CN110129814B

CN110129814B - Electrocatalytic electrode with ditungsten carbide inverse opal composite micro-nano structure and preparation and hydrogen evolution application thereof

Info

Publication number: CN110129814B
Application number: CN201910276623.4A
Authority: CN
Inventors: 孙志鹏; 方路峻; 张海峰; 余锦超; 吴方丹; 史晓艳; 邵涟漪
Original assignee: Guangdong University of Technology; Dongguan South China Design and Innovation Institute
Current assignee: Guangdong University of Technology; Dongguan South China Design and Innovation Institute
Priority date: 2019-04-08
Filing date: 2019-04-08
Publication date: 2021-03-26
Anticipated expiration: 2039-04-08
Also published as: CN110129814A

Abstract

The invention belongs to the technical field of clean energy materials, and discloses ditungsten carbide (W)₂C) An electrocatalytic electrode with an inverse opal composite micro-nano structure, a preparation method and hydrogen evolution application thereof. The electrocatalysis electrode is prepared by vertically placing a pretreated substrate into a polystyrene microsphere suspension emulsion, drying I, forming a multilayer template with the polystyrene microspheres in a self-assembly manner on the surface of the substrate in a compact and ordered arrangement manner, taking out the multilayer template, drying II, and soaking the template in WO₃Drying III in the precursor solution in air, heating I to 500-550 ℃, preserving I, and naturally cooling to room temperature to obtain WO₃Inverse opals; in WO₃And (3) electrodepositing polypyrrole on the surface of the inverse opal, heating to 800-850 ℃ in a mixed atmosphere of argon and hydrogen, preserving heat and naturally cooling to room temperature to obtain the catalyst. The method is simple, and the obtained W₂The C inverse opal has large specific surface area and high conductivity, and has wide application potential in the aspect of electrocatalytic hydrogen evolution.

Description

Electrocatalytic electrode with ditungsten carbide inverse opal composite micro-nano structure and preparation and hydrogen evolution application thereof

Technical Field

The invention belongs to the technical field of clean energy materials, and particularly relates to ditungsten carbide (W)₂C) An electrocatalytic electrode with an inverse opal composite micro-nano structure, and preparation and hydrogen evolution applications thereof.

Background

Hydrogen energy has attracted a high attention as a clean combustion fuel to solve global warming and energy crisis. Cost-effective production of hydrogen energy resources is a key to achieving hydrogen energy economy. Among various hydrogen production methods, the Hydrogen Evolution Reaction (HER) is considered to be an environmentally friendly, economical, and high-purity hydrogen production method. Taking the example of electrolysis of water in an acidic electrolyte, HER is usually accompanied by three reaction steps. Firstly, a Volmer step: h⁺+e^-→H_adsA proton is reduced to generate a hydrogen atom (H) after getting an electron_ads) And adsorbed on the electrode surface. H_adsAfter formation, the HER process goes through a Tafel step (2H)_ads→H₂) Or the Heyrovsky step (H)_ads+H⁺+e^-→H₂) Or both. In addition, the development of highly active and durable electrocatalysts is a great challenge for their practical use on a large scale.

However, for HER, the high performance catalyst is mostly limited to noble metals (Pt, Ir, Ru, etc.), which can reduce the generation of H on the electrode surface₂The activation energy of (3). Numerous theoretical calculations and experimental test results indicate the high catalytic activity of Pt, but the content of Pt on the earth as a noble metal is very low, and the high price becomes a limit to the large-scale industrial application of Pt. Researchers have conducted extensive research to obtain high performance HER electrocatalysts while reducing costs. Currently, there are four following strategies for HER electrocatalyst research: (1) the Pt is subjected to structural nano-atomization to expose more catalytic active sites, so that the Pt is reducedCapacity and utilization rate are improved; (2) the low | Delta G is designed and synthesized by a research mode combining theoretical calculation and experiments_H*A non-noble metal based catalyst with a value of | and the site with the highest catalytic activity is explored; (3) attention is paid to synergistic enhancement between two or more materials to achieve "1 +1>2 "; (4) the three-dimensional self-supporting HER electrode is prepared by adopting current collectors such as carbon cloth (paper), foamed Ni (Cu/Fe and the like), Ti (Mo/W and the like) sheets (nets) and the like, so that the exposure of active sites of the catalyst is prevented from being influenced by the use of adhesives such as Nafion and the like.

