Tungsten and zinc co-doped Ni2P / Co2P composite material and preparation method and application thereof

Abstract

The invention discloses a tungsten and zinc co-doped Ni2P / Co2P composite material and a preparation method and application thereof.The preparation method comprises the steps that firstly, Zn-doped NiCo-LDH is obtained through a hydrothermal method, then W doping is conducted through an ion exchange method to obtain W and Zn co-doped NiCo-LDH, and finally, W / Zn-NiCo-LDH is phosphatized through a calcination method to obtain the tungsten and zinc co-doped Ni2P / Co2P composite material. The tungsten-zinc co-doped Ni2P / Co2P composite material has good HER and HzOR catalytic activity and stability under the industrial-grade current density, and has excellent hydrazine oxidation assisted water electrolysis hydrogen production performance. In addition, the adopted raw materials are wide in source and easy to obtain, the preparation process is simple, and large-scale industrial production and application are facilitated.

Description

TECHNICAL FIELD

[0001] The application relates to an electrode catalytic material for hydrogen production by electrolysis of water, in particular to a tungsten-zinc co-doped Ni2P / Co2P composite material and a preparation method and application thereof, and belongs to the technical field of hydrogen production by electrolysis of water. BACKGROUND

[0002] In recent years, due to the increasingly severe energy crisis and environmental pollution problems caused by the large use of fossil fuels, clean, economic and sustainable energy has gradually become a research hotspot. At the same time, the proposal of the strategic goal of "carbon peak" and "carbon neutralization" in China also puts forward higher requirements for current energy and environmental problems, promotes in-depth exploration of clean, economic and renewable new energy, and becomes an important research direction in the field of new energy. Among them, the oxygen evolution reaction (OER) is a complex process involving four-electron transfer, the reaction kinetics is slow, the theoretical potential is high (1.23 V vs. RHE), and there is a large overpotential and high hydrogen production cost. In addition, the oxygen generated by OER may form an explosive mixture with the hydrogen produced by HER, which has a safety hazard in practical application. The above problems seriously restrict the large-scale commercial application of hydrogen production technology by electrolysis of water. In order to solve the above problems, researchers have proposed to replace the slow kinetics of oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR), which has an ultra-low theoretical oxidation potential (-0.33 V vs. RHE) and fast electro-oxidation kinetics. In addition, HzOR does not produce any greenhouse gases during the reaction process, only generates nitrogen and water, and has significant environmental advantages.

[0003] However, in the prior art, after combining the hydrazine oxidation reaction and the hydrogen evolution reaction, the electrode catalytic material not only needs to consider its catalytic effect on HER but also needs to consider the catalytic effect of HzOR, so the electrode catalytic material generally depends on the use of Pt, Pd, Rh and other noble metals as raw materials to prepare, which has extremely high economic cost and is difficult to be applied in large-scale industrialization, which seriously restricts the development of hydrazine oxidation and hydrogen evolution reaction combined electrolysis of water hydrogen production technology. SUMMARY

[0004] In view of the problem that existing noble metal catalytic materials are not conducive to the development of hydrogen production by water electrolysis through hydrazine oxidation synergistic catalysis due to poor economy, the present application provides a tungsten-zinc co-doped Ni2P / Co2P composite material, a preparation method and use thereof. Non-noble metals such as nickel, cobalt, zinc and tungsten are used as raw materials, and the tungsten-zinc co-doped Ni2P / Co2P composite material is obtained through a low-cost process of hydrothermal method, ion exchange method and phosphorization in sequence. The local coordination environment of Ni and Co is adjusted by the synergistic doping of tungsten and zinc, the electron transfer between the Ni2P and Co2P heterostructures is promoted, which is conducive to the formation of an internal electric field in the composite material. The double-metal doping can not only enhance the binding ability between metal atoms and the carrier, but also adjust the electronic state between different metal atoms, thereby improving the catalytic performance. The composite material can exhibit excellent HER and HzOR catalytic performance under alkaline conditions.

[0005] To achieve the above technical purposes, the technical solutions adopted by the present application are as follows:

[0006] According to a first embodiment of the present application, a tungsten-zinc co-doped Ni2P / Co2P composite material is provided.

[0007] The tungsten-zinc co-doped Ni2P / Co2P composite material comprises a substrate and nickel phosphide and cobalt phosphide loaded on the substrate, and the nickel phosphide and the cobalt phosphide are doped with elemental zinc and elemental tungsten.

[0008] As a preferred, in the composite material, the molar ratio of the nickel phosphide to the cobalt phosphide is 1:0.5-1.5, preferably 1:0.7-1.2. Preferably, the total loading amount of the nickel phosphide and the cobalt phosphide is not more than 20% of the total mass of the substrate, preferably 5-15% of the total mass of the substrate, more preferably 8-12% of the total mass of the substrate, and further preferably 9-11% of the total mass of the substrate.

[0009] As a preferred, in the composite material, the molar ratio of the zinc element to the nickel phosphide is 0.01-0.2:1, preferably 0.03-0.15:1, and more preferably 0.05-0.1:1. The molar ratio of the zinc element to the tungsten element is 1:0.8-1.2, preferably 1:0.9-1.1.

[0010] As a preferred, the substrate is one or more of foamed nickel, foamed copper, carbon material (such as carbon cloth, carbon felt, carbon rod, graphene, carbon cloth, carbon paper, etc.), and preferably foamed nickel.

[0011] According to a second embodiment of the present application, a method for preparing a tungsten-zinc co-doped Ni2P / Co2P composite material is provided.

[0012] A method for preparing a tungsten-zinc co-doped Ni2P / Co2P composite material or a method for preparing the tungsten-zinc co-doped Ni2P / Co2P composite material as described in the first embodiment, the method comprising the following steps:

[0013] 1) A mixed solution is obtained by dissolving a nickel source, a cobalt source, a zinc source and a regulator. Then, a substrate is placed in the mixed solution for hydrothermal reaction. After the reaction is completed, the solid product is taken out and subjected to cleaning and drying treatment to obtain a Zn-NiCo-LDH material.

