Benzothiadiazole modified monatomic zirconium 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 benzothiadiazole-modified monatomic zirconium-doped metal copper electrode material and a preparation method and application thereof, and the preparation method comprises the following steps: dissolving an inorganic copper salt and an inorganic zirconium salt, and then adding an alkaline solution; carrying out hydrothermal reaction to obtain a monatomic zirconium-doped copper oxide precursor; dissolving benzothiadiazole, and adding the dissolved benzothiadiazole into the dispersion liquid of the monatomic zirconium-doped copper oxide precursor to obtain a mixed solution; spraying the mixed solution on a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a benzothiadiazole modified monatomic zirconium doped copper oxide precursor electrode material; and performing electrochemical reduction treatment to obtain the benzothiadiazole modified monatomic zirconium doped metal copper electrode material. The electrode material is used as a working electrode to be applied to a carbon dioxide electroreduction reaction, shows excellent CO2 electroreduction performance in an acid environment, and realizes high-selectivity preparation of 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 benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material, a preparation method thereof, and applications thereof. Background Art

[0002] The over-exploitation of traditional fossil energy has led to excessive emissions of carbon dioxide (CO2), causing serious environmental problems. Reducing CO2 emissions while capturing and utilizing it is an important way to reduce environmental problems. Among them, electrochemical reduction of CO2 to high-value-added multi-carbon (C 2+ ) products, such as ethylene (C2H4), ethanol (C2H5OH), acetic acid (CH3COOH) and propanol (C3H7OH) and other chemicals, are considered to be one of the most promising technical directions for realizing carbon cycle in the future. At present, most of the electroreduction reactions of CO2 are carried out in alkaline or neutral electrolytes, so carbonates are inevitably formed, resulting in reduced CO2 utilization efficiency, and CO2 regeneration also requires additional energy consumption, thereby reducing the overall energy efficiency. The use of acidic electrolytes for electroreduction of CO2 can effectively solve the above problems, but the competitive electrolysis of water and hydrogen evolution reaction is more likely to occur in acidic environments, making the conversion of CO2 into high value-added C 2+ The product efficiency is reduced, so achieving the electroreduction of CO2 to high-value-added chemicals at industrial-grade current density in an acidic environment still faces major challenges.

[0003] Copper-based catalysts have the ability to deeply reduce CO2 to hydrocarbon products and have moderate adsorption energy for most carbon-containing intermediates, and are widely used in the electroreduction of CO2. However, due to the linear structure of CO2 molecules, the initial activation process is very difficult. At the same time, the electroreduction of CO2 is a multi-step proton-coupled electron transfer process with slow reaction kinetics, resulting in a single copper-based catalyst being unable to generate specific C 2+ The selectivity of the product is low, so it is necessary to develop a method that can effectively activate CO2 molecules and efficiently convert them into high value-added C 2+ The copper-based catalyst of the product is very necessary. At present, introducing a second component metal to dope the copper-based catalyst is one of the effective means of modifying it. For example, the Chinese patent document with publication number CN118727045A discloses a rare earth doped nanoporous copper-based catalyst and its preparation method and application. Since rare earth elements have unique electron orbits and exhibit excellent electron transfer ability, introducing them into the nanoporous copper-based catalyst can significantly improve C 2+ The Faradaic efficiency of the product is high, and the competitive hydrogen evolution reaction is effectively inhibited, thereby improving the stability.

[0004] Carbon-carbon (CC) coupling is usually considered to be 2+The key reaction step that determines the rate in the product formation process, however, the intermediate *CO is easy to desorb and the CC coupling reaction energy barrier is high, which greatly limits its reaction kinetics. Therefore, strengthening the adsorption of the intermediate *CO and reducing the CC coupling reaction energy barrier are effective methods to increase the rate of formation of the key intermediate *COCO (*COCOH). In recent years, the strategy of using organic molecules to modify the surface of electrode materials is a direct and effective modification method that can regulate the concentration of reactants on the catalyst surface and adjust the adsorption strength of reaction intermediates to improve performance, and has therefore been widely studied. For example, the Chinese patent document with publication number CN117070980A discloses an alkaline ionic liquid functionalized copper and its application in the electrocatalytic reduction of CO2 to prepare multi-carbon products. By introducing alkaline ionic liquid to functionalize the surface of the copper electrode, the performance of the electroreduction of CO2 has been significantly improved, C 2+ The Faradaic efficiency of the product is greater than 70%, which is significantly better than that of the unmodified copper electrode.

