• 专利标题:   Preparation of copper-based catalyst by preparing solution in which metal salt precursor is dissolved, stirring with nanoscale powder containing copper oxide, and binder, spraying on conductive substrate, placing in electrolyte, performing electrochemical reduction, and forming copper electrode.
  • 专利号:   CN115821318-A
  • 发明人:   GUO W, NIU W, ZHANG B
  • 专利权人:   UNIV FUDAN
  • 国际专利分类:   C25B011/091, C25B003/07, C25B003/25, C25B003/26
  • 专利详细信息:   CN115821318-A 21 Mar 2023 C25B-011/091 202330 Chinese
  • 申请详细信息:   CN115821318-A CN11575788 09 Dec 2022
  • 优先权号:   CN11575788

▎ 摘  要

NOVELTY - Preparation method of copper-based catalyst, involves (a) preparing a first solution in which a metal salt precursor is dissolved, (b) adding the nanoscale powder containing copper oxide, adding the first binder, and stirring to produce a uniformly dispersed mixed slurry, (c) spraying or dropping-coating on the conductive substrate, and (d) placing the conductive substrate in the corresponding electrolyte, and in introduction of carbon monoxide, applying a reduction potential to the conductive substrate to perform an electrochemical reduction, using the reduced copper to cover the conductive substrate to form a copper electrode, eluting atoms of the regulator metal element, depositing on the copper electrode in situ, bonding to the copper lattice of the copper electrode, forming a copper-based catalyst doped with the regulator metal element, and enriching the distribution of atoms of the regulator metal element. USE - The method is used for preparation of copper-based catalyst for preparing a copper-based catalytic electrode for an electrochemical electrolysis device (all claimed). ADVANTAGE - Most of the modifier metal elements are distributed at the grain boundaries of the copper lattice surface, and forming a defect-rich copper-based catalyst component. The method achieves strong carbon monoxide bonds and high surface carbon monoxide coverage on the copper surface, and stabilizes the carbon monoxide (OCCO) dimer and promoting the subsequent bound oxygen (COOCCOH) coupling to form the effect of C3 products, Enhancing the selectivity of single multi-carbon products in the carbon dioxide/carbon monoxide electrochemical reduction reaction. The method improves the reaction rate, energy conversion efficiency and reactant conversion rate. DETAILED DESCRIPTION - Preparation method of copper-based catalyst, involves (a) preparing a first solution in which a metal salt precursor is dissolved, where the metal salt precursor contains at least one regulator metal element, and the regulator metal element includes at least one transition metal element or main group metal element with an atomic radius larger than that of copper, (b) adding the nanoscale powder containing copper oxide into the first solution, and further adding the first binder, and stirring to produce a uniformly dispersed mixed slurry, (c) spraying or dropping-coating the mixture slurry on the conductive substrate placed on the hot table, and (d) placing the above-mentioned conductive substrate in the corresponding electrolyte, and in the environment of continuous introduction of carbon monoxide, applying a reduction potential to the conductive substrate to perform an electrochemical reduction reaction, using the reduced copper to cover the conductive substrate to form a copper electrode, eluting atoms of the regulator metal element and depositing on the copper electrode in situ, further bonding to the copper lattice of the copper electrode, forming a copper-based catalyst doped with the regulator metal element, in the copper-based catalyst, enriching the distribution of atoms of the regulator metal element at the grain boundaries of the copper lattice than at other positions of the copper lattice, where the regulator metal element is selected from lead, antimony, tin, indium, gold, bismuth, cadmium and mercury. The atomic molar ratio of the copper element in the copper-based catalyst to the regulator metal element is 1: Y, where Y is 0.005 to 0.1. The continuous feeding of carbon monoxide has a flow rate of not less than 20 ml/minute. The first adhesive is selected from at least one of Nafion(RTM: Sulfonated tetrafluoroethylene based fluoropolymer-copolymer) solution, polyvinylidene fluoride monomer solution and polytetrafluoroethylene monomer solution. INDEPENDENT CLAIMS are included for: a copper-based catalyst obtained by the preparation method having a copper lattice and atoms of a regulator metal element attached to the copper lattice by metallic bonds, where the modifier metal element includes at least one transition metal element or main group metal element with an atomic radius larger than that of copper, and the distribution of atoms of the regulator metal element at the grain boundaries of the copper lattice is more enriched than at other positions of the copper lattice. The regulator metal element is selected from at least one of lead, antimony, tin, indium, gold, bismuth, cadmium and mercury, and the atomic molar ratio of the copper element in the copper-based catalyst to the regulator metal element is 1:Y, wherein Y is 0.005 to 0.1; a method for preparing a copper-based catalytic electrode, comprising adopting the preparation method of the copper-based catalyst to obtain the copper-based catalyst on the conductive substrate as the electrode substrate, and washing the electrode substrate and drying to obtain a copper-based catalytic electrode, where the conductive substrate is selected from one of conductive glass, conductive metal sheet and stainless steel plate, and the thickness of the conductive substrate is 0.5-2 mm, and the loading amount of the copper-based catalyst in the copper-based catalytic electrode is 0.2-5 mg/cm; or comprising adopting the preparation method of copper-based catalyst to obtain a copper-based catalyst on a conductive substrate, peeling off the copper-based catalyst layer from the conductive substrate, after stripping the obtained copper-based catalyst for washing, mixing with water, a second binder and an organic solvent to produce a catalyst slurry, spraying or dropping-coating the catalyst slurry on the conductive diffusion layer and drying the slurry to form a gas diffusion electrode covered with a copper-based catalyst layer, where the second adhesive is selected from at least one of (RTM: Sulfonated tetrafluoroethylene based fluoropolymer-copolymer) solution, polyvinylidene fluoride monomer solution, PTFE monomer solution, polyethylene-tetrafluoroethylene copolymer monomer solution, and (RTM: Ion exchange resin solution, and the organic solvent is selected from at least one of ethanol, methanol, n-propanol, isopropanol, ethylene glycol, glycerol, acetone and N,N-dimethylformamide, and where the conductive diffusion layer can be selected from hydrophobic carbon paper, PTFE film of thermally evaporated copper or PTFE film of ion beam sputtered copper, and the thickness of the conductive diffusion layer is 0.1-2 mm, and the loading capacity of the copper-based catalyst in the formed gas diffusion electrode is 1-10 mg/cm;2NafionDowex2 a copper-based catalytic electrode obtained by the preparation method; and an electrochemical electrolysis device having the copper-based catalytic electrode, and futher having an oxygen-producing electrode or a urea oxidation electrode.