[0014] 2) A tungsten-containing solution is obtained by dissolving a tungsten source. Then, the Zn-NiCo-LDH material is placed in the tungsten-containing solution for water bath reaction. After the reaction is completed, the solid product is taken out and subjected to cleaning and drying treatment to obtain a W / Zn-NiCo-LDH material.

[0015] 3) The W / Zn-NiCo-LDH material is subjected to phosphating reaction with a phosphating agent to obtain the tungsten-zinc co-doped Ni2P / Co2P composite material.

[0016] Preferably, in step 1), the nickel source is a soluble nickel salt, preferably one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, and nickel carbonate.

[0017] Preferably, in step 1), the cobalt source is a soluble cobalt salt, preferably one or more of cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, and cobalt carbonate.

[0018] Preferably, in step 1), the zinc source is a soluble zinc salt, preferably one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, and zinc carbonate.

[0019] Preferably, in step 1), the regulator is one or more of urea, hexamethylenetetramine, ammonium carbonate, and cetyltrimethylammonium bromide, preferably urea.

[0020] Preferably, in step 1), the substrate is one or more of nickel foam, copper foam, and carbon material, preferably nickel foam.

[0021] Preferably, in step 1), the molar ratio of the nickel source, the cobalt source, the zinc source, and urea is 1:0.5-1.5:0.01-0.2:1.5-4, preferably 1:0.7-1.2:0.03-0.15:2-3.5, and more preferably 1:0.9-1.1:0.05-0.1:2.2-3.

[0022] Preferably, in step 2), the tungsten source is a soluble tungsten salt or a tungsten-containing acid, preferably one or more of sodium tungstate, potassium tungstate, ammonium tungstate, sodium metatungstate, ammonium metatungstate, phosphotungstic acid, and tungstic acid.

[0023] As preferred, in step 2), the molar amount of the tungsten source is 0.8-1.2 times, preferably 0.9-1.1 times, the molar amount of the zinc source.

[0024] As preferred, in step 3), the phosphating agent is a soluble phosphorus salt, preferably one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, sodium phosphite, potassium phosphite, and ammonium phosphite.

[0025] As preferred, in step 3), the molar amount of the phosphating agent is 0.5-2 times, preferably 0.7-1.5 times, the total molar amount of the nickel source and the cobalt source.

[0026] As preferred, step 1) specifically comprises: weighing the nickel source, the cobalt source, the zinc source, and the urea in proportion, and then dissolving them in a solvent (e.g., deionized water and / or ethanol) to obtain a mixed solution. The mixed solution is placed in a reactor (e.g., a reaction kettle), and then the cleaned substrate is immersed in the mixed solution, followed by hydrothermal reaction at 80-150°C for 4-24h. After the reaction is completed, the solid product is taken out and washed with deionized water for multiple times (e.g., 3-10 times), and finally the cleaned solid product is placed in a drying box (preferably a vacuum drying box) for drying treatment at 50-80°C for 6-24h to obtain the Zn-NiCo-LDH material.

[0027] As preferred, step 2) specifically comprises: dissolving the tungsten source in a solvent (e.g., deionized water and / or ethanol) to obtain a tungsten-containing solution. Then the Zn-NiCo-LDH material is immersed in the tungsten-containing solution and placed in a water bath, and after the tungsten-containing solution is heated to 30-100°C by heating the water bath, the water bath reaction is carried out for 0.1-5h. After the reaction is completed, the solid product is taken out and washed with deionized water for multiple times (e.g., 3-10 times), and finally the cleaned solid product is placed in a drying box (preferably a vacuum drying box) for drying treatment at 50-80°C for 6-24h to obtain the W / Zn-NiCo-LDH material.

[0028] As preferred, step 3) specifically comprises: placing the phosphating agent and the W / Zn-NiCo-LDH material in the upstream and downstream of a phosphating reactor (e.g., a tube furnace) respectively, then replacing the air in the phosphating reactor with nitrogen or inert gas, and finally heating (e.g., at a heating rate of 1-10°C / min) to 200-500°C in the atmosphere of nitrogen or inert gas for phosphating reaction for 0.5-5h. After the reaction is completed, the tungsten-zinc co-doped Ni2P / Co2P composite material is obtained.

[0029] According to a third embodiment of the present application, there is provided a use of a tungsten-zinc co-doped Ni2P / Co2P composite material:

[0030] Use of a tungsten-zinc co-doped Ni2P / Co2P composite material or a tungsten-zinc co-doped Ni2P / Co2P composite material prepared by the method according to the first embodiment or the second embodiment, for electrolysis of water to produce hydrogen, preferably for hydrazine-oxidation-assisted electrolysis of water to produce hydrogen.

[0031] In the present application, the nickel salt, the cobalt salt, the zinc salt, the tungsten salt, the phosphorus salt, etc. as the nickel source, the cobalt source, the zinc source, the tungsten source, the phosphorizing agent, etc. not only include their anhydrous salts, but also include their hydrous salts. For example, when the phosphorus salt is sodium hypophosphite, not only anhydrous sodium hypophosphite is included, but also sodium hypophosphite monohydrate, etc. are included. When the nickel salt is nickel nitrate, not only anhydrous nickel nitrate is included, but also nickel nitrate hexahydrate, etc. are included.

[0032] In the present application, the "solubility" of the soluble nickel salt, the soluble cobalt salt, the soluble zinc salt, etc. not only refers to the common water solubility, but also includes acid solubility, alkali solubility, oil solubility (refers to solubility in organic solvents such as alcohol, alkane, glycerol, etc.) and also includes solubility in any mixed solvent of water, acid, alkali, oil, etc.

[0033] In the present application, when the nickel source, the cobalt source, the zinc source, the adjusting agent (for adjusting pH and promoting the formation of morphology in the hydrothermal process) are dissolved in the solvent (preferably deionized water) to obtain a mixed solution, the amount of the solvent is generally such that the concentration of the nickel salt in the mixed solution is 1-500 g / L, the concentration of the cobalt salt is 1-100 g / L, the concentration of the zinc salt is 1-100 g / L, and the concentration of urea is 1-100 g / L. When the tungsten salt is dissolved in the solvent (preferably a mixed solvent of deionized water and ethanol, the mixed volume ratio of deionized water and anhydrous ethanol is 0.01-100:1) to obtain a tungsten-containing solution, the amount of the mixed solvent is generally such that the concentration of the tungsten salt in the tungsten-containing solution is 1-500 g / L.

