Three-dimensional porous copper oxide-zinc bimetallic film electrode for electrically reducing carbon dioxide and preparation and application of three-dimensional porous copper oxide-zinc bimetallic film electrode

Abstract

The invention belongs to the technical field of electro-catalysis carbon dioxide reduction, and particularly relates to a three-dimensional porous copper oxide-zinc bimetallic film electrode for electro-reduction of carbon dioxide and preparation and application of the three-dimensional porous copper oxide-zinc bimetallic film electrode. The preparation method comprises the following steps: firstly, carrying out surface pretreatment on a copper substrate, then carrying out pulse current electrodeposition and dynamic etching on the surface of an electrode in a mixed electrolyte containing zinc salt, copper salt and sodium salt, and finally, carrying out constant current structure reconstruction on the electrode by adopting a long-time reduction method to prepare the three-dimensional porous copper oxide-zinc bimetallic film electrode. The electrode has a unique nano pore channel structure, rapid transfer of interface charges is promoted, and the electrode has rich active sites due to the synergistic effect of a heterostructure. The preparation method has the dynamic regulation and control advantage of pulse deposition and the structural stability of constant-current deposition, a template agent does not need to be added in the preparation process, and the process controllability is high. The obtained electrode shows excellent CO product selectivity, activity and stability in an electro-catalysis carbon dioxide reduction reaction.

Description

Technical Field

[0001] The present invention belongs to the technical field of electro-reduction of carbon dioxide, and relates to a preparation method and application of a three-dimensional porous copper oxide-zinc bimetallic film electrode for electro-reduction of carbon dioxide. Background Art

[0002] As the content of carbon dioxide in the atmosphere increases sharply, the global average temperature rises year by year, and a series of extreme climate problems further triggered are imminent. Therefore, reducing the content of carbon dioxide in the atmosphere and its emissions, and converting it into value-added chemicals has multiple practical significances in terms of energy, environment and economy. In recent years, for the resource utilization of carbon dioxide, relevant workers have mainly used biological methods, photocatalytic methods, chemical methods and electrochemical methods to conduct research. Electrochemical reduction of carbon dioxide (ERCO2) is an environmentally friendly technology that can utilize clean energy and has a controllable reaction path. Through electrochemical reduction of carbon dioxide, it can be converted into C1 chemicals such as CO, formic acid, methane and methanol, as well as C2 and C 2+ Chemicals such as ethanol and ethylene. This conversion not only helps reduce carbon emissions but also stores renewable energy in high-value-added chemicals. Future research may focus on improving the stability of the catalyst, reducing energy consumption, improving selectivity, and achieving industrial-scale application.

[0003] Copper (Cu) and zinc (Zn) as non-precious metal elements have important catalytic prospects in the field of ERCO2 technology. The introduction of zinc can optimize the electronic structure of copper and promote * Coupling of CO intermediates can improve the selectivity of products. Zinc is often used as a promoter or alloy component in catalysts. Its high hydrogen overpotential can inhibit the hydrogen evolution reaction (HER) and regulate *The CO adsorption strength can be adjusted to regulate the selectivity of the catalyst. However, the structure and composition of the Cu-Zn alloy will directly affect the distribution of the products. The preparation method of the catalyst directly affects the structure and composition of the catalyst, thereby determining the selectivity of different products. By regulating the preparation conditions of the catalyst, the reconstruction of Cu nanoparticles and Zn materials can be induced, thereby improving the selectivity of the catalyst. The multiphase catalyst system with Cu-Zn bimetallic active centers as the core exhibits excellent product selectivity regulation capabilities in the carbon dioxide reduction reaction. By systematically regulating key parameters such as the active site structure, surface electronic properties and reaction microenvironment, the synergistic optimization of its catalytic activity, selectivity and stability was successfully achieved. Zeng et al. prepared a coupled Cu-Zn catalyst composed of polycrystalline submicron Cu and single-crystalline nano-sized ZnO particles by microwave-assisted solvothermal method. The synergistic effect led to enhanced performance of the bimetallic material, which was used for efficient electrochemical reduction of carbon dioxide to carbon monoxide with a Faradaic efficiency of 70% ([1] Zeng J, Rino T, Bejtka K, et al. Coupled Copper–Zinc Catalysts for Electrochemical Reduction of Carbon Dioxide[J]. ChemSusChem, 2020, 13 (16): 4128-4139.). However, this method usually has a complex preparation process and harsh conditions, which greatly limits the large-scale production and industrial application of composite materials. The inventors used (202010723993.0) to provide a photoelectrocatalytic system with a zinc-doped cuprous oxide film on the cathode surface for efficient electrochemical reduction of carbon dioxide to acetic acid. However, the copper-zinc-based catalyst prepared by this method still has problems such as excessive energy consumption due to high overpotential, poor stability and chemical life of the catalyst. The inventors used (202311067089.9) to prepare a Cu electrocatalyst by performing asymmetric cyclic voltage pulses in an electrolyte solution. The catalyst surface was continuously and rapidly regenerated through periodic redox cycles (i.e., oxidation at the anode potential and reduction at the cathode potential). However, the Cu catalyst prepared by this method is mainly a mixture of Cu-Cu2O, and the product of the catalyst is mainly methane, with essentially no CO produced. The present invention uses a pulsed current electrodeposition technique coupled with a long-term in-situ reduction technique to in situ grow a three-dimensional porous copper oxide-zinc on a Cu substrate. This method does not require additional additives and is simple and easy to prepare. The developed Cu-Zn bimetallic catalyst, due to its unique electronic structure and synergistic effect, can effectively convert carbon dioxide into CO, an important component of synthesis gas, and has important application value in the chemical industry.By regulating the ratio and structure of copper and zinc through the pulse method of electrodeposition, the electronic structure and surface properties of copper can be adjusted. Through long-term constant current reduction technology, the performance of the catalyst is optimized, thereby improving the selectivity for CO. By adjusting the atomic ratio of Cu and Zn, an asymmetric catalyst is formed. * Active sites with high CO adsorption capacity improve the selectivity of the catalyst for CO. Summary of the Invention