[0005] Although electroreduction of CO2 to synthesize high value-added C 2+ The research on products has made some progress, but there are still many challenges in achieving high current density and high selectivity electroreduction of CO2 under acidic conditions, especially single C 2+ The efficient and targeted synthesis of products still needs further exploration. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material. The prepared benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material exhibits excellent performance in the electroreduction of CO2 at industrial-grade current density in an acidic environment.

[0007] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:

[0008] A method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material, the preparation method comprising the following steps:

[0009] (1) dissolving an inorganic copper salt and an inorganic zirconium salt and then adding an alkaline solution to obtain a single-atom zirconium-doped copper oxide precursor through a hydrothermal reaction;

[0010] (2) dissolving benzothiadiazole and adding it to a dispersion of a single-atom zirconium-doped copper oxide precursor to obtain a mixed solution;

[0011] (3) spraying the mixed solution prepared in step (2) onto a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor electrode material;

[0012] (4) The benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor electrode material prepared in step (3) is subjected to electrochemical reduction treatment to obtain a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material.

[0013] The preparation principle of the benzothiadiazole-modified single-atom zirconium-doped metal copper electrode material provided by the present invention is as follows: in a mixed solution of an inorganic copper salt and an inorganic zirconium salt uniformly dispersed, an alkaline solution is added to adjust the pH to alkaline, so that Cu 2+ 、Zr 4+ With OH - It can combine to form a precursor, and then undergo a high-temperature hydrothermal reaction to obtain a single-atom zirconium-doped copper oxide precursor; it is then mixed with benzothiadiazole and evenly sprayed on a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor electrode material; then, a constant-current electrochemical reduction is performed to obtain a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material. Among them, the doping of single-atom zirconium effectively adjusts the electronic structure of metallic copper and strengthens the activation of CO2 molecules, allowing CO2 to be converted into *CO intermediates at a lower potential. The introduction of benzothiadiazole enhances the adsorption of *CO intermediates and stabilizes *CO, thereby facilitating further CC coupling to generate high-value-added C 2+ product.

[0014] The inorganic copper salt described in step (1) is a soluble salt. Preferably, the copper salt is copper nitrate trihydrate.

[0015] The inorganic zirconium salt described in step (1) is a soluble salt. Preferably, the zirconium salt is zirconium nitrate pentahydrate.

[0016] The molar ratio of the zirconium salt to the copper salt described in step (1) is 0.005 to 0.03:1. The present invention prepares copper oxide precursors with different zirconium doping ratios by changing the amount of zirconium salt used. When the molar concentration of the zirconium salt is too low, due to its too small doping amount, it has little effect on the electronic structure of the overall catalyst, resulting in its performance in activating CO2 molecules is not obvious; when the molar concentration of the zirconium salt is too high, obvious zirconium dioxide particles will be present on the copper oxide precursor, which significantly reduces the performance of electroreduction of CO2.

[0017] The alkaline solution described in step (1) is potassium hydroxide or sodium hydroxide solution. Preferably, the alkaline solution is potassium hydroxide solution; the volume of the added potassium hydroxide solution is 10 mL, and the molar concentration is 0.01 M.

[0018] The stirring time after adding the potassium hydroxide solution in step (1) is 15 to 30 minutes. A long stirring time will affect the morphology of the copper oxide precursor and thus affect the electrocatalytic CO2 performance. Preferably, the stirring time is 15 minutes.

[0019] The solvent for dissolving the benzothiadiazole and the single-atom zirconium-doped copper oxide precursor in step (2) is methanol, ethanol and isopropanol. Preferably, the solvent is methanol.

[0020] The mass ratio of the benzothiadiazole to the single-atom zirconium-doped copper oxide precursor in step (2) is 0.0017 to 0.01:1. When the mass ratio is low, the adsorption of the stable intermediate *CO is not obvious; when the mass ratio is high, the competitive reaction is more obvious and hydrogen evolution is significantly increased. Preferably, the mass ratio of the benzothiadiazole to the single-atom zirconium-doped copper oxide precursor is 0.0034 to 0.01:1, which is conducive to further improving the performance of the electroreduction of CO2.

