite in the step (3) is 0-5: 5-0.

5. WP according to claim 1 or 4₂/Cu₃The preparation method of the P composite nano-structure catalyst for producing hydrogen by electrolyzing water is characterized by comprising the following steps: the phosphating temperature in the step (3) is 500-900 ℃, and the duration time is 1-5 h.

Technical Field

The invention relates to the field of electrochemistry, and a novel composite nano-structure catalyst is synthesized by a method of high-temperature phosphorization of sodium hypophosphite and applied to an electrolytic water hydrogen evolution reaction.

Background

In recent years, with the rapid development of modern industries of various countries in the world, the demand of energy is also sharply increased, but since the end of the twentieth century, people face huge energy crisis and increasingly serious environmental pollution problems, so that the conservation of limited energy and the pollution treatment are urgent. In many energy systems, hydrogen is known as a clean and sustainable alternative to fossil fuels. Hydrogen technology, in which hydrogen is used as an energy carrier, is gaining more and more favor and attention due to its advantages such as cleanliness and high energy density, and a hydrogen fuel cell vehicle has been classified as one of the ultimate energy technologies in the 21 st century. The sustainable hydrogen production technology is a necessary prerequisite for the economic development of hydrogen energy in the future, the water electrolysis technology driven by renewable resource electricity is an important way for supporting the sustainable development of hydrogen energy economy, and the development and utilization of the hydrogen evolution catalyst with high activity and low cost are key factors for improving the water electrolysis efficiency and reducing the cost.

The electrolyzed water plays a key role in the sustainable energy development in the future and can be divided into two half-reactions, namely a cathodic Hydrogen Evolution Reaction (HER) and an anodic Oxygen Evolution Reaction (OER). The thermodynamic process of water splitting reaction is difficult and requires higher gibbs free energy, wherein two-electron transfer (HER) and four-electron proton coupling reaction (OER) pathways have larger barrier effect on kinetics, thereby seriously slowing down the electrocatalytic water splitting kinetic process. In order to accelerate the slow evolving reactions of hydrogen and oxygen (HER and OER), electrocatalysts are crucial to reduce their kinetic energy barriers and ultimately to improve the energy efficiency of the electrical conversion to hydrogen.

Non-noble metal phosphides are of great interest because of their excellent electrocatalytic properties and versatility. Among them, a semimetal WP₂Is considered to be a promising catalyst. However, catalytic materials are typically synthesized in one-or two-dimensional structures that tend to randomly aggregate when fabricated into working electrodes. Such disordered agglomerates not only inhibit the diffusion of electrons and electrolyte ions, but also block the active sites, greatly limiting the performance of the catalyst. Therefore, there is a need for a simple strategy to fabricate binderless HER electrodes with active materials directly integrated onto a substrate that not only effectively improves electron conductivity, but also avoids clogging of the active sites.

Disclosure of Invention

The invention is mainly used in the electrolytic water hydrogen evolution reaction, aims to reduce the overpotential of the hydrogen evolution reaction, and is used as a low-cost hydrogen evolution catalyst for replacing noble metals. And the sodium hypophosphite is phosphorized at high temperature, so that the production process is simple, efficient, energy-saving and low in cost.

In order to achieve the purpose of the invention, the following technical scheme is provided:

phosphosphosphorus synthesis of WP from sodium hypophosphite₂/Cu₃The preparation method of P is as follows:

(1) copper (Cu) foam pretreatment

The pure copper net is cleaned before use, and the method comprises the following steps: the mixture was soaked in acetone for 10 minutes and sonicated for 5 minutes, then rinsed clean with deionized water, then soaked in 2M/L hydrochloric acid for 30 minutes, and rinsed with deionized water. Finally, washing with ethanol for multiple times and storing for later use.

(2) Synthesis of precursor

The oxide precursor is synthesized by a hydrothermal method. Dissolving a certain amount of metal salt into deionized water, stirring vigorously, adjusting the pH of the solution with 2M/L hydrochloric acid, adding a certain amount of oxalic acid and ammonium sulfate, adding water, diluting, mixing uniformly, and placing into two copper nets (the thickness is 1.6 mm). Finally, the polytetrafluoroethylene vial containing the solution and the copper mesh is placed into a stainless steel autoclave and subjected to hydrothermal process in an oven. And after the hydrothermal process is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box for drying.

(3) Experiment of phosphating

Taking out the dried two pieces of copper mesh loaded with the oxide precursor, placing the two pieces of copper mesh in a quartz boat, placing the two pieces of copper mesh in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio, placing the two pieces of sodium hypophosphite in the quartz boat, and placing the two pieces of sodium hypophosphite in the upper half area of the gas flow direction. And (4) heating for phosphorization.

WP, in contrast to other hydrogen evolution catalysts₂/Cu₃The P composite nano material has the following advantages:

the adhesion behavior of the hydrogen bubbles can be adjusted by constructing a special nano structure for the catalyst, so that the low adhesion is achieved, the release of the hydrogen bubbles is effectively promoted, and the active surface area of the electrode is increased. Thus, mutually coordinated loads are designedThe three-dimensional electrode material with the special nano-structure catalyst is the key for improving the excellent performance of HER. WP₂/Cu₃The P composite nanomaterial is a nanowire-based catalyst directly grown on a conductive substrate, which has gained wide attention as an HER electrode and well embodies the advantages described above.