[0004] To overcome the shortcomings of existing technologies, the present invention provides a method for preparing and applying a three-dimensional porous copper oxide-zinc bimetallic film for carbon dioxide electroreduction. A carbon dioxide electroreduction electrode material with a high active site density is synthesized through a synergistic construction strategy of pulse co-deposition and long-term constant current reduction. This method requires no complex additives and is simple and controllable. The prepared catalyst has a regular, loose, and porous structure (particle size ranges from 10 nm to 250 nm, and the pore volume of the surface catalytic layer is 2 cm). 3 g -1 ~6 cm 3 g -1 , pore size distribution is 1 nm to 20 nm), which significantly improves the electrochemical activity and selectivity of carbon dioxide reduction to CO.

[0005] The above-mentioned object of the present invention is achieved through the following technical solutions: A three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide comprises the following steps: ultrasonically treating a copper mesh in HCl, and ultrasonically cleaning the mesh in anhydrous ethanol and then ultrapure water; mixing zinc salt, copper salt, and sodium salt and adding them to deionized water; electrochemically depositing and etching the copper mesh substrate by a pulsed current method; then subjecting the electrode to long-term constant current reduction in an H-type electrolytic cell to promote structural reconstruction of the pulsed deposited layer; and rinsing the electrode in anhydrous ethanol and then ultrapure water to obtain the three-dimensional porous copper oxide-zinc bimetallic film electrode, wherein the proportion of copper oxide is 1 to 40 wt%, and the proportion of copper oxide is preferably 5 to 30 wt%.

[0006] The method specifically comprises the following steps: Step 1): Place 0.5cm 2 ~6 cm 2 The copper mesh substrate is placed in 10 mL to 100 mL of 0.1 M to 5.0 M HCl for chemical etching for 5 min to 40 min, and then ultrasonically cleaned in anhydrous ethanol and water in sequence, and dried to obtain the pretreated copper mesh T-CM; Step 2): placing the pretreated copper mesh T-CM obtained after treatment into an electrolyte for pulse current electrodeposition, wherein the pulse current has an oxidation current density I1 and an oxidation time T1, and a reduction current density I2 and a reduction time T2, and the exchange cycle is performed more than 10 times under the conditions of I1 and I2; Step 3): The pulse current electrodeposited electrode obtained in step 2) is rinsed in anhydrous ethanol and water in sequence, and electroreduced on the electrode surface in an alkaline electrolyte at room temperature using a long-term constant current reconstruction method under the protection of an inert atmosphere; Step 4): The electrode prepared in step 3) is rinsed in anhydrous ethanol and water in sequence, and then dried to prepare a three-dimensional porous copper oxide-zinc bimetallic film electrode.

[0007] Furthermore, in step 1), the mesh size of the copper mesh is 100-300 mesh, preferably 150-250 mesh; the wire diameter is 0.01 mm-0.3 mm, preferably 0.05 mm-0.2 mm; the size of the copper mesh is preferably 1 cm 2 ~3 cm 2 .

[0008] Furthermore, the preferred chemical etching solution HCl concentration in step 1) is preferably 0.1M to 10M; and the preferred chemical etching time is 10 min to 20 min.

[0009] Furthermore, the copper oxide in the surface catalytic layer of the three-dimensional porous copper oxide-zinc electrode in step 1) is one or both of Cu2O and CuO, and the loading amount of the surface catalytic layer is 5 mg cm -2 ~20 mg cm -2 , the preferred loading is 10 mg cm -2 ~15 mg cm -2 .

[0010] Furthermore, the electrolyte in step 2) is zinc salt, copper salt and sodium salt dissolved in 100 mL to 300 mL of deionized water to form a copper-zinc deposition solution, the zinc salt is one or more of zinc nitrate, zinc sulfate and zinc chloride, and the concentration of the zinc salt is 0.01 M to 2 M, preferably 0.01 M to 1 M; the copper salt is one or more of copper nitrate, copper sulfate and copper chloride, and the concentration of the copper salt is 0.001 M to 0.5 M, preferably 0.05 M to 0.1 M; the sodium salt is one or more of sodium nitrate, sodium sulfate and sodium chloride, and the concentration of the sodium salt is 0.01 M to 1 M, preferably 0.01 M to 0.5 M.

[0011] Furthermore, the oxidation current density I1 in step 2) is 5 mA cm-2 ~60 mA cm -2 , the preferred current density is 10 mA cm -2 ~40 mA cm -2 ; Reduction current density I2 is -10 mA cm -2 ~-80 mA cm -2 , the preferred current density is -30 mA cm -2 ~-60 mA cm -2 ; The oxidation time T1 is 0.2 s to 20 s, preferably 0.5 s to 10 s; the reduction time T2 is 0.4 s to 25 s, preferably 0.8 s to 15 s; the number of cycles under the conditions of I1 and I2 is 10 to 1000 cycles, preferably 200 to 500 cycles.

[0012] Furthermore, the alkaline electrolyte in step 3) is one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate, dissolved in 100 mL to 300 mL of deionized water, and the electrolyte concentration is 0.01 M to 2 M, preferably 0.05 M to 1 M.