[0021] The copper nanoparticle layer supported on the polytetrafluoroethylene membrane in step (3) has a thickness of 100 to 200 nm. Preferably, the copper nanoparticle layer has a thickness of 200 nm.

[0022] The loading amount of the copper oxide precursor doped with benzothiadiazole-modified single-atom zirconium on the polytetrafluoroethylene film substrate loaded with copper nanoparticles in step (3) is 0.5-1 mg cm -2 Preferably, the loading amount of the benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor is 1 mg cm -2 .

[0023] The constant current density of the electrochemical reduction in step (4) 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.

[0024] The present invention also provides a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material obtained by the above preparation method.

[0025] In the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material, the atomic ratio of zirconium to copper is 0.005-0.03:1, and the thickness of the copper nanoparticle layer supported on the polytetrafluoroethylene film is 100-200 nm.

[0026] The present invention also provides the above-mentioned benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material for use as a working electrode in an electroreduction CO2 reaction.

[0027] Furthermore, the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material is used as a working electrode to achieve the application of CO2 electroreduction at industrial-grade current density in an acidic environment.

[0028] The benzothiadiazole-modified single-atom zirconium-doped copper electrode material provided by the present invention is used as a working electrode and exhibits excellent industrial-grade current density (200-1000 mA cm) in an acidic environment. -2 )Electroreduction performance of CO2.

[0029] In the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material provided by the present invention, the doping of the zirconium single atom effectively enhances the activation of CO2 molecules at low potential, providing more reaction intermediates *CO for the subsequent CC coupling reaction; at the same time, the benzothiadiazole modification effectively stabilizes the intermediate *CO, thereby enhancing the adsorption of *CO to inhibit the direct escape of *CO to generate carbon monoxide (CO), effectively promoting CC coupling and increasing C 2+ The selectivity of the products is of great significance for the production of high-value-added chemicals by electroreduction of CO2 under industrial conditions in acidic environments.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material provided by the present invention achieves high selective CO2 electroreduction performance in an acidic environment;

[0032] (2) The benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material provided by the present invention effectively regulates the electronic structure of metallic copper by doping with single zirconium atoms, and enhances the activation of CO2 molecules at low potentials. The introduction of benzothiadiazole is beneficial to stabilize the intermediate *CO and enhance the adsorption of the *CO intermediate, thereby promoting the subsequent CC coupling to generate C 2+ The product showed excellent performance in the electroreduction of CO2 under acidic conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The precursor Zr prepared in Example 1 1.0％ - Transmission electron microscopy image of CuO;

[0034] Figure 2 The precursor Zr prepared in Example 1 1.0％ -Spherical aberration correction of CuO - high angle dark field scanning transmission electron microscopy image;

[0035] Figure 3 The electrode material Zr prepared in Example 1 1.0％ - X-ray diffraction pattern of Cu;

[0036] Figure 4 The electrode materials prepared in Example 1 and Comparative Example 1 were 100-700 mA cm in an environment with pH = 1.5 in the application example. -2Faradaic efficiency of different products obtained by CO2 electroreduction at different current densities.

[0037] Figure 5 The electrode materials prepared in Examples 1 to 3 were 600 mA cm in an environment with pH = 1.5 in the application example. -2 Faradaic efficiency of different products obtained by electroreduction of CO2 at different current densities

[0038] Figure 6 The electrode materials prepared in Comparative Examples 1 to 4 are subjected to the following conditions: CO, H2, C2H4 and C 2+ Faradaic efficiency of the product.

[0039] Figure 7 The electrode materials prepared in Comparative Examples 1 and 4 were 100-700 mA cm in an environment with pH = 1.5 in the application example. -2 Faradaic efficiency and reaction potential of CO at different current densities.

[0040] Figure 8 The electrode material prepared in Example 1 is 300 mA cm in an environment with pH = 1.5 in the application example. -2 Stability test under current density. DETAILED DESCRIPTION

[0041] 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.

[0042] Example 1

[0043] (1) Weigh 1208 mg of copper nitrate trihydrate solid particles and 21.5 mg of zirconium nitrate pentahydrate solid particles, dissolve them in 50 mL of deionized water solution, stir at room temperature until transparent, then add 10 mL of 0.01 M potassium hydroxide solution dropwise and stir for 15 min; transfer the obtained mixed solution to a 50 mL hydrothermal kettle, hydrothermally react at 120 ° C for 4 h, then centrifuge and wash with water and ethanol for more than 3 times respectively, and finally dry in a vacuum oven at 60 ° C for 12 h to obtain a single-atom zirconium-doped copper oxide precursor.