[0034] In the present application, in order to realize the excellent catalytic activity and stability of the non-noble metal bifunctional catalyst in hydrogen evolution reaction and hydrazine oxidation reaction, a small amount of foreign atoms is introduced into the crystal lattice of the main material through multi-atom doping, so as to realize the regulation of the electronic structure of the material and the enhancement of the surface growth kinetics of the material, that is, through the synergistic effect of different atoms, more abundant electronic structure and more diversified active sites are provided, so that the catalytic performance is greatly improved. In the present application, nickel and cobalt are used as main materials, and tungsten and zinc are used as doping atoms. The synergistic doping of tungsten and zinc adjusts the local coordination environment of nickel and cobalt, promotes the electron transfer between Ni2P and Co2P heterostructure, and is beneficial to the formation of internal electric field of the catalyst, so that the tungsten-zinc co-doped Ni2P / Co2P composite material (i.e. W / Zn-Ni2P / Co2P) exhibits excellent HER and HzOR catalytic performance under alkaline conditions. Further, the design of Ni2P and Co2P heterojunction can integrate the catalytic activity of single component, so as to realize strong coupling between different components and interfaces, and improve the electronic conductivity of the catalyst and its stability in the catalytic process.

[0035] In the present application, a plurality of specific non-noble metal materials are coupled through interfaces to form a heterostructure composite catalyst. The catalyst optimizes the adsorption energy of reaction intermediates by regulating the electronic structure at the interface, thereby improving the catalytic performance. At the same time, a plurality of different materials also provide a plurality of reaction active sites, which are beneficial to realize good HER and HzOR bifunctional catalytic performance. In addition, the synergistic doping of W and Zn not only can enhance the binding ability between the catalyst and the substrate (preferably foam nickel), so that the stability of the catalyst is significantly improved, but also can regulate the growth kinetics of the crystal, so that more nanostructures grow on the surface of the catalyst, thereby providing sufficient reaction active sites for the catalytic reaction. At the same time, the doping of the two metals promotes the formation of internal electric field of the heterostructure, accelerates the electron transfer, and helps to greatly improve the catalytic performance.

[0036] In the present application, the substrate generally needs to be cleaned before use to remove the stains on the surface. Then, the Zn-doped NiCo-LDH is obtained by sequentially carrying out precipitation reaction on the substrate (preferably foam nickel) by hydrothermal method, and the W-doped Zn-NiCo-LDH is obtained by further carrying out water bath method on the Zn-NiCo-LDH, and finally the W / Zn-Ni2P / Co2P bifunctional composite electrocatalytic material is obtained by carrying out phosphating treatment on the W / Zn-NiCo-LDH by calcination method. Compared with the undoped catalyst, the formation of internal electric field of the catalyst causes charge transfer, the electronic structure is regulated, and the catalytic performance of HER and HzOR is improved. The W and Zn co-doped Ni2P / Co2P electrode material prepared in the present application has good HER and HzOR catalytic activity and stability under industrial current density, and has excellent hydrazine oxidation assisted water electrolysis hydrogen production performance.

[0037] Compared with the prior art, the beneficial technical effects of the present application are as follows:

[0038] 1: The present application innovatively combines W and Zn double-doped Ni2P / Co2P heterojunction to prepare a brand-new tungsten-zinc double-metal co-doped Ni2P / Co2P composite material.

[0039] 2: The present application can not only enhance the binding ability between the catalyst and the nickel foam through the synergistic doping of W and Zn, but also make the catalyst surface grow more nanostructures, thereby providing more reaction active sites. In addition, the double-metal doping further promotes the internal electric field of the heterostructure to accelerate electron transfer and improve the catalytic performance.

[0040] 3: The tungsten-zinc co-doped Ni2P / Co2P electrode material prepared by the present application has good HER and HzOR catalytic activity and stability under industrial-grade current density, and has excellent hydrazine oxidation assisted electrolytic water hydrogen production performance.

[0041] 4: The various raw materials used in the present application are inexpensive and easy to obtain, the synthesis process is simple and controllable, and the economic efficiency is excellent, and has the potential for large-scale industrial production and application. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 SEM image of the W / Zn-Ni2P / Co2P composite material prepared in Example 1 of the present application.

[0043] Figure 2 XRD image of the W / Zn-Ni2P / Co2P composite material prepared in Example 1 of the present application.

[0044] Figure 3 X-ray photoelectron spectroscopy (XPS) of the four composite materials prepared in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 of the present application.

[0045] Figure 4 LSV spectrum of HzOR of the W / Zn-Ni2P / Co2P catalyst prepared in Example 1 of the present application in a 0.5 mol·L -1 hydrazine hydrate and 1.0 mol·L -1 potassium hydroxide mixed solution.

[0046] Figure 5 LSV spectrum of HER of the W / Zn-Ni2P / Co2P catalyst prepared in Example 1 of the present application in 1.0 mol·L -1 potassium hydroxide.

[0047] Figure 6Figure of performance test of two-electrode full electrolysis water of W / Zn-Ni2P / Co2P catalyst prepared for Example 1 of the present application, which is used as cathode and anode at the same time.

[0048] Figure 7 W / Zn-Ni2P / Co2P prepared for Example 1 of the present application in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 Hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 Potassium hydroxide solution by means of potential-time curve (E~t) in three-electrode system.

[0049] Figure 8 W / Zn-Ni2P / Co2P catalyst prepared for Example 1 of the present application in 1.0 mol·L-1 potassium hydroxide solution by means of potential-time curve (E~t) in three-electrode system. -1 Potassium hydroxide solution by means of potential-time curve (E~t) in three-electrode system.

[0050] Figure 9 Zn-Ni2P / Co2P catalyst prepared for Comparative Example 1 of the present application in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 Hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 LSV spectrum of HzOR in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution.

[0051] Figure 10 Zn-Ni2P / Co2P catalyst prepared for Comparative Example 1 of the present application in 1.0 mol·L-1 potassium hydroxide solution. -1 LSV spectrum of HER in 1.0 mol·L-1 potassium hydroxide solution.