[0013] Furthermore, the reduction current density in step 3) is -2 mA cm -2 ~-100 mA cm -2 , the preferred reduction current density is -5 mA cm -2 ~-20 mA cm -2 , the preferred reduction time t is 4500s to 12000s, and the preferred reduction time t is 5000s to 9000s.

[0014] The thin film electrode obtained by the above preparation method is used in the electrochemical reduction reaction of carbon dioxide, and the thin film electrode serves as the cathode of the reaction. The specific application is: a three-electrode system is used to construct an electrochemical system, the prepared charged catalyst electrode is used as the working electrode of the electrochemical reduction reaction of carbon dioxide, a 1cm×1cm platinum sheet is used as the counter electrode of the electrochemical reduction reaction of carbon dioxide, and an Ag / AgCl electrode is used as the reference electrode of the electrochemical reduction reaction of carbon dioxide; the cathode chamber and the anode chamber of the electrolytic cell are separated by a proton exchange membrane, the cathode chamber is filled with 40mL of 0.1M KHCO3 solution, and the anode chamber is filled with 40mL of 0.1M KHCO3 solution. The working electrode is placed in the cathode chamber, the counter electrode is placed in the anode chamber, and the reference electrode is placed in the cathode chamber; during the electrocatalytic reduction of carbon dioxide reaction, carbon dioxide is passed into the cathode chamber for 25 minutes, and the carbon dioxide flow rate is set to 40 mLmin -1; The voltages applied between the working electrode and the counter electrode were -1.6 V, -1.65 V, -1.7 V, -1.75 V, and -1.8 V (Ag / AgCl). The catalytic reduction products were CO and H2, and the catalytic reduction products were detected every 15 minutes.

[0015] The beneficial effects of the present invention compared with the prior art are: The present invention adopts a multi-cycle pulse current deposition method, which realizes a dynamic dissolution-redeposition process on the copper mesh substrate by flexibly adjusting the pulse parameters (current intensity and number of cycles). Compared with the traditional pulse voltage method, this method realizes a dynamic dissolution-redeposition process on the copper mesh substrate by periodically switching the oxidation current density (10 mA cm -2 ~40 mA cm -2 ) and reduction current density (-30 mA cm -2 ~-60 mA cm -2 ), precisely controlling the redox reaction in a copper-zinc salt electrolyte: the oxidation process prevents excessive etching of the substrate, while the reduction phase reconstructs the catalyst's near-surface layer to form precursor sites. The alternating pulse action promotes periodic reorganization and regeneration of the catalyst surface, significantly increasing the specific surface area and active site density in a dynamic equilibrium, ultimately achieving optimized catalytic performance and controlled product distribution.

[0016] This invention, centered on the synergistic technology of pulsed current and long-term constant-current electroreduction, employs a copper and zinc non-precious metal system and dynamically optimizes the coating composition and microstructure by manipulating pulse parameters. The pulsed technology, through multiple cycles, induces directional aggregation of particles on the copper mesh surface, forming loose, continuous copper oxide-zinc nanoparticles, simultaneously achieving efficient deposition and morphology control at room temperature and pressure. The long-term constant-current electroreduction principle precisely controls the product loading (Q = i × t) through a constant electron supply. This continuous driving force promotes the gradual reduction of metal ions, enabling refined control of nanoparticle size. The synergistic effect of these two methods results in a catalyst exhibiting highly uniform coatings, fine grains, and controllable loading, providing a stable and reliable technical path for low-cost, large-scale production.

[0017] The present invention uses in-situ copper matrix etching technology to simultaneously construct a three-dimensional porous structure, copper oxide-zinc heterogeneous interface and oxygen vacancies / step sites through atomic-level zinc doping. The three-dimensional porous skeleton significantly increases the density of active sites, and the heterogeneous interface induces charge redistribution to optimize the reaction path. Among them, oxygen vacancies (O v ) and Cu + Synergistic reduction * COOH intermediate adsorption energy, while Zn sites simultaneously weaken through electron induction effect * This structure-electron synergistic regulation mechanism effectively reduces the reaction energy barrier and enables the catalyst to exhibit excellent activity and product selectivity in the carbon dioxide reduction reaction.

[0018] The present invention significantly improves the performance of the catalyst through a synergistic strategy of pulse electrodeposition and long-time constant current electroreduction technology. Pulse electrodeposition precisely controls the distribution of active sites, and combined with the long-time directional reconstruction of constant current electroreduction, metal atoms are orderly enriched at the defect sites of the carrier, forming a stable active layer with a dense porous structure. After pulse deposition, there may be incompletely reduced CuO on the surface (which is not conducive to CO formation). Constant current reduction further reduces CuO to a more active Cu2O phase through continuous electron supply. The present invention is based on the synergistic technology of pulse current method and long-time constant current electroreduction. Through the periodic deposition-etching process on the electrode surface, the distribution of active sites is precisely controlled, and combined with the long-time directional reconstruction of constant current electroreduction, metal atoms are orderly enriched at the defect sites of the carrier, forming a stable active layer with a dense porous structure. This process dynamically controls the metal deposition rate, avoiding surface oversaturation and strengthening the reactant diffusion channel, while simultaneously achieving the construction of high-density edges. Especially for copper-based catalysts, this composite process effectively overcomes the defects of loose structure and easy deactivation of the traditional constant potential method, so that the catalyst has high selectivity, reaction stability and long-term durability in the electrochemical reduction of carbon dioxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 : CO and H2 selectivity distribution diagram of the electrocatalyst in Example 1 in a 0.1M KHCO3 solution saturated with carbon dioxide, and the total current density of CO.

