Proton sponge modified fluorine atom doped metal copper electrode material and preparation method and application thereof

Abstract

The invention relates to the field of electrocatalyst development and technology, and discloses a preparation method and application of a proton sponge modified fluorine atom doped metal copper electrode material, and the preparation method comprises the following steps: adding a dispersion liquid of proton sponge into a dispersion liquid of a copper hydroxyfluoride precursor to obtain a mixed solution; uniformly spraying the mixed solution on a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a proton sponge modified hydroxyl copper fluoride precursor electrode material; and performing electrochemical reduction to obtain the proton sponge modified fluorine atom doped metal copper electrode material. The invention further discloses the proton sponge modified fluorine atom doped metal copper electrode material obtained through the preparation method and application of the proton sponge modified fluorine atom doped metal copper electrode material serving as a working electrode to a carbon dioxide electroreduction reaction. The electrode material provided by the invention shows excellent CO2 electroreduction performance in an acid environment, and realizes high selectivity for preparing a high-added-value C2 + product under the industrial-grade current density.

Description

Technical Field

[0001] The present invention relates to the field of electrocatalyst development and technology, and in particular to a proton sponge-modified fluorine atom-doped metallic copper electrode material, a preparation method thereof, and applications thereof. Background Art

[0002] The electroreduction of carbon dioxide (CO2) driven by renewable energy provides a promising technical path for the capture, conversion and utilization of CO2. The electroreduction of CO2 technology can achieve efficient conversion and utilization of CO2 using renewable electricity under mild conditions. Among them, ethylene (C2H4), ethanol (C2H5OH), acetic acid (CH3COOH) and propanol (C3H7OH) with high energy density are the most widely used carbon dioxide (CO2) products. 2+ ) compounds as ideal value-added products can not only provide green raw materials for the chemical industry, but also effectively alleviate the contradiction between climate change and energy demand, thus attracting extensive attention from academia and industry. 2+ Product selectivity. The electrolyte of most CO2 electroreduction reactions is alkaline or neutral. However, carbonates formed by CO2 electroreduction reactions in alkaline or neutral environments will precipitate at the cathode or migrate to the anode, causing CO2 crossover problems, reducing the utilization efficiency of CO2, and the regeneration process also requires a lot of additional energy consumption. In contrast, CO2 electroreduction reactions in acidic environments can reduce the protons (H + ) is combined with carbonate to convert into CO2, thereby improving the overall energy efficiency, but it is accompanied by a large amount of H + Preferentially combined with the side reaction of hydrogen evolution in water electrolysis, resulting in C 2+ The selectivity of the product is reduced. Therefore, the development of electrocatalysts that can significantly improve the performance of CO2 electroreduction in acidic environments and effectively inhibit the hydrogen evolution side reaction still faces great challenges.

[0003] To date, copper-based catalysts have been widely used in the electroreduction of CO2 due to their unique electronic structure and excellent carbon-carbon (CC) coupling ability. Most studies have improved the intrinsic catalytic activity of copper-based catalysts by regulating their own electronic structure and chemical composition. Common regulation strategies include element doping, crystal plane regulation, defect formation, alloying, etc. Among them, the core advantage of the element doping strategy lies in the precise regulation of the "electronic structure-geometric structure-surface properties" of the catalyst, thereby breaking through the performance limitations of a single element component. For example, the Chinese patent document with publication number CN119433589A discloses an in-situ synthesized halogen-modified bismuth nanoelectrocatalytic electrode, its preparation method and application, which synthesizes a precursor by grafting halogen atoms on the surface of basic copper bismuthate through water bath treatment, and then obtains a halogen-modified bismuth nanomaterial by electrochemical reduction, which effectively inhibits the hydrogen evolution reaction, improves the reaction current density, and exhibits excellent performance in the electroreduction of CO2 to prepare formic acid.

[0004] With the continuous deepening of research on improving the performance of CO2 electroreduction reaction, it is not limited to the optimization of the intrinsic performance of electrocatalysts, but has gradually turned to the regulation of the microenvironment of the electrode material reaction interface, providing a new approach for improving the performance of CO2 electroreduction reaction. For example, the Chinese patent document with publication number CN119593013A discloses a preparation method and application of a CO2 gas capture functional molecule modified nano-gold catalyst. After the functional molecule is added to an organic solvent and heated in an oil bath with the nano-gold catalyst, an organic molecule modified nano-gold catalyst with CO2 gas capture function is obtained. After the organic molecule modification, a hydrophobic microenvironment at the interface is provided that is conducive to the CO2 reduction reaction, significantly enhancing the diffusion of CO2 gas and effectively reducing the hydrogen evolution side reaction, thereby improving the selectivity of the CO2 electroreduction reaction.