[0052] Figure 11 Ni2P / Co2P catalyst prepared for Comparative Example 2 of the present application in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 Hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 LSV spectrum of HzOR in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution.

[0053] Figure 12 Ni2P / Co2P catalyst prepared for Comparative Example 2 of the present application in 1.0 mol·L-1 potassium hydroxide solution. -1 LSV spectrum of HER in 1.0 mol·L-1 potassium hydroxide solution.

[0054] Figure 13 W-Ni2P / Co2P catalyst prepared for Comparative Example 3 of the present application in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 Hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution. -1 LSV spectrum of HzOR in 0.5 mol·L-1 hydrazine hydrate and 1.0 mol·L-1 potassium hydroxide mixed solution.

[0055] Figure 14 W-Ni2P / Co2P catalyst prepared for Comparative Example 3 of the present application in 1.0 mol·L-1 potassium hydroxide solution. -1LSV profile of HER in potassium hydroxide solution. DETAILED DESCRIPTION

[0056] The technical solutions of the present application are illustrated below, and the scope of protection requested by the present application includes but is not limited to the following examples.

[0057] Example 1

[0058] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and clean foamed nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6 hours to obtain the precursor Zn-NiCo-OH.

[0059] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then a water bath was used to heat the tungsten salt solution to 85 ℃ for 15 min. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6 hours to obtain the precursor W / Zn-NiCo-OH.

[0060] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed upstream and downstream of a tube furnace respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in an N2 environment, and then heated to 350 ℃ at a heating rate of 5 ℃ / min and kept for 2 hours. The solid product taken out from the downstream of the tube furnace was W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.064:1, and the molar ratio of Zn to W is about 1:1).

[0061] Example 2

[0062] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 25.2 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-NiCo-OH.

[0063] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 °C for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Zn-NiCo-OH.

[0064] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed upstream and downstream of a tube furnace, respectively. After replacing the air in the tube furnace with N2, the tube furnace was maintained in an N2 environment, and then heated to 350 °C at a heating rate of 5 °C / min and kept for 2 hours. The solid product taken from the downstream of the tube furnace was W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.04% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:0.7, the molar ratio of Zn to Ni2P is about 0.064:1, and the molar ratio of Zn to W is about 1:1).

[0065] Example 3

[0066] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 25.2 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-NiCo-OH.

[0067] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution, and then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution. Subsequently, the tungsten salt solution was heated to 85 °C using a water bath for 15 min. After the reaction was completed, the solid product was washed with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Zn-NiCo-OH.

[0068] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed upstream and downstream of a tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was heated to 350 °C at a heating rate of 5 °C / min and then held for 2 h. The solid product downstream of the tube furnace was removed to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.00% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:0.5, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to W is about 1:1).

[0069] Example 4

[0070] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 14.4 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O, and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then, the mixed solution and cleaned nickel foam (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 h. After the reaction was completed, the solid product was washed with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-NiCo-OH.

[0071] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution, and then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution. Subsequently, the tungsten salt solution was heated to 85 °C using a water bath for 15 min. After the reaction was completed, the solid product was washed with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Zn-NiCo-OH.

[0072] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively, and after the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 9.99% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:0.4, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to W is about 1:1).

[0073] Example 5

[0074] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 43.2 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0075] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution, and then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution. Then the tungsten salt solution was heated to 85 ℃ in a water bath for 15 min. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0076] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.05% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1.2, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0077] Example 6

[0078] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 54 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6 hours to obtain the precursor Zn-NiCo-OH.

[0079] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6 hours to obtain the precursor W / Zn-NiCo-OH.

[0080] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.04% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1.5, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to W is about 1:1).

[0081] Example 7

[0082] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 61.2 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0083] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0084] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1.7, the molar ratio of Zn to Ni2P is about 0.064:1, and the molar ratio of Zn to W is about 1:1).

[0085] Example 8

[0086] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 8.4 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0087] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0088] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.07% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.061:1, and the molar ratio of Zn to W is about 1:1).

[0089] Example 9

[0090] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 7 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0091] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0092] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.04% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.052:1, and the molar ratio of Zn to W is about 1:1).

[0093] Example 10

[0094] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 4.2 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0095] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0096] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.01% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.032:1, and the molar ratio of Zn to W is about 1:1).

[0097] Example 11

[0098] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 1.4 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0099] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0100] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.012:1, and the molar ratio of Zn to W is about 1:1).

[0101] Example 12

[0102] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9.8 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0103] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0104] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.03% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.070:1, and the molar ratio of Zn to W is about 1:1).

[0105] Example 13

[0106] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 14.1 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0107] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0108] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.05% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.101:1, and the molar ratio of Zn to W is about 1:1).

[0109] Example 14

[0110] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 16.9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0111] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0112] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.04% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.121:1, and the molar ratio of Zn to W is about 1:1).

[0113] Example 15

[0114] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 21.1 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0115] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0116] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.15:1, and the molar ratio of Zn to W is about 1:1).

[0117] Example 16

[0118] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 28.1 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0119] Preparation of W / Zn-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0120] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.03% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.199:1, and the molar ratio of Zn to W is about 1:1).

[0121] Example 17

[0122] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0123] Preparation of W / Zn-NiCo-LDH: 9.9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0124] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.06% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.066:1, and the molar ratio of Zn to W is about 1:1.1).

[0125] Example 18

[0126] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0127] Preparation of W / Zn-NiCo-LDH: 10.8 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0128] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.04% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to W is about 1:1.2).

[0129] Example 19

[0130] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0131] Preparation of W / Zn-NiCo-LDH: 11.7 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0132] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.03% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1.3).

[0133] Example 20

[0134] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0135] Preparation of W / Zn-NiCo-LDH: 8.1 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0136] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.01% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.064:1, and the molar ratio of Zn to W is about 1:0.9).

[0137] Example 21

[0138] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0139] Preparation of W / Zn-NiCo-LDH: 7.2 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0140] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.064:1, and the molar ratio of Zn to W is about 1:0.8).

[0141] Example 22

[0142] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0143] Preparation of W / Zn-NiCo-LDH: 6.3 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0144] Preparation of W / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to W is about 1:0.7).