[0020] Figure 2 The electrochemical reduction of carbon dioxide test was performed on the electrocatalyst prepared in Example 1 and Comparative Examples 1, 2, 3, and 4, i.e., a CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0021] Figure 3 Electrochemical reduction of carbon dioxide tests at different oxidation currents were performed on the electrocatalysts prepared in Example 1, Example 2, Example 3, and Example 4, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0022] Figure 4 Electrochemical reduction of carbon dioxide tests at different reduction currents were performed on the electrocatalysts prepared in Examples 1, 5, 6, and 7, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0023] Figure 5 Electrochemical reduction of carbon dioxide tests at different cycle numbers were performed on the electrocatalysts prepared in Examples 1, 8, 9, and 10, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0024] Figure 6 Electrochemical reduction of carbon dioxide tests at different reduction times were performed on the electrocatalysts prepared in Example 1, Example 11, and Example 12, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0025] Figure 7 Electrochemical reduction of carbon dioxide tests at different reduction times were conducted on the electrocatalysts prepared in Example 1, Example 13, Example 14, and Example 15, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0026] Figure 8 Electrochemical reduction of carbon dioxide tests at different reduction times were performed on the electrocatalysts prepared in Example 1, Example 16, Example 17, and Example 18, i.e., CO Faraday efficiency diagram in 0.1 M KHCO3 solution.

[0027] Figure 9 These are SEM images of the three-dimensional porous copper oxide-zinc bimetallic electrocatalyst prepared in Example 1, wherein (a) is an image at a magnification of 10k, and (b) is an image at a magnification of 20k.

[0028] Figure 10 2 are SEM images of the three-dimensional porous copper oxide-zinc bimetallic electrocatalyst prepared in Comparative Example 1, wherein (a) is an image at a magnification of 10k, and (b) is an image at a magnification of 20k.

[0029] Figure 11 This is the EDS image of the three-dimensional porous copper oxide-zinc bimetallic electrocatalyst prepared in Example 1.

[0030] Figure 12 This is the XRD pattern of the three-dimensional porous copper oxide-zinc bimetallic electrocatalyst prepared in Example 1.

[0031] Figure 13 It is an H-type electrolytic cell device for constant current reduction process. DETAILED DESCRIPTION

[0032] The present invention is described in detail below by specific examples, but the scope of protection of the present invention is not limited. Unless otherwise specified, the experimental methods adopted in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be obtained from commercial channels.

[0033] The present invention provides a method for preparing and applying a three-dimensional porous copper oxide-zinc bimetallic film electrode for the electroreduction of carbon dioxide. This method requires no additional additives and is simple and easy to prepare. The catalyst prepared by the present invention enhances the electrochemical effect and improves the selectivity of carbon dioxide reduction to CO.

[0034] The present invention is further described below: The present invention provides a method for in-situ growth of a copper oxide-zinc bimetallic electrode on a copper substrate through a synergistic construction strategy of pulse co-deposition and constant current reduction. This method uses an HCl-treated copper mesh as a substrate and forms a copper oxide-zinc nanofilm on its surface through a combination of electrochemical pulse deposition and long-term constant current reduction. This improves the selectivity of carbon dioxide reduction to CO. The method for preparing the three-dimensional porous copper oxide-zinc bimetallic film electrode comprises: Place a 100-300 mesh copper mesh in 10 mL-100 mL of 0.1 M-5 M HCl for chemical etching, place it in anhydrous ethanol and then in ultrapure water for ultrasonic cleaning for 20 min, and then dry it for later use; the mesh size of the copper mesh is preferably 150-250 mesh; the HCl concentration is preferably 0.1 M-10 M; Zinc salt, copper salt and sodium salt are dissolved in 100 mL to 300 mL of deionized water to form a copper-zinc deposition solution. Under inert atmosphere protection and room temperature, the treated copper mesh T-CM is placed in an electrolyte for pulse current electrodeposition. The oxidation current I1 is carried out for an oxidation time T1, and the reduction current I2 is carried out for a reduction time T2. A certain number of exchange cycles are performed under the conditions of I1 and I2. The preferred concentration of the zinc salt is 0.01M to 1M; the preferred concentration of the copper salt is 0.001M to 0.1M; the preferred concentration of the sodium salt is 0.01M to 0.5M; and the preferred current density of the oxidation current I1 is 10 mA cm -2 ~40 mA cm -2 ; The optimal current density of the reduction current I2 is -30 mA cm -2 ~-60 mA cm -2 ; The preferred oxidation time T1 is 0.5 s to 10 s; the preferred reduction time T2 is 0.8 s to 15 s; the preferred number of cycles is 200 to 500 times; Prepare 100 mL to 300 mL of alkaline solution, rinse the prepared electrode in anhydrous ethanol and ultrapure water, and perform electroreduction on the electrode surface using a long-term constant current reduction method at room temperature under inert atmosphere protection. Set the reduction current density to -2 mA cm -2 ~-100 mA cm -2 The reduction time t is 4500s~12000s; the preferred concentration of the electrolyte is 0.05M-1M; the preferred reduction current density is -5 mA cm -2 ~-20 mA cm -2 , the reduction time t is preferably 5000s to 9000s; The prepared electrode was rinsed in anhydrous ethanol and ultrapure water, and then dried in a vacuum drying oven to prepare a CuZn / CM thin film electrode.

[0035] Example 1 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM thin film electrode.

[0036] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.6 mg cm -2SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size ranges from 10 nm to 200 nm. The pore volume of the surface catalytic layer is 4.321 cm 3 g -1 The pore size distribution is between 2 nm and 10 nm, which is a three-dimensional porous copper oxide-zinc bimetallic electrocatalyst.

[0037] Example 2 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +10 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 The reduction time t was 5400s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I1 = +10 mA cm -2 )electrode.