[0044] (2) Weigh 20 mg of the single-atom zirconium-doped copper oxide precursor obtained in step (1) and disperse it in 3 mL of methanol and 60 μL of Nafion dispersion. Dissolve benzothiadiazole in the methanol solution to obtain a 2.5-15 mM mixed solution. Then, take 100 μL of a 5 mM molar concentration of benzothiadiazole and methanol mixed solution and add it to the dispersion of the single-atom zirconium-doped copper oxide precursor. After mixing evenly, the mass ratio of benzothiadiazole to the single-atom zirconium-doped copper oxide precursor is 0.0034:1.

[0045] (3) Measure the mixed solution prepared in step (2) and spray it evenly to 2*2cm 2 The polytetrafluoroethylene film substrate loaded with copper nanoparticles was weighed before and after to determine the loading capacity of 1 mg cm -2 , in 3M KCl (pH = 1.5) electrolyte, 100mA cm -2 Under a current density of 0.5, the constant current electrochemical reduction reaction was carried out for 300 seconds to obtain a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material.

[0046] The macroscopic morphology of the single-atom zirconium-doped copper oxide precursor prepared above was observed by transmission electron microscopy. Figure 1 As shown, its morphological structure is a lamellar structure. Figure 2 As shown in FIG, it can be clearly seen that zirconium is doped in the copper oxide precursor lattice in the form of a single atom. The X-ray diffraction pattern of the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material prepared in this embodiment is shown in FIG. Figure 3 As shown, the characteristic peaks of the metallic copper crystal phase can be seen, indicating the successful preparation of benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode materials.

[0047] Example 2

[0048] According to the preparation process of Example 1, the molar concentration of the mixed solution of benzothiadiazole and methanol in step (2) was changed to 2.5 mM, and the mass ratio of benzothiadiazole to the single-atom zirconium-doped copper oxide precursor was 0.0017:1.

[0049] Example 3

[0050] According to the preparation process of Example 1, the molar concentration of the mixed solution of benzothiadiazole and methanol in step (2) was changed to 15 mM, and the mass ratio of benzothiadiazole to the single-atom zirconium-doped copper oxide precursor was 0.01:1.

[0051] Comparative Example 1

[0052] According to the preparation process of Example 1, 100 μL of a mixed solution of benzothiadiazole and methanol with a molar concentration of 5 mM was measured and taken without performing step (2), to obtain a single-atom zirconium-doped metallic copper electrode material.

[0053] Comparative Example 2

[0054] According to the preparation process of Example 1, the mass of zirconium nitrate pentahydrate particles in step (1) was changed to 10.7 mg, and 100 μL of a mixed solution of benzothiadiazole and methanol with a molar concentration of 5 mM in step (2) was not performed.

[0055] Comparative Example 3

[0056] According to the preparation process of Example 1, the mass of zirconium nitrate pentahydrate particles in step (1) was changed to 64.4 mg, and 100 μL of a mixed solution of benzothiadiazole and methanol with a molar concentration of 5 mM in step (2) was not performed.

[0057] Comparative Example 4

[0058] According to the preparation process of Example 1, the mass of zirconium nitrate pentahydrate particles in step (1) was changed to 0 mg, and 100 μL of a mixed solution of benzothiadiazole and methanol with a molar concentration of 5 mM in step (2) was not performed.

[0059] Application example: CO2 electroreduction at industrial-grade current density in acidic environments

[0060] The prepared electrode material was first placed as the working electrode in a three-electrode flow electrolysis cell measuring apparatus consisting of two compartments separated by a cation exchange membrane (Nafion 117). A 0.5M H2SO4 solution, adjusted to pH 1.5, was used as the catholyte in a 3.0M KCl solution. A 0.05M H2SO4 solution served as the anolyte. A platinum sheet was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode.

[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 40 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] Faraday efficiency (FE) test: switch the program to constant current-time test. During the constant current test, use gas chromatography to measure the concentration of gas phase products and calculate the Faraday efficiency of gas phase products. Gas chromatography (GC, Fuli 9790II) online quantitative, use 1 The Faradaic efficiency of the liquid product was analyzed by H nuclear magnetic resonance spectroscopy using the internal standard method with dimethyl sulfoxide as the standard.