[0145] Example 23

[0146] Preparation of Zn-NiCo-LDH: 72 mmol of Ni(NO3)2·6H2O, 72 mmol of Co(NO3)2·6H2O, 18 mmol of Zn(NO3)2·6H2O and 18 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0147] Preparation of W / Zn-NiCo-LDH: 18 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0148] Preparation of W / Zn-Ni2P / Co2P: 18 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 11.03% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0149] Example 24

[0150] Preparation of Zn-NiCo-LDH: 144 mmol of Ni(NO3)2·6H2O, 144 mmol of Co(NO3)2·6H2O, 36 mmol of Zn(NO3)2·6H2O and 36 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0151] Preparation of W / Zn-NiCo-LDH: 36 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0152] Preparation of W / Zn-Ni2P / Co2P: 36 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively, and the tube furnace was kept in N2environment after N2replacement of the air in the tube furnace, and then heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 12.12% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0153] Example 25

[0154] Preparation of Zn-NiCo-LDH: 18 mmol of Ni(NO3)2·6H2O, 18 mmol of Co(NO3)2·6H2O, 4.5 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0155] Preparation of W / Zn-NiCo-LDH: 4.5 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution, and then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0156] Preparation of W / Zn-Ni2P / Co2P: 4.5 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment and heated to 350 ℃ at a heating rate of 5 ℃ / min, and then kept for 2 hours. The solid product in the downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 9.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.066:1, and the molar ratio of Zn to W is about 1:1).

[0157] Example 26

[0158] Preparation of Zn-NiCo-LDH: 9 mmol of Ni(NO3)2·6H2O, 9 mmol of Co(NO3)2·6H2O, 2.3 mmol of Zn(NO3)2·6H2O and 2.3 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned foam nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 ℃ for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor Zn-NiCo-OH.

[0159] Preparation of W / Zn-NiCo-LDH: 2.3 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Zn-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 ℃ for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 ℃ for 6h to obtain the precursor W / Zn-NiCo-OH.

[0160] Preparation of W / Zn-Ni2P / Co2P: 2.3 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of a tube furnace, respectively, the air in the tube furnace was replaced with N2, and then the temperature was raised to 350 °C at a rate of 5 °C / min under N2, and then the temperature was kept for 2 hours, and then the solid product downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 7.98% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0161] Comparative Example 1

[0162] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and the cleaned nickel foam (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours, and then the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 hours to obtain the precursor Zn-NiCo-OH.

[0163] Preparation of Zn-Ni2P / Co2P: 2.3 mmol of NaH2PO2·H2O and the precursor W / Zn-NiCo-OH were placed in the upstream and downstream of a tube furnace, respectively, the air in the tube furnace was replaced with N2, and then the temperature was raised to 350 °C at a rate of 5 °C / min under N2, and then the temperature was kept for 2 hours, and then the solid product downstream of the tube furnace was taken out to obtain the W / Zn-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 7.98% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0164] Comparative Example 2

[0165] Preparation of NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor NiCo-OH.

[0166] Preparation of Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor NiCo-OH were placed upstream and downstream of the tube furnace, respectively. After the tube furnace was replaced with N2, it was kept in an N2 environment. The temperature was raised to 350 °C at a rate of 5 °C / min, and then held for 2 hours. The solid product obtained from the downstream of the tube furnace was Ni2P / Co2P composite material (wherein: the total loading of Ni2P / Co2P was about 10.04% of the total mass of the substrate, and the molar ratio of Ni2P to Co2P was about 1:1).

[0167] Comparative Example 3

[0168] Preparation of NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor NiCo-OH.

[0169] Preparation of W-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 °C for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W-NiCo-OH.

[0170] Preparation of W-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W-NiCo-OH were placed upstream and downstream of the tube furnace, respectively. After replacing the air in the tube furnace with N2, the tube furnace was kept in an N2 environment. The temperature was raised to 350 °C at a rate of 5 °C / min, and then held for 2 h. The solid product downstream of the tube furnace was removed to obtain the W-Ni2P / Co2P composite material (wherein: the total loading amount of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, and the molar ratio of W to Ni2P is about 0.065:1).

[0171] Comparative Example 4

[0172] Preparation of Zn-CoFe-LDH: 36 mmol of Co(NO3)2·6H2O, 36 mmol of Fe(NO3)3·9H2O, 9 mmol of Zn(NO3)2·6H2O, and urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then, the mixed solution and clean foamed nickel (NF) were transferred to a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 h. After the reaction was completed, the solid product was washed with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-CoFe-OH.

[0173] Preparation of W / Zn-CoFe-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then, the precursor Zn-CoFe-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 °C for 15 min using a water bath. After the reaction was completed, the solid product was washed with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Zn-CoFe-OH.

[0174] Preparation of W / Zn-Co2P / Fe2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-CoFe-OH were placed upstream and downstream of the tube furnace, respectively. After replacing the air in the tube furnace with N2, the tube furnace was kept in an N2 environment. The temperature was raised to 350 °C at a rate of 5 °C / min, and then held for 2 h. The solid product downstream of the tube furnace was removed to obtain the W / Zn-Co2P / Fe2P composite material (also referred to as a catalytic electrode material, wherein: the total loading amount of Co2P / Fe2P is about 10.07% of the total mass of the substrate, the molar ratio of Co2P to Fe2P is about 1:1, the molar ratio of Zn to Co2P is about 0.064:1, and the molar ratio of Zn to W is about 1:1).

[0175] Comparative Example 5

[0176] Preparation of Zn-NiFe-LDH: A mixed solution was prepared by dissolving 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Fe(NO3)3·9H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea in 45 mL of deionized water. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-NiFe-OH.

[0177] Preparation of W / Zn-NiFe-LDH: A tungsten salt solution was prepared by dissolving 9 mmol of NaWO4·2H2O in a mixture of 40 mL of deionized water and 10 mL of anhydrous ethanol. Then the precursor Zn-NiFe-OH was immersed in the tungsten salt solution, and a water bath was used to heat the tungsten salt solution to 85 °C for 15 min. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Zn-NiFe-OH.