The invention prepares WP growing in situ on a foamy copper net by using a hydrothermal synthesis and high-temperature phosphorization method₂The nanowire material is used as a hydrogen evolution reaction electrode material, and Cu is formed due to the influence of the depth of phosphorization₃P/WP₂A three-dimensional electrode material. Thus, the increased effective catalyst loading and enhanced charge transport kinetics result in a significant enhancement of the catalytic activity of the material. This result is Cu₃P/WP₂As an electrode material with great application prospect, a new way is opened up for the design and manufacture of other high-efficiency electrodes.

Drawings

FIG. 1 is a scanning electron micrograph of a cuprous phosphide catalyst material synthesized in example 1 of the present invention;

FIG. 2 is a scanning electron micrograph of a tungsten oxide precursor catalyst material synthesized in example 2 of the present invention;

FIG. 3 is WP synthesized in example 7 of the invention₂/Cu₃Scanning electron microscope photograph of P catalyst material;

FIG. 4 is WP synthesized in example 7 of the invention₂/Cu₃An X-ray diffraction pattern of the P catalyst material;

FIG. 5 is WP synthesized in example 7 of the invention₂/Cu₃The polarization curve of the P catalyst material is compared with that of metal platinum;

FIG. 6 shows WP synthesized in example 7 of the present invention₂/Cu₃The tafel slope of the P catalyst material is compared to that of platinum metal.

Detailed Description

The following provides a detailed description of specific embodiments of the present invention.

Example 1

Cutting commercially available pure copper mesh into multiple strips of 1cm × 2cmThen soaking the mixture in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the mixture by using deionized water, then soaking the mixture in 2M/L hydrochloric acid for 30 minutes, then respectively washing the mixture by using deionized water and ethanol for 3 times, and then naturally airing the mixture for later use. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursors, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (0: 1) of the precursors to the sodium hypophosphite, placing the sodium hypophosphite in the quartz boat in the upper half area of the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. The obtained product is Cu with rough surface₃A P nanostructured catalyst.

Example 2

Cutting a pure copper net purchased in the market into a plurality of strips with the size of 1cm multiplied by 2cm, soaking the strips in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the strips clean by deionized water, then soaking the strips in 2M/L hydrochloric acid for 30 minutes, respectively washing the strips for 3 times by using the deionized water and ethanol, and then naturally airing the strips for later use. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two copper net devices loaded with tungsten oxide precursorsPlacing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (1: 0) of the precursor to the sodium hypophosphite, placing the sodium hypophosphite in the upper half area of the quartz boat in the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining product in the form of strands₃A nanostructured catalyst.

Example 3

Cutting a pure copper net purchased in the market into a plurality of strips with the size of 1cm multiplied by 2cm, soaking the strips in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the strips clean by deionized water, then soaking the strips in 2M/L hydrochloric acid for 30 minutes, respectively washing the strips for 3 times by using the deionized water and ethanol, and then naturally airing the strips for later use. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursors, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (1: 1) of the precursors to the sodium hypophosphite, placing the sodium hypophosphite in the quartz boat in the upper half area of the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining the product as WP₂With a small amount of Cu₃P-composite and bulk pure copper substrates.

Example 4

Cutting commercially available pure copper mesh into strips of 1cm × 2cm, soaking in acetone for 10 min and ultrasonic treating for 5 min, washing with deionized water, soaking in 2M/L hydrochloric acid for 30 min, and removingWashing with ionized water and ethanol for 3 times, and air drying. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursors, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (1: 2) of the precursors to the sodium hypophosphite, placing the sodium hypophosphite in the quartz boat in the upper half area of the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining the product as WP₂With a portion of Cu₃P-composite and pure copper substrates.

Example 5

Cutting a pure copper net purchased in the market into a plurality of strips with the size of 1cm multiplied by 2cm, soaking the strips in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the strips clean by deionized water, then soaking the strips in 2M/L hydrochloric acid for 30 minutes, respectively washing the strips for 3 times by using the deionized water and ethanol, and then naturally airing the strips for later use. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursor, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, and weighing the two pieces of copper mesh according to the molar ratio (1: 3) of the precursor to the sodium hypophosphiteSuitable sodium hypophosphite was placed in a quartz boat in the upper half of the gas flow. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining the product as WP₂With a majority of Cu₃P-composite and pure copper substrates.