Under the urgent need, great efforts are made to find non-noble metal catalysts. During the past decade, many transition metal nitride, sulfide and phosphide catalysts have been considered as promising candidates for replacing precious metals for energy conversion and storage, particularly in the HER field. In fact, transition metals (MoS)₂、MoC、MoP、WC、W₂C、WS₂WP, etc.) shows great potential for replacing platinum group noble metal catalysts, with their unique electronic structure and abundant earth resources. Tungsten carbide in particular is reported to have superior surface properties, with the electron density of states at the fermi level being very similar to that of platinum due to electron transfer from the carbon interstitial atoms to the W5 d orbital. Early studies focused primarily on WC, which has excellent thermal and chemical stability. However, other compounds in this carbide family have been studied less and theoretical calculations indicate that, due to W₂The density of electronic states on the C Fermi level is higher, the Gibbs free energy for absorbing hydrogen is lower, and the catalyst is more suitable for HER. To overcome thermodynamic and kinetic barriers, the carbon atoms are incorporated into a metallic lattice, high temperature>950K) High temperatures are necessary, however, which lead to uncontrolled particle aggregation, to extremely low specific surface areas, relatively low conductivities, large initial overvoltages and thus to poor catalytic activity.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention provides a W₂C inverse opal composite micro-nano structure electro-catalysis electrode. The composite micro-nano structure electrocatalysis electricityHas a large specific surface area and high conductivity.

It is another object of the present invention to provide the above-mentioned W₂A preparation method of an electrocatalytic electrode with a C-inverse opal composite micro-nano structure. The method is suitable for preparing inverse opal structures with different pore sizes, and has short preparation period and simple process.

It is still another object of the present invention to provide the above W₂Application of the C inverse opal composite micro-nano structure electro-catalysis electrode.

The purpose of the invention is realized by the following technical scheme:

w₂C, putting the pretreated substrate into the polystyrene microsphere suspension emulsion vertically, drying I, forming a multilayer template in a close and ordered arrangement on the surface of the substrate by the polystyrene microspheres in a self-assembly manner, taking out the multilayer template, drying II, and soaking the template in WO₃Drying III in the precursor solution in air, heating I to 500-550 ℃, preserving I, and naturally cooling to room temperature to obtain WO₃Inverse opals; in WO₃And (3) electrodepositing polypyrrole on the surface of the inverse opal, heating to 800-850 ℃ in a mixed atmosphere of argon and hydrogen, preserving heat and naturally cooling to room temperature to obtain the catalyst.

Preferably, the particle size of the polystyrene microspheres in the suspoemulsion is 400-500 nm, and the volume ratio of the polystyrene microspheres to water in the suspoemulsion is 1: (25-50).

Preferably, the substrate is a Ti sheet, a stainless steel sheet, FTO, quartz or a silicon sheet.

Preferably, the temperature of the drying I is 70-75 ℃, and the time for drying I is 10-12 h; the temperature of the drying II is 90-100 ℃, and the time of drying III is 3-5 h.

Preferably, said WO₃Dissolving ammonium metatungstate in a mixed solution of deionized water and anhydrous methanol, and performing ultrasonic treatment for 3-5 min to obtain the precursor solution, wherein the volume ratio of the deionized water to the anhydrous methanol is 1: (2-3); said WO₃The concentration of the precursor solution is 0.1-0.2 mol/L.

Preferably, the rate of temperature rise I is 1-2 ℃/min, the time of heat preservation I is 3-5, the rate of temperature rise II is 3-5 ℃/min, and the time of heat preservation II is 3-5 h.

Preferably, the volume ratio of the argon to the hydrogen is (9-19): 1.

w is₂The preparation method of the electrocatalytic electrode with the C-inverse opal composite micro-nano structure comprises the following specific steps:

s1, adding water to dilute polystyrene microspheres, and then carrying out ultrasonic treatment to obtain a uniform and stable suspension emulsion; putting the substrate into a mixed solution of sulfuric acid and hydrogen peroxide for hydrophilic treatment, finally washing with deionized water, and drying with nitrogen;

s2, vertically placing a substrate into the suspension emulsion, drying the substrate I at a constant temperature of 70-75 ℃, and forming a plurality of layers of templates which are arranged in a close and ordered manner on the surface of the substrate in a self-assembly manner by using polystyrene microspheres; taking out the multi-layer template, drying at 90-100 ℃, and then soaking the template in WO₃Drying III in the precursor solution in air, heating I to 500-550 ℃, preserving I, and naturally cooling to room temperature to obtain WO₃Inverse opals;

s3. in WO₃Electrodepositing polypyrrole on the surface of the inverse opal, heating to 800-850 ℃ in a mixed atmosphere of argon and hydrogen, preserving heat, and naturally cooling to room temperature to obtain W₂C inverse opal.