[0178] Preparation of W / Zn-Ni2P / Fe2P: 9 mmol of NaH2PO2·H2O and the precursor W / Zn-NiFe-OH were placed upstream and downstream of a tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was maintained in an N2 environment and heated to 350 °C at a rate of 5 °C / min, and then held at this temperature for 2 hours. The solid product downstream of the tube furnace was removed to obtain the W / Zn-Ni2P / Fe2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading of Ni2P / Fe2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Fe2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.065:1, and the molar ratio of Zn to W is about 1:1).

[0179] Comparative Example 6

[0180] Preparation of Cr-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Cr(NO3)3·9H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Cr-NiCo-OH.

[0181] Preparation of W / Cr-NiCo-LDH: 9 mmol of NaWO4·2H2O was dissolved in a mixed solution of 40 mL of deionized water and 10 mL of anhydrous ethanol to obtain a tungsten salt solution. Then the precursor Cr-NiCo-OH was immersed in the tungsten salt solution, and then the tungsten salt solution was heated to 85 °C for 15 min using a water bath. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor W / Cr-NiCo-OH.

[0182] Preparation of W / Cr-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor W / Cr-NiCo-OH were placed in the upstream and downstream of the tube furnace, respectively. After the air in the tube furnace was replaced with N2, the tube furnace was kept in N2 environment, and then heated to 350 °C at a heating rate of 5 °C / min and kept for 2 hours. The solid product taken out from the downstream of the tube furnace was W / Cr-Ni2P / Co2P composite material (which can also be referred to as a catalytic electrode material, wherein: the total loading amount of Ni2P / Co2P is about 10.05% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Cr to Ni2P is about 0.064:1, and the molar ratio of Cr to W is about 1:1).

[0183] Comparative Example 7

[0184] Preparation of Zn-NiCo-LDH: 36 mmol of Ni(NO3)2·6H2O, 36 mmol of Co(NO3)2·6H2O, 9 mmol of Zn(NO3)2·6H2O and 9 mmol of urea were dissolved in 45 mL of deionized water to prepare a mixed solution. Then the mixed solution and cleaned nickel foam (NF) were transferred into a 100 mL Teflon-lined reaction kettle. The reaction kettle was sealed and heated to 120 °C for 8 hours. After the reaction was completed, the solid product was cleaned with deionized water and then placed in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Zn-NiCo-OH.

[0185] A mixed solution was prepared by dissolving 6H2O, 9 mmol of Zn(NO3)2·6H2O, and 9 mmol of urea in 45 mL of deionized water. The mixed solution and cleaned nickel foam (NF) were then transferred to a 100 mL Teflon-lined reactor. The reactor was sealed and heated to 120 °C for 8 hours. After the reaction was complete, the solid product was washed with deionized water and then dried in a vacuum drying oven at 60 °C for 6 hours to obtain the precursor Zn-NiCo-OH.

[0186] Preparation of Mo / Zn-NiCo-LDH: 9 mmol of Na₂MoO₄·2H₂O was dissolved in a mixed solution of 40 mL deionized water and 10 mL anhydrous ethanol to obtain a tungsten salt solution. The precursor Zn-NiCo-OH was then immersed in the tungsten salt solution, and the solution was heated to 85 °C in a water bath for 15 min. After the reaction was complete, the solid product was washed with deionized water and then dried in a vacuum drying oven at 60 °C for 6 h to obtain the precursor Mo / Zn-NiCo-OH.

[0187] Preparation of Mo / Zn-Ni2P / Co2P: 9 mmol of NaH2PO2·H2O and the precursor Mo / Zn-NiCo-OH were placed upstream and downstream of a tube furnace, respectively. After replacing the air in the tube furnace with N2, the temperature was raised to 350 ℃ at a heating rate of 5 ℃ / min under N2 environment and held for 2 hours. The solid product at the downstream of the tube furnace was taken out to obtain the Mo / Zn-Ni2P / Co2P composite material (also known as catalytic electrode material, wherein: the total loading of Ni2P / Co2P is about 10.02% of the total mass of the substrate, the molar ratio of Ni2P to Co2P is about 1:1, the molar ratio of Zn to Ni2P is about 0.063:1, and the molar ratio of Zn to Mo is about 1:1).

[0188] Application Example 1

[0189] The composite materials prepared in Examples 1-27 and Comparative Examples 1-7 were used as catalytic electrodes to test their hydrogen evolution performance. The specific process is as follows: using a saturated calomel electrode (SCE) as the reference electrode and a Pt sheet electrode as the counter electrode, the composite materials prepared in Examples 1-20 and Comparative Examples 1-7 were used as working electrodes. Their HER reaction activity was tested in a three-electrode system using cathodic polarization curves (LSV). In the test conditions, the KOH solution concentration was 1 mol·L⁻¹. -1 The volume is 100mL.

[0190] The composite materials prepared in Examples 1-27 and Comparative Examples 1-7 were used as catalytic electrodes for hydrazine oxidation performance test, and the specific process was as follows: a saturated calomel electrode (SCE) was used as a reference electrode, a Pt sheet electrode was used as a counter electrode, and the composite materials prepared in Examples 1-27 and Comparative Examples 1-7 were used as working electrodes, respectively, and the HzOR reaction activity was tested by means of cathode polarization curve (LSV) in a three-electrode system. In the test conditions, the concentration of hydrazine in the hydrazine solution was 0.5 mol·L -1 , the concentration of KOH was 1 mol·L -1 , and the volume was 100 mL.

[0191] Table 1 shows the results of hydrogen evolution performance test and hydrazine oxidation performance test of different catalysts

[0192]

[0193]

[0194] In the present application, it can be known from Figure 1 that the W / Zn-Ni2P / Co2P composite catalytic material of Example 1 is loaded with rich nanowires on the surface, showing a “nano lawn” structure, which provides rich active sites for the catalyst.

[0195] It can be known from Figure 2 that the XRD pattern of W / Zn-Ni2P / Co2P is well matched with Ni2P and Co2P, and no diffraction peaks related to W and Zn are seen, indicating that W and Zn are successfully doped.

[0196] It can be known from Figure 3 that the XPS spectra of the three catalysts (W / Zn-Ni2P / Co2P, Ni2P / Co2P and Zn-Ni2P / Co2Pe) prepared in Example 1, Comparative Example 1 and Comparative Example 2 all have peaks of Ni 2p, Co 2p and P 2p, and the addition of W and Zn elements also has peaks of W 4f and Zn 2p, which confirms the successful preparation of W / Zn-Ni2P / Co2P.