[0038] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.0 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 4.088 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0039] Example 3 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +30 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2The reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I1 = +30 mA cm -2 )electrode.

[0040] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.3 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh surface, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.801 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0041] Example 4 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +40 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 The reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I1 = +40 mA cm -2 )electrode.

[0042] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.5 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.511 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0043] Example 5 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -30mA cm -2, the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 The reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I2 = -30 mA cm -2 )electrode.

[0044] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.0 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.916 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0045] Example 6 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm-2 The oxidation time is T1 = 1s; the reduction current density is I2 = -40mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 The reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I2 = -40 mA cm -2 )electrode.

[0046] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.8 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.466 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0047] Example 7 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -60mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 The reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence and then dried in a vacuum drying oven to prepare CuZn / CM (I2 = -60 mA cm -2 )electrode.

[0048] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 10.1 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 4.217 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0049] Example 8 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 150 times, and the pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (150 times) electrode.

[0050] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.4 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.309 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0051] Example 9 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 450 times, and the pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (450 times) electrode.

[0052] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.1 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 4.001 cm3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0053] Example 10 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 600 times, and the pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (600 times) electrode.

[0054] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 9.76 mg cm -2SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 3.991 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0055] Example 11 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc sulfate, 0.0015 M copper sulfate, and 0.05 M sodium sulfate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (sulfate deposition system) electrode.

[0056] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 30 wt% and Zn accounting for 70 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 10.9 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 4.212 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0057] Example 12 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc chloride, 0.0015 M copper chloride, and 0.05 M sodium chloride were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2, the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (chloride salt deposition system) electrode.

[0058] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 30 wt% and Zn accounting for 70 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.1 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.743 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0059] Example 13

[0060] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M NaHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (sodium bicarbonate reduction system) electrode.

[0061] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 10wt% and Zn accounting for 90wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 10.31mgcm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 3.872 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0062] Example 14

[0063] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M Na2CO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (sodium carbonate reduction system) electrode.

[0064] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20wt% and Zn accounting for 80wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 9.83mgcm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 25 nm to 200 nm. The pore volume of the surface catalytic layer is 3.68 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0065] Example 15

[0066] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm-2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M K2CO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 5400 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (potassium carbonate reduction system) electrode.

[0067] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20wt% and Zn accounting for 80wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 9.03mgcm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 3.352 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0068] Example 16

[0069] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm-2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere protection, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M Na2CO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -8 mA cm -2 The reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare CuZn / CM (I 还原 =-8 mAcm -2 system) electrodes.

[0070] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 20wt% and Zn accounting for 80wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.14 mg / cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.419 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0071] Example 17

[0072] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M Na2CO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -10 mA cm -2 The reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare CuZn / CM (I 还原 = -10mA cm -2 system) electrodes.

[0073] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 10wt% and Zn accounting for 90wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.82mgcm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.734 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0074] Example 18

[0075] A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M Na2CO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -14 mA cm -2 The reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare CuZn / CM (I 还原 = -14mA cm -2 system) electrodes.

[0076] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20wt% and Zn accounting for 80wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.29mgcm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 4.212 cm 3 g-1 , the pore size distribution is between 5 nm and 20 nm.

[0077] Comparative Example 1 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 0 s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (t=0 s) electrode.

[0078] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and ZnO, with CuO accounting for 10 wt% and ZnO accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.5 mg cm -2SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and ZnO. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 2.956 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0079] Comparative Example 2 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t was 1800 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (t=1800s) electrode.

[0080] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 12.3 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.335 cm 3 g -1 , the pore size distribution is between 2 nm and 10 nm.

[0081] Comparative Example 3 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2, the reduction time t was 3600 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (t=3600s) electrode.

[0082] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.7 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 3.948 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0083] Comparative Example 4 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2 The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t is 2000s, and the prepared electrocatalyst electrode is rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (t=2000s) electrode.

[0084] XRD and XPS analysis showed that the surface catalytic layer was composed of Cu2O and Zn, with Cu2O accounting for 10 wt% and Zn accounting for 90 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 9.98 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50nm to 250nm. The pore volume of the surface catalytic layer is 3.996 cm 3 g -1 , the pore size distribution is between 5 nm and 20 nm.

[0085] Comparative Example 5 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system, with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, with the oxidation voltage E1 set to -0.2 V (vs. AgCl) and the oxidation time T1 = 1 s; the reduction voltage E2 was set to -0.6 V (vs. AgCl) and the reduction time T2 = 1 s. The number of cycles was 300 to obtain a pulsed current electrodeposited layer. The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere, electroreduction was carried out on the surface of the pulsed current electrode by long-term constant current reduction at room temperature. In 180 mL of 0.1 M KHCO3 solution, a copper mesh electrode treated with pulsed current electrodeposition was used as the working electrode, a 1 cm × 1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the reduction current density was set to -12 mA cm -2 , the reduction time t was 5400 s, and the prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (E1=-0.2V, E2=-0.6 V) electrode.

[0086] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of CuO and Zn, with CuO accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 11.65 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of CuO and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 10 nm to 200 nm. The pore volume of the surface catalytic layer is 3.46 cm 3 g -1 The pore size distribution is between 2 nm and 10 nm. In the electrochemical reduction of carbon dioxide test, the highest Faradaic efficiency of CO generation is only 62.7%.