[0064] The benzothiadiazole-modified single-atom zirconium-doped copper electrode material prepared in Example 1 exhibited excellent CO2 electroreduction performance in an acidic environment. Figure 4 As shown, in pH = 1.5 electrolyte, at 600mA cm -2 Under the current density, C2H4 and C 2+ The selectivity of the product is as high as 56.0% and 74.9%. Compared with the electroreduction performance of CO2 in Comparative Example 1 (metal copper without zirconium doping and metal copper electrode material modified with benzothiadiazole), the overall C 2+ The Faradaic efficiency of the product increased by 17.3%, providing the possibility for industrial application.

[0065] The electrode materials prepared in Examples 1 to 3 were subjected to a 600 mA cm -2 The electroreduction performance of CO2 at current density of Figure 5 As shown, the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material prepared in Example 1 performs better than those in Example 2 and Example 3 in an acidic environment.

[0066] The electrode materials prepared in Comparative Examples 1 to 4 were subjected to a 600 mA cm -2 The electroreduction performance of CO2 at current density of Figure 6 As shown, the performance of the single-atom zirconium-doped metallic copper electrode material prepared in Comparative Example 1 is better than that of Comparative Examples 2 to 4 in an acidic environment.

[0067] The single-atom zirconium-doped metallic copper electrode materials and the metallic copper electrode materials without zirconium doping prepared in Comparative Examples 1 and 4 were subjected to a 100-700 mA cm -2 The performance under current density is compared, and the results are as follows Figure 7 As shown, the reaction potential of Comparative Example 1 is lower at the same current density, and the activation effect on CO2 molecules is stronger.

[0068] The stability test of Example 1 was carried out in a flow electrolysis cell. The results are as follows Figure 8 As shown, at 300mA cm -2 It can operate stably for 24 hours at a current density of 100 nm, and the Faradaic efficiency of C2H4 remains above 40%.

Claims

1. A method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material, characterized in that: The preparation method comprises the following steps: (1) dissolving an inorganic copper salt and an inorganic zirconium salt and then adding an alkaline solution to obtain a single-atom zirconium-doped copper oxide precursor through a hydrothermal reaction; (2) dissolving benzothiadiazole and adding the solution to a dispersion of a single-atom zirconium-doped copper oxide precursor to obtain a mixed solution; (3) spraying the mixed solution prepared in step (2) onto a polytetrafluoroethylene film substrate loaded with copper nanoparticles to obtain a benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor electrode material; (4) The benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor electrode material prepared in step (3) is subjected to electrochemical reduction treatment to obtain a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material.

2. The method for preparing the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 1, characterized in that: In step (1), the molar ratio of the inorganic zirconium salt to the inorganic copper salt is 0.005-0.03:

1.

3. The method for preparing the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 1, characterized in that: In step (2), the mass ratio of the benzothiadiazole to the single-atom zirconium-doped copper oxide precursor is 0.0017 to 0.01:

1.

4. The method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 1, characterized in that: In step (3), the thickness of the copper nanoparticle layer loaded on the polytetrafluoroethylene membrane is 100 to 200 nm.

5. The method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 1, characterized in that: In step (3), the loading amount of the benzothiadiazole-modified single-atom zirconium-doped copper oxide precursor on the polytetrafluoroethylene film-supported copper nanoparticle substrate is 0.5 to 1-2 mg cm.

6. The method for preparing a benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 1, characterized in that: In step (4), the constant current density of the electrochemical reduction is 50-100 mA cm -2 , the time is 100 to 300 seconds.

7. A metallic copper electrode material doped with benzothiadiazole-modified single-atom zirconium obtained by the preparation method according to any one of claims 1 to 6.

8. The benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material according to claim 7, characterized in that: The atomic ratio of zirconium to copper in the benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material is 0.005-0.03:1, and the thickness of the copper nanoparticle layer supported on the polytetrafluoroethylene film is 100-200 nm.

9. A metallic copper electrode material doped with benzothiadiazole-modified single-atom zirconium according to claim 7, used as a working electrode in an electroreduction of carbon dioxide reaction.

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

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