[0005] There has been some progress in the research on the modification of CO2 electroreduction reaction catalysts and the regulation of the reaction interface microenvironment, but there are still many challenges in achieving high selectivity and high stability of CO2 electroreduction reaction under acidic conditions and clarifying its microscopic reaction mechanism. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a proton sponge (1,8-bisdimethylaminonaphthalene) modified fluorine atom-doped metallic copper electrode material. The prepared proton sponge modified fluorine atom-doped metallic copper electrode material exhibits excellent CO2 electroreduction reaction performance in an acidic environment at industrial-grade current density.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A method for preparing a proton sponge-modified fluorine atom-doped metallic copper electrode material, the method comprising the following steps:

[0009] (1) adding a dispersion of proton sponge (1,8-bis(dimethylaminonaphthalene)) to a dispersion of a hydroxycopper fluoride precursor to obtain a mixed solution;

[0010] (2) spraying the mixed solution onto a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a proton sponge-modified copper hydroxyfluoride precursor electrode material;

[0011] (3) The proton sponge-modified hydroxy copper fluoride precursor electrode material prepared in step (2) is electrochemically reduced to obtain a proton sponge-modified fluorine atom-doped metallic copper electrode material.

[0012] The preparation principle of the proton sponge-modified fluorine-doped metallic copper electrode material provided by the present invention is as follows: a hydroxy copper fluoride (Cu(OH)F) precursor is mixed with a proton sponge and then evenly sprayed on a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a proton sponge-modified Cu(OH)F precursor electrode material, which is then subjected to constant current electrochemical reduction to obtain a proton sponge-modified fluorine-doped metallic copper electrode material. Fluorine atoms doping metallic copper promote the migration of hydrated potassium ions to the electrode interface and repel H + The migration of ions is used to suppress the occurrence of hydrogen evolution side reaction. The electrode surface effectively regulates the local electric field of the reaction interface by introducing a proton sponge, changes the dipole moment of the intermediate *CO to enhance its adsorption, thereby reducing the reaction energy barrier of CC coupling and improving the preparation of high value-added C 2+ Product performance.

[0013] Preferably, in step (1), the preparation method of the hydroxycopper fluoride precursor is: dissolving an inorganic copper salt in an N,N-dimethylformamide solvent, adding ammonium bifluoride and stirring, and performing a hydrothermal reaction and then centrifugation drying to obtain a hydroxycopper fluoride precursor.

[0014] In a mixed solution of N,N-dimethylformamide in which copper nitrate is uniformly dispersed, ammonium bifluoride is added as a fluorine source, and a hydroxy copper fluoride (Cu(OH)F) precursor is synthesized under weak alkaline conditions through a high-temperature hydrothermal reaction. In the present invention, the use of a weak alkaline solution and ammonium bifluoride is conducive to the synthesis of a more uniform hydroxy copper fluoride precursor.

[0015] Preferably, the inorganic copper salt is copper nitrate trihydrate.

[0016] Preferably, the stirring and mixing time is 15 to 30 minutes. Preferably, the stirring time is 30 minutes.

[0017] Preferably, the hydrothermal reaction temperature is 120-160°C, and the reaction time is 2-4 hours. If the hydrothermal temperature is too low, a highly crystalline, shaped Cu(OH)F precursor cannot be formed. If the hydrothermal time is too short, complete reaction of the copper ions cannot be ensured. Preferably, the hydrothermal reaction temperature is 160°C, and the reaction time is 4 hours.

[0018] In step (1), the proton sponge and the copper hydroxyfluoride precursor are dissolved in a solvent to form a dispersion; the solvent is methanol, ethanol and isopropanol. Preferably, the solvent is methanol.