[0087] Comparative Example 6 A 200-mesh copper mesh with a size of 1 cm × 1 cm (length × width) was placed in 20 mL of 2M HCl and ultrasonically treated for 20 min. It was then ultrasonically cleaned in anhydrous ethanol and ultrapure water for 20 min, and dried for later use (i.e., the treated copper mesh). The wire diameter of the copper mesh was 0.1 mm. 0.05 M zinc nitrate, 0.0015 M copper nitrate, and 0.05 M sodium nitrate were dissolved in 180 mL of deionized water to form a copper-zinc deposition solution. Under room temperature conditions, the treated copper mesh substrate was placed in the deposition solution and pulsed current electrodeposition was performed in a three-electrode system with the treated copper mesh as the working electrode, a 1 cm × 1 cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A VERSA STAT3 electrochemical workstation was used, and the oxidation current density I1 was set to +20 mA cm -2The oxidation time is T1 = 1s; the reduction current density is I2 = -50mA cm -2 , the reduction time is T2=1s; the number of cycles is 300 times, and a pulse current electrodeposition layer is obtained; The prepared electrocatalyst was washed in anhydrous ethanol and ultrapure water in sequence; Under nitrogen atmosphere protection, at room temperature, electroreduction was carried out on the surface of the pulse current electrodeposited electrode by long-term constant current reduction method. In 180 mL of 0.1 M KHCO3 solution, the copper mesh electrode treated with pulse current electrodeposition was used as the working electrode, a 1 cm×1 cm platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Using a VERSA STAT3 electrochemical workstation, the reduction current voltage was set to -1.5 V (vs. AgCl), and the reduction time t was 5400 s. The prepared electrocatalyst electrode was rinsed in anhydrous ethanol and ultrapure water in sequence, and then dried in a vacuum drying oven to prepare a CuZn / CM (E=-1.5 V) electrode.

[0088] XRD and XPS analysis showed that the surface catalytic layer attached to the copper mesh was composed of Cu2O and Zn, with Cu2O accounting for 20 wt% and Zn accounting for 80 wt%. The loading capacity of the surface catalytic layer on the three-dimensional porous copper oxide-zinc electrode was 10.93 mg cm -2 SEM analysis showed that the surface catalytic layer is composed of nanoparticles. The nanoparticles are bimetallic composite particles composed of Cu2O and Zn. The nanoparticles are evenly distributed around the mesh on the copper mesh, showing a regular loose porous structure. The particle size is 50 nm to 250 nm. The pore volume of the surface catalytic layer is 3.844 cm 3 g -1 The pore size distribution is between 5 nm and 20 nm. In the electrochemical reduction of carbon dioxide test, the highest Faradaic efficiency of CO generation is only 71.7%.

[0089] Application Example 1 The electrocatalyst electrodes with copper oxide and zinc prepared in Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were respectively used as cathodes of the electrochemical catalytic reduction of carbon dioxide reaction system. A three-electrode system was used to construct the electrochemical system. The prepared charged catalyst electrode was used as the working electrode for the electrochemical reduction of carbon dioxide reaction. A 1 cm×1 cm platinum sheet was used as the counter electrode for the electrochemical reduction of carbon dioxide reaction. An Ag / AgCl electrode was used as the reference electrode for the electrochemical reduction of carbon dioxide reaction. The cathode chamber and the anode chamber of the electrolytic cell were separated by a proton exchange membrane. The cathode chamber was filled with 40 mL of a 0.1 M KHCO3 solution, and the anode chamber was filled with 40 mL of a 0.1 M KHCO3 solution. The working electrode was placed in the cathode chamber, the counter electrode was placed in the anode chamber, and the reference electrode was placed in the cathode chamber. During the electrocatalytic reduction of carbon dioxide reaction, carbon dioxide was passed into the cathode chamber for 25 min, and the carbon dioxide flow rate was set to 40 mL min -1 ; The voltages applied between the working electrode and the counter electrode were -1.6 V, -1.65 V, -1.7 V, -1.75 V, and -1.8 V (Ag / AgCl). The catalytic reduction products were CO and H2, and the catalytic reduction products were detected every 15 minutes.

[0090] Application Example 2 The electrocatalyst electrodes with Cu2O and Zn prepared in Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, and Example 12 were respectively used as cathodes of the electrochemical catalytic reduction of carbon dioxide reaction system. A three-electrode system was used to construct the electrochemical system. The prepared charged catalyst electrode was used as the working electrode for the electrochemical reduction of carbon dioxide reaction. A 1 cm×1 cm platinum sheet was used as the counter electrode for the electrochemical reduction of carbon dioxide reaction. An Ag / AgCl electrode was used as the reference electrode for the electrochemical reduction of carbon dioxide reaction. The cathode chamber and the anode chamber of the electrolytic cell were separated by a proton exchange membrane. The cathode chamber was filled with 40 mL of 0.1 M KHCO3 solution, and the anode chamber was filled with 40 mL of 0.1 M KHCO3 solution. The working electrode was placed in the cathode chamber, the counter electrode was placed in the anode chamber, and the reference electrode was placed in the cathode chamber. During the electrocatalytic reduction of carbon dioxide reaction, carbon dioxide was passed into the cathode chamber for 25 min, and the carbon dioxide flow rate was set to 40 mLmin -1 The voltages applied between the working electrode and the counter electrode were -1.6 V, -1.65 V, -1.7 V, -1.75 V, and -1.8 V (Ag / AgCl). The catalytic reduction products were CO and H2, and the catalytic reduction products were detected every 15 minutes. The results are as follows: Experimental results analysis from Figure 1It can be seen that the highest Faradaic efficiency of Example 1 for generating CO at -1.65 V is 94.3%, the Faradaic efficiency for generating H2 is 16.2%, and the total current density reaches 9.63 mA cm -2 .