[0197] Figure 4 represents the LSV spectrum of HzOR of the W / Zn-Ni2P / Co2P catalyst of Example 1 in a mixed solution of 0.5 mol·L -1 hydrazine hydrate and 1.0 mol·L -1 potassium hydroxide, and the scan speed is 5 mV·s -1 . It can be known from Figure 4 that the W / Zn-Ni2P / Co2P catalyst obtained in Example 1 has excellent HzOR catalytic activity, and its current density is 1000 mA·cm -2The oxidation potential of hydrazine at the current density is 4.15 mV.

[0198] Figure 5 This refers to the W / Zn-Ni2P / Co2P catalyst of Example 1 at 1.0 mol·L⁻¹ -1 The LSV spectrum of HER in potassium hydroxide was obtained with a scan rate of 5 mV·s. -1 .from Figure 5 As can be seen from the above, the W / Zn-Ni2P / Co2P catalyst obtained in Example 1 exhibits excellent HER catalytic activity, which can be achieved at 1000 mA·cm⁻¹. -2 The hydrogen evolution potential at the current density is 142.7 mV.

[0199] from Figure 6 As can be seen from this, when the electrolyte does not contain hydrazine hydrate, the W / Zn-Ni2P / Co2P catalyst obtained in Example 1 exhibits good performance at 1000 mA·cm⁻¹. -2 The water decomposition voltage of the overcurrent system (OWS) was 2.24V. With the addition of hydrated hydrazine molecules, the water decomposition voltage of the hydrazine oxidation-assisted overcurrent system (OHzS) was 0.72V, a decrease of 1.52V. This confirms that hydrazine oxidation-assisted water electrolysis for hydrogen production can save energy and effectively reduce production costs.

[0200] Figure 7 The W / Zn-Ni2P / Co2P prepared in Example 1 of this invention was prepared at 0.5 mol·L⁻¹ -1 hydrazine hydrate and 1.0 mol·L -1 The HzOR stability test results of potassium hydroxide mixed solution were obtained using the potential-time curve (E~t) in a three-electrode system. Figure 7 As can be seen from the above, the W / Zn-Ni2P / Co2P catalyst obtained in Example 1 exhibits good performance at 100 mA·cm⁻¹. -2 After a long-term test at current density for 100 hours, the HzOR catalytic potential showed little change, confirming its good HzOR catalytic stability.

[0201] Figure 8 This refers to the W / Zn-Ni2P / Co2P catalyst prepared in Example 1 at 1.0 mol·L⁻¹ -1 In potassium hydroxide solution, the HER stability test results were obtained using the potential-time curve (E~t) in a three-electrode system. Figure 8 As can be seen from the data, the W / Zn-Ni2P / Co2P catalysts at 100 mA·cm⁻¹... -2 and 200 mA·cm -2 After a long-term test at current density for 7 days, its HER catalytic potential did not change much, which also confirms its excellent HER catalytic stability.

[0202] Figure 9 This indicates that the Zn-Ni2P / Co2P catalyst prepared in Comparative Example 1 of this invention is at a concentration of 0.5 mol·L⁻¹. -1 hydrazine hydrate and 1.0 mol·L -1 The LSV spectrum of HzOR in a potassium hydroxide mixed solution, with a scan rate of 5 mV·s. -1 .from Figure 9 As can be seen from the data, the Zn-Ni2P / Co2P catalyst obtained in Comparative Example 1 exhibits high performance at 1000 mA·cm⁻¹. -2 The oxidation potential of hydrazine at the current density is approximately 172 mV.

[0203] Figure 10 This indicates that the Zn-Ni2P / Co2P catalyst prepared in Comparative Example 1 of this invention is at 1.0 mol·L⁻¹ -1 The LSV spectrum of HER in potassium hydroxide was obtained with a scan rate of 5 mV·s. -1 .from Figure 10 As can be seen from the data, the Zn-Ni2P / Co2P catalyst obtained in Comparative Example 1 exhibits high performance at 1000 mA·cm⁻¹. -2 The hydrogen evolution potential at the current density is approximately 322.6 mV.

[0204] Figure 11 This indicates that the Ni2P / Co2P catalyst prepared in Comparative Example 2 of this invention is at a concentration of 0.5 mol·L⁻¹. -1 hydrazine hydrate and 1.0 mol·L -1 The LSV spectrum of HzOR in a potassium hydroxide mixed solution, with a scan rate of 5 mV·s. -1 .from Figure 11 As can be seen from the data, the Ni2P / Co2P catalyst obtained in Comparative Example 2 exhibits performance at 1000 mA·cm⁻¹. -2 The oxidation potential of hydrazine at the current density is approximately 590 mV.

[0205] Figure 12 This indicates that the Ni2P / Co2P catalyst prepared in Comparative Example 2 of this invention is at 1.0 mol·L⁻¹ -1 The LSV spectrum of HER in potassium hydroxide was obtained with a scan rate of 5 mV·s. -1 .from Figure 12 As can be seen from the data, the Ni2P / Co2P catalyst obtained in Comparative Example 2 exhibits performance at 1000 mA·cm⁻¹. -2 The hydrogen evolution potential at the current density is approximately 142.7 mV.

[0206] from Figure 13 As can be seen from the data, the W-Ni2P / Co2P catalyst obtained in Comparative Example 3 exhibits performance at 1000 mA·cm⁻¹. -2 The oxidation potential of hydrazine at the current density is approximately 282.8 mV.

[0207] From Figure 14 Example 3, the W-Ni2P / Co2P catalyst obtained in Comparative Example 3 has a hydrogen evolution potential of about 335 mV at a current density of 1000 mA·cm -2 .

[0208] In the present application, the sources of the reagents used in the present application are as follows:

[0209] Ni(NO3)2·6H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0210] Co(NO3)2·9H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0211] Zn(NO3)2·6H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0212] Fe(NO3)3·9H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0213] Cr(NO3)3·9H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0214] Na2MoO4·2H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0215] Urea was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0216] Foamed nickel was purchased from Tianjin Metal Material Co., Ltd.