[0019] In step (1), the mass ratio of the proton sponge to the hydroxy copper fluoride precursor is 0.04 to 0.065:1. When the mass ratio is low, the intermediate *CO is enhanced to be adsorbed and converted into C 2+ The effect of the product is not obvious; when its mass ratio is high, single C 2+ The selectivity of the product ethylene (C2H4) decreases. Preferably, the mass ratio of the proton sponge to the hydroxy copper fluoride precursor is 0.05 to 0.065:1, which is beneficial to improve the selectivity of the single C 2+ Selectivity of the product ethylene (C2H4).

[0020] In step (2), the loading amount of the proton sponge-modified hydroxy copper fluoride precursor on the polytetrafluoroethylene film substrate loaded with copper nanoparticles is 0.5-1 mg cm -2 Preferably, the loading amount of the proton sponge-modified copper hydroxyfluoride precursor is 1 mg cm -2 .

[0021] In step (2), the copper nanoparticle layer loaded on the polytetrafluoroethylene membrane has a thickness of 200 to 400 nm. Thicker copper nanoparticles help enhance the conductivity of the substrate. Preferably, the copper nanoparticle layer has a thickness of 400 nm.

[0022] In step (3), the constant current density of the electrochemical reduction is 50-100 mA cm -2 , time is 100~300s. Preferably, the constant current density of electrochemical reduction is 100mA cm -2 , time is 300s.

[0023] The present invention also provides a proton sponge-modified fluorine atom-doped metallic copper electrode material obtained according to the above preparation method.

[0024] In the proton sponge-modified fluorine atom-doped metallic copper electrode material, the mass ratio of the proton sponge to the hydroxy copper fluoride precursor is 0.04-0.065:1, and the thickness of the copper nanoparticle layer on the polytetrafluoroethylene membrane is 200-400 nm.

[0025] The present invention also provides the above-mentioned proton sponge-modified fluorine atom-doped metal copper electrode material for use as a working electrode in an electroreduction CO2 reaction.

[0026] Furthermore, the proton sponge modified fluorine atom-doped metal copper electrode material is used as a working electrode to realize the application of CO2 electroreduction in an acidic environment at an industrial-grade current density.

[0027] The proton sponge modified fluorine atom doped metal copper electrode material provided by the present invention exhibits an industrial grade current density (200-1000 mA cm) as a working electrode. -2 )Excellent performance in electroreduction of CO2 in acidic environment.

[0028] The fluorine atom doping in the proton sponge modified fluorine atom-doped metal copper electrode material provided by the present invention promotes the enrichment of hydrated potassium ions at the reaction interface, inhibits H + The migration of ions to the electrode interface greatly reduces the hydrogen evolution side reaction. At the same time, the proton sponge modification effectively regulates the local electric field strength of the reaction interface, affects the dipole moment of the intermediate *CO to enhance its adsorption of *CO, and reduces the reaction energy barrier of CC coupling to increase its production of high value-added C 2+ The performance of the product has practical significance for realizing the electroreduction of CO2 in an acidic environment under industrial conditions.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The proton sponge modified fluorine atom doped metal copper electrode material provided by the present invention realizes high selective electroreduction of CO2 to prepare high value-added C in acidic environment 2+ The product performance provides the possibility for further industrial application;

[0031] (2) The proton sponge modified fluorine atom-doped metal copper electrode material provided by the present invention achieves the enrichment effect of hydrated potassium ions at the electrode interface by fluorine atom doping, thereby inhibiting H + The ions migrate to the electrode interface, effectively reducing the hydrogen evolution side reaction. The introduction of the proton sponge is beneficial to regulating the local electric field strength at the electrode reaction interface, enhancing the adsorption of the intermediate *CO, and reducing the CC coupling reaction energy barrier, thereby promoting the generation of C 2+ The product demonstrated excellent performance in acidic electroreduction of CO2 at industrial-grade current density. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a scanning electron microscope image of the precursor Cu(OH)F prepared in Example 1;

[0033] Figure 2X-ray diffraction pattern of the electrode material Cu-F prepared in Example 1;

[0034] Figure 3 X-ray photoelectron spectrum of the Cu-F electrode material prepared in Example 1;

[0035] Figure 4 The electrode material prepared in Example 1 has a flow rate of 100-1000 mA cm when the electrolyte pH is 1.5 and pH is 1.0. -2 In the current density range, C2H4 and C 2+ Faradaic efficiency of the product;

[0036] Figure 5 The electrode materials prepared in Examples 1 to 3 are 100 to 1000 mA cm-2 when the electrolyte pH is 1.5 in the application example. -2 In the current density range, C2H4 and C 2+ Faradaic efficiency of the product;