[0091] from Figure 2 It can be seen that the reduction time t of the constant current reduction changes. As the reduction time t changes from 0 s to 7200 s, the CO yield of the three-dimensional porous copper oxide-zinc bimetallic thin film electrode at a reduction time of t=5400 s is significantly higher than that of the electrodes prepared under other oxidation current conditions; at a potential of -1.65 V, its CO yield is 94.3%, which is better than the thin film electrodes prepared under other reduction time conditions, thus proving that the three-dimensional porous copper oxide-zinc bimetallic thin film electrode has the best selectivity and catalytic activity for the electrochemical reduction of carbon dioxide to CO at a reduction time of t=5400 s.

[0092] from Figure 3 It can be seen that the oxidation current I1 of the multi-cycle pulse current has changed. As the oxidation current density I1 changes from +10 mA cm -2 Change to +40mA cm -2 The three-dimensional porous copper oxide-zinc bimetallic film electrode has an oxidation current density of I1 = +20 mA cm -2 The CO yield of the three-dimensional porous copper oxide-zinc bimetallic film electrode at an oxidation current density of I1 = +20 mA cm-3 was significantly higher than that of the electrodes prepared under other oxidation current conditions; at a potential of -1.65 V, its CO yield was 94.3%, which was better than that of the film electrodes prepared under other oxidation current conditions. -2 It has the best selectivity and catalytic activity for the electrochemical reduction of carbon dioxide to CO.

[0093] from Figure 4 It can be seen that the reduction current I2 of the multi-cycle pulse current has changed. As the reduction current density I2 changes from -20 mA cm -2 Change to -60mA cm -2 , the three-dimensional porous copper oxide-zinc bimetallic film electrode was subjected to a reduction current density of I2 = -50 mA cm -2 The CO yield of the three-dimensional porous copper oxide-zinc bimetallic thin film electrode at a reduction current density of I2 = -50 mA cm-3 was significantly higher than that of the electrodes prepared under other oxidation current conditions; at a potential of -1.65 V, its CO yield was 94.3%, which was better than that of the thin film electrodes prepared under other reduction current conditions. -2 It has the best selectivity and catalytic activity for the electrochemical reduction of carbon dioxide to CO.

[0094] from Figure 5 It can be seen that the number of cycles of the multi-cycle pulse current has changed. As the number of cycles changes from 150 to 600, the CO yield of the three-dimensional porous copper oxide-zinc bimetallic thin film electrode at 300 cycles is significantly higher than that of the electrodes prepared under other oxidation current conditions; at a potential of -1.65 V, its CO yield is 94.3%, which is better than that of the thin film electrodes prepared under other reduction current conditions, thus proving that the three-dimensional porous copper oxide-zinc bimetallic thin film electrode has the best selectivity and catalytic activity for the electrochemical reduction of carbon dioxide to CO at 300 cycles.

[0095] from Figure 6 It can be seen that the copper-zinc deposition solutions subjected to multi-cycle pulse current are different. The maximum Faraday efficiency for generating CO at -1.65 V in Example 1 is 94.3%; the maximum Faraday efficiency for generating CO at -1.7 V in Example 11 is only 84.1%; and the maximum Faraday efficiency for generating CO at -1.75 V in Example 12 is only 82.4%.

[0096] from Figure 7 It can be seen that the electrolytes used for long-term constant current reduction are different. The maximum Faraday efficiency for generating CO at -1.65 V in Example 1 is 94.3%; the maximum Faraday efficiency for generating CO at -1.65 V in Example 13 is only 72.6%; the maximum Faraday efficiency for generating CO at -1.7 V in Example 14 is only 65.7%; and the maximum Faraday efficiency for generating CO at -1.7 V in Example 15 is only 53.8%.

[0097] from Figure 8 It can be seen that the copper-zinc deposition solutions subjected to multi-cycle pulse current are different. The maximum Faraday efficiency for generating CO at -1.65 V in Example 1 is 94.3%; the maximum Faraday efficiency for generating CO at -1.65 V in Example 16 is only 62.7%; the maximum Faraday efficiency for generating CO at -1.7 V in Example 17 is only 70.2%; and the maximum Faraday efficiency for generating CO at -1.7 V in Example 18 is only 78.3%.

[0098] from Figure 9 It can be seen from the SEM image of the three-dimensional porous copper oxide-zinc bimetallic thin film electrode prepared in Example 1 that the nanoparticles are evenly distributed on the surface, presenting a regular loose porous structure, and the particle size is 10 nm to 200 nm.

[0099] from Figure 10 It can be seen from the SEM image of the copper oxide-zinc bimetallic thin film electrode prepared in Comparative Example 1 that large nano-flower-like particles (particle size ~5 μm) are formed on its surface.

[0100] from Figure 11 It can be seen from the EDS image of the three-dimensional porous copper oxide-zinc bimetallic thin film electrode prepared in Example 1 that the Zn element is dispersed in the form of large particles and is more concentrated than other areas, while the Cu element appears as uniform and dense nano-oxide particles. The O element signal is evenly distributed, confirming the successful construction of the three-dimensional electrode.

[0101] from Figure 12 It can be seen that the three-dimensional porous copper oxide-zinc bimetallic thin film electrode prepared in Example 1 presents a triple phase: copper substrate, elemental Zn, a small amount of ZnO and Cu2O. Analysis confirmed that the reduction process triggered a partial transformation of ZnO to Zn and a gradient reduction of CuO to Cu2O / Cu.

[0102] from Figure 13 It can be seen that the H-type electrolytic cell device for the constant current reduction process uses a three-electrode system to construct an electrochemical system, with the catalyst electrode as the working electrode, a 1cm×1cm platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode; the cathode chamber and the anode chamber of the electrolytic cell are separated by a proton exchange membrane, the cathode chamber is filled with 40mL of 0.1M KHCO3 solution, the anode chamber is filled with 40mL of 0.1M KHCO3 solution, the working electrode is placed in the cathode chamber, the counter electrode is placed in the anode chamber, and the reference electrode is placed in the cathode chamber.

