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CN-120485862-B - Proton sponge modified fluorine atom doped metal copper electrode material and preparation method and application thereof

CN120485862BCN 120485862 BCN120485862 BCN 120485862BCN-120485862-B

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 metallic copper electrode material, wherein the preparation method comprises the following steps of adding a dispersion liquid of a proton sponge into a dispersion liquid of a hydroxyl copper fluoride precursor to obtain a mixed solution; uniformly spraying the mixed solution on a polytetrafluoroethylene film substrate loaded with copper nano particles 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 also discloses a proton sponge modified fluorine atom doped metal copper electrode material prepared by the preparation method and application of the proton sponge modified fluorine atom doped metal copper electrode material serving as a working electrode in the electro-reduction carbon dioxide reaction. The electrode material provided by the invention has excellent performance of electric reduction of CO 2 in an acidic environment, and realizes high selectivity of preparing a high-added-value C 2+ product under industrial-grade current density.

Inventors

  • HOU YANG
  • ZHAO ZILIN
  • LEI LECHENG
  • YANG BIN
  • LI ZHONGJIAN

Assignees

  • 浙江大学

Dates

Publication Date
20260508
Application Date
20250523

Claims (8)

  1. 1. The preparation method of the proton sponge modified fluorine atom doped metal copper electrode material is characterized by comprising the following steps of: (1) Adding the dispersion liquid of the proton sponge into the dispersion liquid of the hydroxyl copper fluoride precursor to obtain a mixed solution; (2) Spraying the mixed solution on a polytetrafluoroethylene film substrate loaded with copper nano particles to obtain a proton sponge modified hydroxyl copper fluoride precursor electrode material; (3) Carrying out electrochemical reduction on the proton sponge modified hydroxyl copper fluoride precursor electrode material prepared in the step (2) to obtain a proton sponge modified fluorine atom doped metal copper electrode material; In the step (1), the mass ratio of the proton sponge to the hydroxyl copper fluoride precursor is 0.04-0.065:1; In the step (3), in the electrolyte with the pH value of 3M KCl and 1.5, the constant current density of electrochemical reduction is 50-100 mA.cm -2 , and the time is 100-300 s.
  2. 2. The preparation method of the proton sponge modified fluorine atom doped metallic copper electrode material according to claim 1, wherein in the step (1), the preparation method of the hydroxyl copper fluoride precursor is characterized in that inorganic copper salt is dissolved in N, N-dimethylformamide solvent, ammonium bifluoride is added to be stirred and mixed, and centrifugal drying is carried out after solvothermal reaction, so that the hydroxyl copper fluoride precursor is obtained.
  3. 3. The method for preparing the proton sponge modified fluorine atom doped metallic copper electrode material according to claim 2, wherein the solvothermal reaction temperature is 120-160 ℃ and the solvothermal reaction time is 2-4 h.
  4. 4. The method for preparing a proton sponge modified fluorine atom doped metallic copper electrode material according to claim 1, wherein in the step (2), the thickness of the copper nanoparticle layer on the polytetrafluoroethylene film is 200-400 nm.
  5. 5. The method for preparing the proton sponge modified fluorine atom doped metallic copper electrode material according to claim 1, wherein in the step (2), the loading amount of the proton sponge modified hydroxyl copper fluoride precursor is 0.5-1 mg.cm -2 on a polytetrafluoroethylene film loaded copper nanoparticle substrate.
  6. 6. A proton sponge-modified fluorine atom-doped metallic copper electrode material obtained by the preparation method of any one of claims 1 to 5.
  7. 7. A proton sponge-modified fluorine atom-doped metallic copper electrode material as claimed in claim 6 applied as a working electrode in an electro-reduction carbon dioxide reaction.
  8. 8. The application of claim 7, wherein the proton sponge modified fluorine atom doped metallic copper electrode material is used as a working electrode to realize the application of electrically reducing carbon dioxide in an acidic environment under industrial-grade current density.