[0037] Figure 6 The electrode materials prepared in Example 1 and Comparative Example 1 are 100-1000 mA cm -2 Faradaic efficiency of CO2 electroreduction to different products within the current density range;

[0038] Figure 7 The electrode materials prepared in Comparative Examples 1 to 5 are 500 mA cm -2 Faradaic efficiency of CO2 electroreduction to different products at different current densities;

[0039] Figure 8 The electrode material prepared in Example 1 is used in the application example when the electrolyte pH is 1.5 and the current is 200 mA cm -2 Stability test under current density. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment.It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.Those skilled in the art will modify or make equivalent replacements based on understanding the technical solution of the present invention, and without departing from the spirit and scope of the technical solution of the present invention, all should be encompassed within the protection scope of the present invention.The raw materials used in the following specific embodiments are all purchased from the market.

[0041] Example 1

[0042] (1) 483.2 mg of copper nitrate trihydrate solid particles were weighed and dissolved in 50 mL of N,N-dimethylformamide solvent, stirred at room temperature until completely dissolved, and then 114.1 mg of ammonium bifluoride solid particles were added and stirred for 30 min; the obtained mixed solution was transferred to a 100 mL hydrothermal reactor and hydrothermally reacted at 160 ° C for 4 h, then centrifuged and washed with water and ethanol for more than 3 times, and finally dried in a vacuum oven at 60 ° C overnight to obtain a hydroxy copper fluoride precursor.

[0043] (2) Weigh 20 mg of the hydroxycopper fluoride precursor obtained in step (1) and disperse it in a dispersion of 2.5 mL of methanol and 80 μL of Nafion. Dissolve the proton sponge in methanol solution to obtain a 40-60 mM dispersion. Then, measure 100 μL of a dispersion of a proton sponge dissolved in methanol with a molar concentration of 50 mM and add it to the dispersion of the hydroxycopper fluoride precursor. After mixing evenly, the mass ratio of the proton sponge to the hydroxycopper fluoride precursor is 0.0536:1.

[0044] (3) Measure the mixed solution prepared in step (2) and spray it evenly to 2*2cm 2 The copper nanoparticles were placed on a polytetrafluoroethylene film substrate, and the substrate mass was weighed before and after to ensure a loading of 1 mg cm -2 , in 3M KCl (pH = 1.5) electrolyte, 100mA cm -2 Under the current density, the constant current electroreduction reaction was carried out for 300s to obtain a proton sponge-modified fluorine atom-doped metallic copper electrode material.

[0045] The macroscopic morphology of the prepared copper hydroxyfluoride precursor was observed by scanning electron microscopy. Figure 1 As shown, it can be seen that its morphological structure is a sheet structure. The X-ray diffraction pattern of the proton sponge modified fluorine atom doped metal copper electrode material is shown in Figure 2 As shown in FIG, the characteristic peaks of the metallic copper crystal phase can be seen. The X-ray photoelectron spectrum of the proton sponge modified fluorine atom doped metallic copper electrode material prepared in this embodiment is shown in FIG. Figure 3 As shown, the characteristic peak of fluorine doping can be seen, indicating the successful preparation of proton sponge modified fluorine atom-doped metal copper electrode material.

[0046] Example 2

[0047] According to the preparation process of Example 1, the 50 mM dispersion of the proton sponge dissolved in methanol in step (2) was changed to 40 mM, and the other steps remained unchanged, to obtain a mass ratio of the proton sponge to the hydroxycopper fluoride precursor of 0.0429:1.

[0048] Example 3

[0049] According to the preparation process of Example 1, the 50 mM dispersion of the proton sponge dissolved in methanol in step (2) was changed to 60 mM, and the other steps remained unchanged, to obtain a mass ratio of the proton sponge to the hydroxycopper fluoride precursor of 0.0643:1.

[0050] Comparative Example 1

[0051] According to the preparation process of Example 1, 100 μL of a dispersion of a proton sponge dissolved in methanol with a molar concentration of 50 mM was added to the dispersion of the hydroxy copper fluoride precursor in step (2) without performing the other steps, and the fluorine atom-doped metallic copper electrode material was obtained.