Preferably, the volume ratio of the sulfuric acid to the hydrogen peroxide in the mixed solution in the step S1 is (3-4): (1-2); the power of the ultrasonic wave is 20-25 kHz, and the time of the ultrasonic wave is 20-30 min.

W is₂The application of the electro-catalysis electrode with the C inverse opal composite micro-nano structure in the field of electro-catalysis hydrogen evolution reaction.

The invention can provide a carbon layer on the surface of the inverse opal by utilizing the electrodeposition technology. The electrodeposition technology has better control capability on the deposition uniformity of the film. To overcome the thermodynamic and kinetic barriers, a higher temperature (>1000K) is required for the incorporation of C atoms into the lattice of the metal W, and an excessively high temperature would lead to uncontrolled particle agglomeration, thereby reducing the specific surface area and thus the catalytic performance of the sample. Compared with gaseous carbon (methane and the like), the solid carbon layer has the advantages that the reaction rate of C and W can be greatly reduced in subsequent high-temperature calcination treatment, and the problem of surface agglomeration is effectively solved. The invention can also continue to grow or deposit other structures and materials on the inverse opal, and the inverse opal structure has large specific surface area, thereby providing large support area for the preparation of subsequent materials. Nanorods, nanosheets and the like can be grown on the inverse opal structure, and the heterostructure can also be prepared by electrodeposition or atomic layer deposition.

The invention firstly utilizes a vertical deposition method to prepare a multilayer polystyrene microsphere template, then uses a precursor to fill in the microsphere gap, and prepares WO after calcination₃Inverse opals, then in WO₃Electrodepositing polypyrrole on the surface of inverse opal, treating the polypyrrole in argon-hydrogen mixed gas at high temperature, converting the polypyrrole into carbon, and then carrying out carbon and WO₃Reaction to form W₂C inverse opal. With W₂Based on the C IO structure, the electrocatalyst without noble metal is synthesized in acid. The design strategy of the invention is as follows: (1) the continuous conductive IO structure not only provides a direct and rapid electron transfer path, but also provides more active sites for electrochemical reaction, and is beneficial to gas release. (2) The solid carbon precursor can slow down the diffusion speed of carbon atoms to tungsten crystal lattices, and avoid excessive carbon deposition. As expected, W₂The C IO electrode provides a superior HER catalytic activity and excellent stability. Thus, by increasing W₂The specific surface area of the C electrode can obviously improve W₂Activity of C catalyst on HER. The design of three-dimensional Inverse Opals (IO) with continuous and periodic pore structures is a promising approach to significantly improve HER activity and stability.

Compared with the prior art, the invention has the following beneficial effects:

1. w of the invention₂The C inverse opal has large specific surface area and high conductivity, and can provide a rapid and direct electron transmission path.

2. W of the invention₂The C inverse opal composite micro-nano structure electro-catalysis electrode has excellent hydrogen evolution performance and excellent stabilityQualitatively, this is because the continuous conductive IO structure not only provides a direct and fast electron transfer path, but also provides more active sites for the electrochemical reaction, which is beneficial to the release of gas.

3. The method is suitable for preparing inverse opal structures with different pore sizes, and has short preparation period and simple process.

4. The pore size of the inverse opal structure prepared by the invention can be accurately controlled by selecting the size of the polystyrene microsphere, the type of the inverse opal surface layer material can be realized by selecting different electro-deposition precursors, and the selection of the materials and the structure obtained on the surface layer of the inverse opal structure is wider.

Drawings

FIG. 1 is a three-dimensional WO of the present invention₃A flow chart for preparing an inverse opal structure.

FIG. 2 shows three-dimensional WO in example 1 (a)₃Inverse opals, (b) is W₂C structural scanning electron microscope picture of inverse opal.

FIG. 3 shows W in example 1₂C inverse opal, WO₃Inverse opal and commercial platinum-carbon electrodes at 0.5M H₂SO₄Linear sweep voltammetry measurements in solution (a); (b) tafel plot; (c) w₂C, a timing current curve of inverse opal; (d) w₂Comparative polarization curve of inverse opal after 3000 cycles of testing.

Detailed Description

The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Example 1

1.WO₃The inverse opal structure was prepared as shown in fig. 1.