Description

Proton sponge modified fluorine atom doped metal copper electrode material and preparation method and application thereof Technical Field The invention relates to the field of electrocatalyst development and technology, in particular to a proton sponge modified fluorine atom doped metal copper electrode material, a preparation method and application thereof. Background The renewable energy driven electro-reduction carbon dioxide (CO 2) reaction provides a very promising technical path for capturing, converting and utilizing CO 2, and the electro-reduction CO 2 technology can realize the efficient conversion and utilization of CO 2 by utilizing renewable electric energy under mild conditions, wherein ethylene (C 2H4), Ethanol (C 2H5 OH), As ideal value-added products, multi-carbon (C 2+) compounds with high energy density, such as acetic acid (CH 3 COOH) and propanol (C 3H7 OH), can not only provide green raw materials for chemical industry, but also effectively relieve contradiction between climate change and energy demand, thus receiving extensive attention from academia and industry. Currently, to increase the selectivity of the C 2+ product, most electrolytes of the electro-reduced CO 2 reaction are alkaline or neutral, however, carbonate formed by the electro-reduced CO 2 reaction in alkaline or neutral environment can precipitate or migrate to the anode at the cathode to cause CO 2 crossover problem, reducing the utilization efficiency of CO 2, and the regeneration process also requires a large amount of additional energy consumption. In contrast, the electro-reduction CO 2 reaction in an acidic environment can combine protons (H +) in the electrolyte with carbonates to convert into CO 2, so that the overall energy efficiency is improved, but a great amount of H + is combined preferentially to generate an electrolyzed water hydrogen evolution side reaction, so that the selectivity of a C 2+ product is reduced, and therefore, development of an electro-catalyst capable of remarkably improving the electro-reduction CO 2 reaction performance in an acidic environment and effectively inhibiting the hydrogen evolution side reaction still faces a great challenge. Copper-based catalysts have heretofore been widely used for the electro-reduction CO 2 reaction due to their unique electronic structure and excellent carbon-carbon (C-C) coupling capability. Most researches improve the intrinsic catalytic activity of the copper-based catalyst by regulating and controlling the electronic structure and chemical composition of the copper-based catalyst, common regulating and controlling strategies comprise element doping, crystal face regulation, defect formation, alloying and the like, wherein the element doping strategy has the core advantage of accurately regulating and controlling the electronic structure, geometric structure and surface property of the catalyst, so that the performance limit of a single element component is broken through. The Chinese patent document of publication No. CN119433589A discloses an in-situ synthesized halogen modified bismuth nano electro-catalytic electrode, a preparation method and application thereof, wherein a precursor is synthesized by grafting halogen atoms on the surface of copper bismuth subate through water bath treatment, and then the halogen modified bismuth nano material is obtained through electrochemical reduction, so that hydrogen evolution reaction is effectively inhibited, reaction current density is improved, and excellent performance of preparing formic acid by electro-reduction CO 2 is presented. With the continuous and deep research on improving the reaction performance of the electric reduction CO 2, the method is not limited to the optimization of the intrinsic performance of the electric catalyst, but gradually turns to the regulation and control of the micro-environment of the electrode material reaction interface, and provides a new thought for the research on improving the reaction performance of the electric reduction CO 2. The Chinese patent document of publication No. CN119593013A discloses a preparation method and application of a CO 2 gas capturing functional molecule modified nano gold catalyst, wherein functional molecules are added into an organic solvent and then are subjected to oil bath heating reaction with the nano gold catalyst, so that the organic molecule modified nano gold catalyst with CO 2 gas capturing function is obtained, an interface hydrophobic microenvironment favorable for CO 2 reduction reaction is provided after the organic molecule modification, CO 2 gas diffusion is remarkably enhanced, hydrogen evolution side reaction is effectively reduced, and the reaction selectivity of electric reduction CO 2 is improved. Research on modification of an electric reduction CO 2 reaction catalyst and micro-environment regulation of a reaction interface thereof has been advanced to a certain extent, but the realization of high selectivi