[0052] Comparative Example 2

[0053] According to the preparation process of Comparative Example 1, the addition of 114.1 mg of ammonium bifluoride solid particles in step (1) was not performed, and step (1) was changed to a hydrothermal reaction at 220° C. for 36 h to obtain a pure metallic copper electrode material.

[0054] Comparative Example 3

[0055] According to the preparation process of Comparative Example 1, 300 mg of ammonium chloride was dissolved in 50 mL of a mixed solution of ethanol and water with a volume ratio of 49:1, and then 50 mg of the hydroxycopper fluoride precursor prepared in step (1) was added. After stirring at room temperature for 36 hours, the mixture was washed and dried to obtain a hydroxycopper chloride precursor. The hydroxycopper fluoride precursor in step (2) was replaced with a hydroxycopper chloride precursor to obtain a chlorine atom-doped metallic copper electrode material.

[0056] Comparative Example 4

[0057] According to the preparation process of Comparative Example 1, 300 mg of ammonium bromide was dissolved in 50 mL of a mixed solution of ethanol and water with a volume ratio of 49:1, followed by the addition of 50 mg of the hydroxycopper fluoride precursor prepared in step (1). The mixture was stirred at room temperature for 36 hours and then washed and dried to obtain a hydroxycopper bromide precursor. The hydroxycopper fluoride precursor in step (2) was replaced with a hydroxycopper bromide precursor to obtain a bromine-doped metallic copper electrode material.

[0058] Comparative Example 5

[0059] According to the preparation process of the comparative example, 300 mg of ammonium iodide was dissolved in a mixed solution of 50 mL of ethanol and water with a volume ratio of 49:1, and then 50 mg of the hydroxy copper fluoride precursor prepared in step (1) was added. After stirring at room temperature for 36 hours, the mixture was washed and dried to obtain a cuprous iodide precursor. The hydroxy copper fluoride precursor in step (2) was replaced with a cuprous iodide precursor to obtain an iodine atom-doped metallic copper electrode material. Application Example Electroreduction of CO2 in an acidic environment at an industrial-grade current density

[0060] The prepared electrode material was first used as the working electrode in a three-electrode flow electrolysis cell. A cation exchange membrane (Nafion 117) separated the flow chambers on either side of the device. The catholyte was a 3.0 M KCl solution (adjusted with a 0.5 M H₂SO₄ solution) at pH 1.5 and pH 1.0, respectively, and the anolyte was 0.05 M H₂SO₄. The reference and counter electrodes were platinum and silver / silver chloride electrodes, respectively.

[0061] Cyclic voltammetry (CV) activation was performed using a Shanghai Chenhua CHI 760E electrochemical workstation with a CV program in the range of -0.5 to -1.9 V vs. RHE at a scan rate of 50 mV s. -1 , the electrode reaches a stable state after 30 cycles of scanning.

[0062] Linear sweep voltammetry (LSV) test: After CV activation, switch the program to LSV program, test the range from -0.5 to -1.9 V vs. RHE, and scan rate of 5 mV s -1 .

[0063] Faradaic efficiency (FE) test: The program was switched to constant current-time test. During the constant current test, the concentration of the gas phase product was quantitatively determined online using gas chromatography (GC, Fuli 9790II), and the concentration of the liquid phase product was determined using nuclear magnetic resonance analysis. The Faradaic efficiency of all products was calculated.

[0064] The proton sponge modified fluorine atom doped copper electrode material prepared in Example 1 was heated to 100-1000 mA cm -2 The current range shows excellent acidic CO2 electroreduction performance, and the results are as follows Figure 4 As shown, when the electrolyte pH is 1.5 and pH is 1.0, at 500mA cm -2 At the current density, the Faradaic efficiency of C2H4 products reached 56.8% and 52.6%, respectively. 2+ The maximum Faradaic efficiency of the products reached 79.5% and 71.5% respectively, and the -2 Within the current density range, the selectivity of C2H4 product remains above 41%.

[0065] The proton sponge modified fluorine atom-doped copper electrode materials prepared in Examples 1 to 3 were subjected to a current of 100 to 1000 mA cm -2 Current range of C2H4 and C 2+ Comparison of products, the results are as follows Figure 5 As shown, the performance of Example 1 is better than that of Example 2 and Example 3.