[0217] NaWO4·2H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0218] Ethanol was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0219] NaH2PO2·H2O was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0220] N2 was purchased from Shenyang Shuntai Special Gas Co., Ltd.

Claims

1. A tungsten-zinc co-doped Ni2P / Co2P composite material, characterized in that: The composite material comprises a substrate and nickel phosphide and cobalt phosphide loaded on the substrate, and the nickel phosphide and the cobalt phosphide are doped with elemental zinc and elemental tungsten.

2. The composite material of claim 1, wherein: In the composite material, the molar ratio of the nickel phosphide to the cobalt phosphide is 1:0.5-1.5, preferably 1:0.7-1.2; preferably, the total loading amount of the nickel phosphide and the cobalt phosphide is not more than 20% of the total mass of the substrate, preferably 5-15% of the total mass of the substrate.

3. The composite material according to claim 1 or 2, characterized in that: In the composite material, the molar ratio of the zinc element to the nickel phosphide is 0.01-0.2:1, preferably 0.05-0.15:1; the molar ratio of the zinc element to the tungsten element is 1:0.8-1.2, preferably 1:0.9-1.

1.

4. The composite material according to any one of claims 1-3, characterized in that: The substrate is one or more of nickel foam, copper foam and carbon material, preferably nickel foam.

5. A method of preparing a tungsten-zinc co-doped Ni2P / Co2P composite material or a method of preparing a tungsten-zinc co-doped Ni2P / Co2P composite material as claimed in any one of claims 1 to 4, characterised in that: The method comprises the following steps: 1) mixing a nickel source, a cobalt source, a zinc source and a regulator to obtain a mixed solution, then placing a substrate in the mixed solution to perform a hydrothermal reaction, taking out a solid product after the reaction is completed, and performing cleaning and drying treatment to obtain a Zn-NiCo-LDH material; 2) dissolving a tungsten source to obtain a tungsten-containing solution, then placing the Zn-NiCo-LDH material in the tungsten-containing solution to perform a water bath reaction, taking out a solid product after the reaction is completed, and performing cleaning and drying treatment to obtain a W / Zn-NiCo-LDH material; 3) performing a phosphating reaction on the W / Zn-NiCo-LDH material with a phosphating agent to obtain a tungsten-zinc co-doped Ni2P / Co2P composite material after the reaction is completed.

6. The method of claim 5, wherein: In step 1), the nickel source is a soluble nickel salt, preferably one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel carbonate; The cobalt source is a soluble cobalt salt, preferably one or more of cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate and cobalt carbonate; The zinc source is a soluble zinc salt, preferably one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate and zinc carbonate; The regulator is one or more of urea, hexamethylenetetramine, ammonium carbonate and cetyltrimethylammonium bromide, preferably urea; The substrate is one or more of nickel foam, copper foam and carbon material, preferably nickel foam; Preferably, the molar ratio of the use amounts of the nickel source, the cobalt source, the zinc source, urea and the regulator is 1:0.5-1.5:0.01-0.2:1.5-4, preferably 1:0.7-1.2:0.05-0.15:2-3.

5.

7. The method according to claim 5 or 6, characterized in that: In step 2), the tungsten source is a soluble tungsten salt or a tungsten-containing acid, preferably one or more of sodium tungstate, potassium tungstate, ammonium tungstate, sodium metatungstate, ammonium metatungstate, phosphotungstic acid and tungstic acid; Preferably, the molar use amount of the tungsten source is 0.8-1.2 times, preferably 0.9-1.1 times, the molar use amount of the zinc source.

8. The method of any one of claims 5-7, wherein: In step 3), the phosphating agent is a soluble phosphorus salt, preferably one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, sodium phosphite, potassium phosphite and ammonium phosphite; Preferably, the molar use amount of the phosphating agent is 0.5-2 times, preferably 0.7-1.5 times, the total molar use amount of the nickel source and the cobalt source.

9. The method according to any one of claims 5-8, characterized in that: Step 1) is specifically: weighing the nickel source, cobalt source, zinc source and urea in proportion, then dissolving them in a solvent (such as deionized water and / or ethanol) to obtain a mixed solution; placing the mixed solution in a reactor (such as a reaction kettle), then immersing the cleaned substrate in the mixed solution, and then hydrothermal reaction at 80-150℃ for 4-24h, after the reaction is completed, the solid product is taken out and washed with deionized water for multiple times (such as 3-10 times), and finally the cleaned solid product is placed in a drying box (preferably a vacuum drying box) and dried at 50-80℃ for 6-24h to obtain the Zn-NiCo-LDH material; and / or Step 2) is specifically: dissolving the tungsten source in a solvent (such as deionized water and / or ethanol) to obtain a tungsten-containing solution; then immersing the Zn-NiCo-LDH material in the tungsten-containing solution and placing it in a water bath, heating the water bath to warm the tungsten-containing solution to 30-100℃, and then water bath reaction for 0.1-5h, after the reaction is completed, the solid product is taken out and washed with deionized water for multiple times (such as 3-10 times), and finally the cleaned solid product is placed in a drying box (preferably a vacuum drying box) and dried at 50-80℃ for 6-24h to obtain the W / Zn-NiCo-LDH material; and / or Step 3) is specifically: placing the phosphating agent and the W / Zn-NiCo-LDH material in the upstream and downstream of the phosphating reactor (such as a tubular furnace) respectively, then replacing the air in the phosphating reactor with nitrogen or inert gas, and finally heating (such as heating rate 1-10℃ / min) to 200-500℃ in the atmosphere of nitrogen or inert gas for phosphating reaction for 0.5-5h, after the reaction is completed, the tungsten-zinc co-doped Ni2P / Co2P composite material is obtained.

10. Use of a tungsten-zinc co-doped Ni2P / Co2P composite material or a tungsten-zinc co-doped Ni2P / Co2P composite material as described in any one of claims 1 to 4 or a tungsten-zinc co-doped Ni2P / Co2P composite material prepared according to the method of any one of claims 5 to 9, characterized in that: The tungsten-zinc co-doped Ni2P / Co2P composite material is used for electrolysis of water to produce hydrogen, preferably for hydrazine oxidation assisted electrolysis of water to produce hydrogen.

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