Example 6

Cutting a pure copper net purchased in the market into a plurality of strips with the size of 1cm multiplied by 2cm, soaking the strips in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the strips clean by deionized water, then soaking the strips in 2M/L hydrochloric acid for 30 minutes, respectively washing the strips for 3 times by using the deionized water and ethanol, and then naturally airing the strips for later use. 0.4125g of sodium tungstate was dissolved in 10mL of deionized water and vigorously stirred for 20 minutes, and then the pH of the solution was adjusted to 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and uniformly mixed, followed by placing the mixture in two copper mesh sheets (thickness: 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursors, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (1: 4) of the precursors to the sodium hypophosphite, placing the sodium hypophosphite in the quartz boat in the upper half area of the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining the product as WP₂With a large amount of Cu₃P composite and a small amount of pure copper substrate.

Example 7

Cutting a pure copper net purchased in the market into a plurality of strips with the size of 1cm multiplied by 2cm, soaking the strips in acetone for 10 minutes and carrying out ultrasonic treatment for 5 minutes, then washing the strips clean by deionized water, then soaking the strips in 2M/L hydrochloric acid for 30 minutes, respectively washing the strips for 3 times by using the deionized water and ethanol, and then naturally airing the strips for later use. 0.4125g of sodium tungstate was dissolvedAfter stirring vigorously for 20 minutes in 10mL of deionized water, the solution was adjusted to pH 1.2 with 2M/L hydrochloric acid, 0.315g of oxalic acid and 0.2g of ammonium sulfate were added, and 25mL of water was added and mixed well, followed by placing two copper mesh sheets (thickness 1.6 mm). The teflon vial containing the solution and copper mesh was placed in a stainless steel autoclave and subjected to a hydrothermal process in an oven, heating to 160 ℃ for 15 hours. After the hydrothermal reaction is finished, taking out the two copper nets in the kettle, repeatedly washing the two copper nets with deionized water and ethanol for many times, and then putting the two copper nets into a drying box to dry for 6 hours at the temperature of 60 ℃. Taking out the dried two pieces of copper mesh loaded with tungsten oxide precursors, placing the two pieces of copper mesh in a quartz boat, placing the quartz boat in the lower half area of the gas flow direction of the vacuum tube furnace, weighing appropriate sodium hypophosphite according to the molar ratio (1: 5) of the precursors to the sodium hypophosphite, placing the sodium hypophosphite in the quartz boat in the upper half area of the gas flow direction. The temperature was raised to 700 ℃ at a rate of 5 ℃/min for 2 hours, then lowered to 250 ℃ at the same rate for 3 hours, and then naturally cooled to room temperature. Finally, argon gas was passed through for 30 minutes. Obtaining the product as WP₂And Cu₃P composite materials, i.e. WP₂/Cu₃P composite nanostructured catalyst material.

The performance test process of the synthesized nanostructured catalyst for the Hydrogen Evolution Reaction (HER) by electrolysis and water separation is as follows:

for 1cm²The metal platinum sheet (Pt foil) is washed with deionized water and ethanol three times respectively, then dried in the air, and then an electrochemical workstation is used for carrying out the test of the hydrogen evolution performance of the electrolytic water.

Linear Sweep Voltammetry (LSV) was measured at CHI760E (Shanghai Chenghua apparatus) electrochemical workstation, where the sweep rate of the LSV was 5mv/s and the losses were compensated by IR correction. This was a test conducted in a conventional three-electrode system with the counter electrode being a carbon rod, the reference electrode being a Hg/HgO electrode, the catalyst materials synthesized in examples 1, 2 and 7 being the working electrode, and the electrolyte being a 1M/L KOH solution. The test was performed under saturated argon. The results of the hydrogen evolution performance test are shown in table 1 below.

TABLE 1 electrochemical hydrogen evolution Performance

	-10mA/cm2	-20mA/cm2	-50mA/cm2	Tafel slope
					Example 1	237mv	272mv	327mv	108mv/dec
Example 2	326mv	384mv	433mv	235mv/dec
					Example 7	162mv	185mv	212mv	62.5mv/dec

FIG. 5 shows WP synthesized in example 7 of the present invention₂/Cu₃Comparison of polarization curves for electrochemical hydrogen evolution Performance of P composite nanostructured catalysts with noble metal platinum flakes (Pt foil), where the composite catalyst has a current density of 50mA/cm²Time overpotential212mv is lower than the overpotential of 250mv of platinum sheet. And it can be seen from the figure that the current density is greater than 50mA/cm²Rear WP₂/Cu₃The electrochemical hydrogen evolution performance of the P composite nano-structured catalyst is far better than that of noble metal platinum.

FIG. 6 shows synthesized WP₂/Cu₃The comparison between the Tafel slope of the electrochemical hydrogen evolution performance of the P composite nano-structured catalyst and a noble metal platinum sheet (Pt foil) shows that the Tafel slope of the metal platinum is 54.6mv/dec, the Tafel slope of the composite material is 62.5mv/dec, the difference between the two values is small, and the dynamic process is similar. It can be seen from this that WP₂/Cu₃The P composite nano-structured catalyst can completely replace a noble metal platinum catalyst which is expensive and not easy to obtain to be applied to hydrogen production by water electrolysis.

The above description is only an example of the present invention, and is not limited thereto. Any simple changes, equivalent substitutions or modifications made based on the present invention to solve substantially the same technical problems or achieve substantially the same technical effects are within the scope of the present invention.