[0066] The electrode materials prepared in Example 1 and Comparative Example 1 were subjected to a 100-1000 mA cm -2 The performance of acidic electroreduction of CO2 within the current density range was compared. The results are as follows Figure 6 As shown in Table 1, the performance of the proton sponge modified fluorine atom doped metal copper electrode material prepared in Example 1 is much better than that of Comparative Example 1 in an acidic environment.

[0067] Table 1 Electrode materials prepared in Example 1 and Comparative Example 1 at 100-1000 mA cm -2 Acidic CO2 electroreduction performance across a range of current densities

[0068]

[0069] The halogen atom-doped copper electrode materials and pure copper electrode materials prepared in Comparative Examples 1 to 5 were heated at 500 mA cm -2 The performance of acidic electroreduction of CO2 under current density is compared. The results are as follows Figure 7 As shown in Table 2, the hydrogen production Faraday efficiency of Comparative Example 1 is the lowest. Compared with the pure metal copper electrode material, the halogen atom doping significantly inhibits the occurrence of the hydrogen evolution side reaction.

[0070] Table 2 Comparative Examples 1 to 5 prepared halogen atom doped copper electrode materials and pure copper electrode materials at 500 mA cm -2 Comparison of acidic CO2 electroreduction performance under different current densities

[0071]

[0072] The electrode material prepared in Example 1 was tested for stability in a flow electrolysis cell. The results are as follows: Figure 8 As shown, at 200mA cm -2 It can operate stably for 24 hours at a current density of 100 nm, and the Faradaic efficiency of the C2H4 product remains above 40%.

Claims

1. A method for preparing a proton sponge-modified fluorine-doped metallic copper electrode material, characterized in that: The preparation method comprises the following steps: (1) adding a dispersion of a proton sponge to a dispersion of a hydroxycopper fluoride precursor to obtain a mixed solution; (2) spraying the mixed solution onto a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a proton sponge-modified copper hydroxyfluoride precursor electrode material; (3) The proton sponge-modified hydroxy copper fluoride precursor electrode material prepared in step (2) is electrochemically reduced to obtain a proton sponge-modified fluorine atom-doped metallic copper electrode material.

2. The method for preparing a proton sponge-modified fluorine atom-doped metallic copper electrode material according to claim 1, characterized in that: In step (1), the preparation method of the hydroxy copper fluoride precursor is as follows: after dissolving an inorganic copper salt in N,N-dimethylformamide solvent, adding ammonium bifluoride and stirring and mixing, after hydrothermal reaction, centrifugation and drying are performed to obtain the hydroxy copper fluoride precursor.

3. The method for preparing a proton sponge-modified fluorine-doped metallic copper electrode material according to claim 2, characterized in that: The hydrothermal reaction temperature is 120-160° C., and the hydrothermal reaction time is 2-4 hours.

4. The method for preparing a proton sponge-modified fluorine atom-doped metallic copper electrode material according to claim 1, characterized in that: In step (1), the mass ratio of the proton sponge to the hydroxycopper fluoride precursor is 0.04-0.065:

1.

5. The method for preparing a proton sponge-modified fluorine-doped metallic copper electrode material according to claim 1, characterized in that: In step (2), the thickness of the copper nanoparticle layer on the polytetrafluoroethylene film is 200 to 400 nm.

6. The method for preparing a proton sponge-modified fluorine-doped metallic copper electrode material according to claim 1, characterized in that: In step (2), the loading amount of the proton sponge-modified copper hydroxyfluoride precursor on the polytetrafluoroethylene film-supported copper nanoparticle substrate is 0.5-1 mg cm -2 .

7. The method for preparing a proton sponge-modified fluorine-doped metallic copper electrode material according to claim 1, characterized in that: In step (3), the constant current density of the electrochemical reduction is 50-100 mA cm -2 , the time is 100 to 300 seconds.

8. A proton sponge-modified fluorine atom-doped metallic copper electrode material obtained by the preparation method according to any one of claims 1 to 7.

9. A proton sponge-modified fluorine atom-doped metallic copper electrode material according to claim 8, used as a working electrode in an electroreduction of carbon dioxide reaction.

10. The use of the proton sponge modified fluorine atom-doped metallic copper electrode material according to claim 9, characterized in that: The proton sponge-modified fluorine atom-doped metal copper electrode material is used as a working electrode to realize the application of electroreduction of carbon dioxide in an acidic environment at an industrial-grade current density.

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