(1) Firstly, Ti sheets are selected as a substrate, mixed solution (volume ratio is 7: 3) of sulfuric acid and hydrogen peroxide is added for hydrophilic treatment, and finally, deionized water is used for washing, and nitrogen is used for drying.

(2) A vertical deposition method is utilized to take a plurality of layers of polystyrene microspheres on a Ti sheet substrate as a template, the size of the polystyrene microspheres is 408nm, the concentration is 0.1%, the deposition temperature is 72 ℃, and the deposition time is 600 min.

(3) And drying the obtained multilayer polystyrene microsphere template in the air, and then putting the template into a constant-temperature drying box for heat treatment at 90 ℃ for 3 hours to enhance the binding force among the PS balls.

(4) Preparation of WO by soaking₃Dissolving 1g ammonium metatungstate in a mixed solution of 1ml deionized water and 2ml anhydrous methanol, and performing ultrasonic treatment for 5min to obtain WO₃And (3) precursor solution. Soaking 1 hydrophilic Ti plate in the above WO₃And (4) waiting for 20min in the precursor solution, taking out the precursor solution and drying the precursor solution in the air.

(5) Calcining at 500 ℃ for 5h with the heating rate of 1 ℃/min to obtain WO₃An inverse opal structure.

2. Electrodeposition of pyrrole onto inverse opals

In WO₃Depositing a layer of polypyrrole on the surface by an electrodeposition method, and specifically comprising the following steps: mixing 0.041g of sodium hydroxide, 0.25g of p-toluenesulfonic acid and 10ml of deionized water, and carrying out ultrasonic treatment for 15min, wherein the pH value is 2; . Then, 0.25ml of pyrrole was added dropwise to the above mixed solution while stirring on a magnetic stirrer. Mixing WO₃The inverse opal is used as a working electrode, the platinum electrode is used as a counter electrode, and the Ag/AgCl is used as a reference electrode. The mixed solution was used as a deposition solution, and the bias voltage was set to 0.5V for 140 seconds. Finally, annealing for 5 hours in argon/hydrogen (hydrogen 5%) mixed atmosphere at 750 ℃ to obtain three-dimensional ordered W₂C inverse opal composite nano-structured electrode.

In FIG. 2, (a) is a three-dimensional WO₃In a planar SEM photograph of inverse opal, periodic hexagonal spherical holes each closely connected by a hole wall were observed with high clarity, and the three small holes below were seen clearly from the top large hole, which had a diameter of about 300nm and a hole wall thickness of about 60 nm. WO₃The inverse opal structure is not only periodic at the top but also at the bottomIs periodic. In FIG. 2, (b) is W₂C scanning electron microscope picture of inverse opal structure. It can be seen that the periodic porous structure is still maintained after the carbon layer is electrodeposited, the hole wall is obviously thickened, the hole wall is about 90nm, the size of a large hole is reduced to about 260nm, and the fact that the carbon obtained by the electrodeposition method is uniformly coated on WO is fully proved₃Surface of inverse opals.

FIG. 3 is W₂C inverse opal, WO₃Inverse opal and commercial platinum-carbon electrodes at 0.5M H₂SO₄And (4) testing the electrochemical performance in the solution. Wherein (a) the linear sweep voltammetry curve; (b) tafel plot; (c) w₂C, a timing current curve of inverse opal; (d) w₂Comparative polarization curve of inverse opal after 3000 cycles of testing. As can be seen from FIG. 3, the Linear Scanning (LSV) curve shows that 10mAcm is generated^–2At catalytic current density of (2), W₂The overpotential required for the C inverse opal is-146 mV; although there is a gap compared with commercial Pt-C electrode, W is prepared₂The electrocatalytic performance of the C inverse opal is superior to that of most of the currently reported non-noble metal electrocatalysts, WO₃Inverse opals exhibit poor electrocatalytic properties.

Tafel plot of the catalyst was used to reveal the kinetics of HER, as shown in (b) of fig. 3, W₂C inverse opal, WO₃The Tafel slopes of the inverse opal and commercial platinum-carbon electrodes were 78mV dec, respectively^-1，126mV dec^-1And 29mV dec^-1. A smaller tafel slope represents a faster hydrogen evolution rate of the catalyst with increasing overpotential. The stability of the catalyst is a crucial factor affecting the catalyst development, and in FIG. 3 (c) is W₂C chronoamperometric curve of inverse opal. It can be seen that W₂The current density of the C inverse opal was only reduced by 3.4% over 10h, demonstrating that W₂The C-inverse opal catalyst has better HER stability. To W₂C inverse opal was subjected to a polarization test of 3000 cycles, as shown in (d) of FIG. 3, and W, which is clearly seen by comparison₂The performance of the C inverse opal after 3000 cycles of testing is reduced by a smaller extent than the initial performance, thus confirming W₂The C inverse opal catalyst has higher stability and can bear accelerated degradation. W prepared by stencil method and electrodeposition method₂The C inverse opal structure has a large specific surface area, the periodic net structure provides an effective path for the rapid transmission of electrons, and W is discovered after a series of electrochemical tests₂The C inverse opal structure shows better electrocatalytic hydrogen evolution performance and stability.