[0103] Experimental verification demonstrates that the thin-film electrode prepared by the present invention exhibits excellent catalytic activity and good selectivity for a single product. Compared with existing technologies, the present invention utilizes a wider range of raw materials, offers low-cost raw materials, and features a simple preparation method, which helps improve carbon dioxide conversion efficiency and meets the "dual carbon" goals.

[0104] The above-described embodiments are only preferred embodiments of the present invention, and are not intended to be all feasible embodiments of the present invention. Any obvious modifications made by a person skilled in the art without departing from the principles and spirit of the present invention should be considered to be included within the scope of protection of the claims of the present invention.

Claims

1. A three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide, characterized by: A three-dimensional porous copper oxide-zinc bimetallic thin film electrode was in situ grown on a copper substrate through a synergistic construction strategy of pulse co-deposition and long-time constant current reduction. First, a pulse method is used to alternately output positive and negative current densities to regulate the periodic deposition-etching process on the electrode surface, and a pulsed current electrodeposition layer is in situ deposited on the substrate surface. The electrode was then subjected to long-term constant current reduction in an H-type electrolytic cell, which caused the pulsed deposited layer to undergo structural reconstruction, forming a three-dimensional porous copper oxide-zinc bimetallic film electrode containing copper oxide and zinc as the surface catalytic layer. The three-dimensional porous copper oxide-zinc bimetallic thin film electrode includes a substrate and a surface catalytic layer attached to the substrate. The copper oxide-zinc bimetallic thin film electrode uses a copper mesh as a substrate, and the surface catalytic layer is composed of copper oxide and zinc, wherein the proportion of copper oxide is 1 to 40 wt%.

2. The three-dimensional porous copper oxide-zinc bimetallic film electrode for carbon dioxide electroreduction according to claim 1, characterized in that: The mesh number of the copper mesh is 100-300 mesh, and the wire diameter is 0.01mm-0.3mm; The copper oxide in the surface catalytic layer of the three-dimensional porous copper oxide-zinc bimetallic film electrode is one or both of Cu2O and CuO, and the loading amount of the surface catalytic layer is 5 mg cm -2 ~20 mg cm -2 ; Nanoparticles on the surface of the copper mesh are evenly distributed around the mesh, presenting a regular loose porous structure with particle sizes ranging from 10 nm to 250 nm. The pore volume of the surface catalytic layer is 2 cm 3 g -1 ~6 cm 3 g -1 , the pore size distribution is between 1 nm and 20 nm.

3. A method for preparing the three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide according to claim 1, characterized in that: The following steps are included: Step 1): Place 0.5cm 2 ~6cm 2 The copper mesh substrate is placed in 10 mL to 100 mL of 0.1 M to 5 M HCl for chemical etching for 5 min to 40 min, and then ultrasonically cleaned in anhydrous ethanol and water in sequence, and dried to obtain the pretreated copper mesh T-CM; Step 2): placing the pretreated copper mesh T-CM obtained after treatment into an electrolyte for pulse current electrodeposition, wherein the pulse current has an oxidation current density I1 and an oxidation time T1, and a reduction current density I2 and a reduction time T2, and the exchange cycle is performed more than 10 times under the conditions of I1 and I2; Step 3): The electrode obtained in step 2) is rinsed in anhydrous ethanol and water in sequence, and a current is applied to the electrode surface in an alkaline electrolyte at room temperature under inert atmosphere and constant current reduction reconstruction method for a long time; Step 4): The electrode prepared in step 3) is rinsed in anhydrous ethanol and water in sequence, and then dried to prepare a three-dimensional porous copper oxide-zinc bimetallic thin film electrode; In step 2), the electrolyte is zinc salt, copper salt and sodium salt dissolved in deionized water to form a copper-zinc deposition solution, the zinc salt is one or more of zinc nitrate, zinc sulfate and zinc chloride, and the concentration of the zinc salt is 0.01 M to 2 M; the copper salt is one or more of copper nitrate, copper sulfate and copper chloride, and the concentration of the copper salt is 0.001 M to 0.5 M; the sodium salt is one or more of sodium nitrate, sodium sulfate and sodium chloride, and the concentration of the sodium salt is 0.01 M to 1 M; In step 3), the alkaline electrolyte is one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate, and the reduction current density of the long-term constant current reduction reconstruction method is -2 mA cm -2 ~-100 mA cm -2 , the reduction time t is 4500s~12000s.

4. The method for preparing a three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide according to claim 3, characterized in that: After chemical etching, ultrasonic cleaning is performed in anhydrous ethanol and water for 3 min to 60 min.

5. The method for preparing a three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide according to claim 3, characterized in that: The oxidation current density I1 is 5 mA cm -2 ~60 mA cm -2 ; The reduction current density I2 is -10 mA cm -2 ~-80 mA cm -2 ; The oxidation time T1 is 0.2 s to 20 s; the reduction time T2 is 0.4 s to 25 s; the number of cycles under I1 and I2 conditions is 10 to 1000 cycles.

6. The method for preparing a three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide according to claim 3, characterized in that: The alkaline electrolyte is dissolved in 100 mL to 300 mL of deionized water, and the electrolyte concentration is 0.01 M to 2 M.

7. Use of the three-dimensional porous copper oxide-zinc bimetallic film electrode for electroreduction of carbon dioxide according to claim 1 or 2, characterized in that: A three-dimensional porous copper oxide-zinc bimetallic film electrode is used as the cathode electrode for the electrochemical reduction of carbon dioxide.

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