Example 2

1.WO₃The inverse opal structure was prepared as shown in fig. 1.

(1) Firstly, FTO is selected as a substrate, mixed solution (volume ratio is 7: 3) of sulfuric acid and hydrogen peroxide is added for hydrophilic treatment, and finally, deionized water is used for washing, and nitrogen is used for drying.

(2) A vertical deposition method is utilized to take a plurality of layers of polystyrene microspheres on an FTO substrate as a template, the size of the polystyrene microspheres is 408nm, the concentration is 0.1%, the deposition temperature is 72 ℃, and the deposition time is 600 min.

(4) Preparation of WO by soaking₃Dissolving 1g ammonium metatungstate in a mixed solution of 1ml deionized water and 2ml anhydrous methanol, and performing ultrasonic treatment for 5min to obtain WO₃And (3) precursor solution. Soaking 1 piece of the FTO subjected to hydrophilic treatment in the above WO₃And (4) waiting for 20min in the precursor solution, taking out the precursor solution and drying the precursor solution in the air.

(5) Calcining at 550 ℃ for 3h at the heating rate of 2 ℃/min to obtain WO₃An inverse opal structure.

2. Electrodeposition of pyrrole onto inverse opals

In WO₃Depositing a layer of polypyrrole on the surface by an electrodeposition method, and specifically comprising the following steps: mixing 0.041g of sodium hydroxide, 0.25g of p-toluenesulfonic acid and 10ml of deionized water, and carrying out ultrasonic treatment for 15min, wherein the pH value is 2; then, 0.25ml of pyrrole was added dropwise to the above mixed solution while stirring on a magnetic stirrer. Mixing WO₃Inverse opal as a toolAs an electrode, a platinum electrode was used as a counter electrode and Ag/AgCl as a reference electrode. The mixed solution was used as a deposition solution, and the bias voltage was set to 0.6V for 120 seconds. Finally annealing for 4 hours in argon/hydrogen (hydrogen 5%) mixed atmosphere at 800 ℃ to obtain three-dimensional ordered W₂C inverse opal composite nano-structured electrode.

Example 3

1.WO₃The inverse opal structure was prepared as shown in fig. 1.

(1) Firstly, a quartz plate is selected as a substrate, mixed solution (volume ratio is 7: 3) of sulfuric acid and hydrogen peroxide is put into the quartz plate for hydrophilic treatment, and finally the quartz plate is washed by deionized water and dried by nitrogen.

(2) Multilayer polystyrene microspheres on a quartz substrate are used as templates by a vertical deposition method, the size of the polystyrene microspheres is 408nm, the concentration is 0.1%, the deposition temperature is 72 ℃, and the deposition time is 600 min.

(4) Preparation of WO by soaking₃Dissolving 1g ammonium metatungstate in a mixed solution of 1ml deionized water and 2ml anhydrous methanol, and performing ultrasonic treatment for 5min to obtain WO₃And (3) precursor solution. Soaking 1 hydrophilic quartz plate in the above WO₃And (4) waiting for 20min in the precursor solution, taking out the precursor solution and drying the precursor solution in the air.

(5) Calcining at 530 ℃ for 5h at the heating rate of 1.5 ℃/min to obtain WO₃An inverse opal structure.

2. Electrodeposition of pyrrole onto inverse opals

In WO₃Depositing a layer of polypyrrole on the surface by an electrodeposition method, and specifically comprising the following steps: mixing 0.041g of sodium hydroxide, 0.25g of p-toluenesulfonic acid and 10ml of deionized water, and carrying out ultrasonic treatment for 15min, wherein the pH value is 2; then, 0.25ml of pyrrole was added dropwise to the above mixed solution while stirring on a magnetic stirrer. Mixing WO₃The inverse opal is used as a working electrode, the platinum electrode is used as a counter electrode, and the Ag/AgCl is used as a reference electrode. The mixed solution is used as a deposition solution, and the bias voltage is setSet to 0.7V and deposit for 100 seconds. Finally annealing for 3 hours in the mixed atmosphere of argon/hydrogen (hydrogen 5%) at 850 ℃ to obtain three-dimensional ordered W₂C inverse opal composite nano-structured electrode.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims

1. The electrocatalysis electrode with the ditungsten carbide inverse opal composite micro-nano structure is characterized in that the electrocatalysis electrode is formed by vertically putting a pretreated substrate into polystyrene microsphere suspension emulsion, forming a plurality of layers of templates which are closely and orderly arranged on the surface of the substrate in a self-assembly mode through drying I, taking out the plurality of layers of templates, soaking the templates in WO after drying II₃Drying III in the precursor solution in air, heating I to 500-550 ℃, preserving I, and naturally cooling to room temperature to obtain WO₃Inverse opals; in WO₃And (3) electrodepositing polypyrrole on the surface of the inverse opal, heating to 800-850 ℃ in a mixed atmosphere of argon and hydrogen, preserving heat and naturally cooling to room temperature to obtain the catalyst.

2. The ditungstened carbide inverse opal composite micro-nano structure electrocatalytic electrode according to claim 1, wherein the particle size of the polystyrene microspheres in the suspoemulsion is 400-500 nm, and the volume ratio of the polystyrene microspheres to water in the suspoemulsion is 1: (25-50).

3. The ditungstened carbide inverse opal composite micro-nano structure electrocatalytic electrode according to claim 1, wherein the substrate is a Ti sheet, a stainless steel sheet, an FTO, quartz or a silicon sheet.

4. The ditungsten carbide inverse opal composite micro-nano structure electrocatalytic electrode as claimed in claim 1, wherein the temperature of drying I is 70-75 ℃, and the time for drying I is 10-12 h; the temperature of the drying II is 90-100 ℃, and the time of drying III is 3-5 h.

5. The ditungstened carbide inverse opal composite micro-nano structure electrocatalytic electrode according to claim 1, wherein the WO is₃Dissolving ammonium metatungstate in a mixed solution of deionized water and anhydrous methanol, and performing ultrasonic treatment for 3-5 min to obtain the precursor solution, wherein the volume ratio of the deionized water to the anhydrous methanol is 1: (2-3); said WO₃The concentration of the precursor solution is 0.1-0.2 mol/L.

6. The ditungsten carbide inverse opal composite micro-nano structure electrocatalytic electrode as claimed in claim 1, wherein the temperature rise rate is 1-2 ℃/min, the temperature preservation time is 3-5 ℃, the temperature rise rate is 3-5 ℃/min, and the temperature preservation time is 3-5 h.

7. The ditungstened carbide inverse opal composite micro-nano structure electrocatalytic electrode according to claim 1, wherein the volume ratio of the argon gas to the hydrogen gas is (9-19): 1.

8. the preparation method of the electrocatalytic electrode with the ditungstened inverse opal composite micro-nano structure according to any one of claims 1 to 7, which is characterized by comprising the following specific steps of:

s1, adding water to dilute the polystyrene microspheres, and then carrying out ultrasonic treatment to obtain uniform and stable suspoemulsion; putting the substrate into a mixed solution of sulfuric acid and hydrogen peroxide for hydrophilic treatment, finally washing with deionized water, and drying with nitrogen;

s2, vertically placing the substrate into the suspoemulsion, drying the substrate I at a constant temperature of 70-75 ℃, and forming a multilayer template which is arranged in a close and ordered manner on the surface of the substrate by the polystyrene microspheres in a self-assembly manner; taking out the multilayer template, drying II at 90-100 ℃, and soaking the template in WO₃Drying III in the precursor solution in air, heating I to 500-550 ℃, preserving I, and naturally cooling to room temperature to obtain WO₃Inverse opals;

s3 in WO₃Electrodepositing polypyrrole on the surface of the inverse opal, heating to 800-850 ℃ in a mixed atmosphere of argon and hydrogen, preserving heat, and naturally cooling to room temperature to obtain W₂C inverse opal.

9. The preparation method of the ditungstened carbide inverse opal composite micro-nano structure electro-catalytic electrode according to claim 8, wherein the volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution in the step S1 is (3-4): (1-2); the power of the ultrasonic wave is 20-25 kHz, and the time of the ultrasonic wave is 20-30 min.

10. The use of the electrocatalytic electrode of ditungsten carbide inverse opal composite micro-nano structure according to any one of claims 1 to 7 in the field of electrocatalytic hydrogen evolution reactions.