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CN-120505663-B - Benzothiadiazole modified single-atom zirconium doped metal copper electrode material and preparation method and application thereof

CN120505663BCN 120505663 BCN120505663 BCN 120505663BCN-120505663-B

Abstract

The invention relates to the field of electrocatalyst development and technology, and discloses a benzothiadiazole modified monoatomic zirconium doped metallic copper electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps of adding an alkaline solution after dissolving inorganic copper salt and inorganic zirconium salt, and obtaining a monoatomic zirconium doped copper oxide precursor through hydrothermal reaction; dissolving benzothiadiazole, adding the dissolved benzothiadiazole into a dispersion liquid of a copper oxide precursor doped with single-atom zirconium to obtain a mixed solution, spraying the mixed solution on a polytetrafluoroethylene film substrate loaded with copper nano particles to obtain a copper oxide precursor electrode material doped with the single-atom zirconium modified by the benzothiadiazole, and carrying out electrochemical reduction treatment to obtain the metal copper electrode material doped with the single-atom zirconium modified by the benzothiadiazole. The electrode material is used as a working electrode for the electro-reduction carbon dioxide reaction, shows excellent electro-reduction CO 2 performance in an acidic environment, and realizes the high-selectivity preparation of a high-added-value C 2+ product under the industrial current density.

Inventors

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

Assignees

  • 浙江大学

Dates

Publication Date
20260508
Application Date
20250522

Claims (7)

  1. 1. The preparation method of the benzothiadiazole modified single-atom zirconium doped metallic copper electrode material is characterized by comprising the following steps of: (1) Dissolving inorganic copper salt and inorganic zirconium salt, adding alkaline solution, and carrying out hydrothermal reaction to obtain a monoatomic zirconium doped copper oxide precursor; (2) Dissolving benzothiadiazole, and then adding the dissolved benzothiadiazole into a dispersion liquid of a single-atom zirconium doped copper oxide precursor to be mixed to obtain a mixed solution; (3) Spraying the mixed solution prepared in the step (2) on a polytetrafluoroethylene film substrate loaded with copper nano particles to obtain a copper oxide precursor electrode material doped with diazosulfide modified monoatomic zirconium; (4) The copper oxide precursor electrode material doped with the single-atom zirconium modified by the benzothiadiazole prepared in the step (3) is subjected to electrochemical reduction treatment to obtain a metal copper electrode material doped with the single-atom zirconium modified by the benzothiadiazole; In the step (1), the molar ratio of the inorganic zirconium salt to the inorganic copper salt is 0.005-0.03:1; in the step (2), the mass ratio of the benzothiadiazole to the monoatomic zirconium doped copper oxide precursor is 0.0017-0.01:1; in the step (4), 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 method for preparing the benzothiadiazole modified single-atom zirconium doped metallic copper electrode material according to claim 1, wherein in the step (3), the thickness of the copper nanoparticle layer loaded on the polytetrafluoroethylene film is 100-200 nm.
  3. 3. The method for preparing the benzothiadiazole modified monatomic zirconium doped metallic copper electrode material according to claim 1, wherein in the step (3), the load of the benzothiadiazole modified monatomic zirconium doped copper oxide precursor is 0.5-1 mg cm -2 on a polytetrafluoroethylene film loaded copper nanoparticle substrate.
  4. 4. A benzothiadiazole-modified monatomic zirconium doped metallic copper electrode material obtained by the preparation method of any one of claims 1 to 3.
  5. 5. The benzothiadiazole modified single-atom zirconium doped metallic copper electrode material according to claim 4, wherein 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 a copper nanoparticle layer loaded on a polytetrafluoroethylene film is 100-200 nm.
  6. 6. A benzothiadiazole-modified single-atom zirconium-doped metallic copper electrode material as a working electrode for an electro-reduction carbon dioxide reaction.
  7. 7. The use according to claim 6, wherein the benzothiadiazole modified monoatomic zirconium doped metallic copper electrode material is used as a working electrode to realize the electroreduction of carbon dioxide under industrial current density in an acidic environment.

Description

Benzothiadiazole modified single-atom zirconium 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 benzothiadiazole modified single-atom zirconium doped metallic copper electrode material, a preparation method and application thereof. Background Excessive development of traditional fossil energy sources results in excessive emission of carbon dioxide (CO 2), which causes serious environmental problems, and re-capture and utilization of CO 2 while reducing its emission is an important way to reduce environmental problems. Wherein the electrochemical reduction of CO 2 to high value added multi-carbon (C 2+) products such as ethylene (C 2H4), ethanol (C 2H5 OH), Chemicals such as acetic acid (CH 3 COOH) and propanol (C 3H7 OH) are considered to be one of the most promising technical directions for achieving carbon recycling in the future. Currently, most reactions for the electroreduction of CO 2 are carried out in alkaline or neutral electrolytes, and thus inevitably form carbonates, resulting in reduced CO 2 utilization efficiency, and CO 2 regeneration also requires additional energy consumption, thus reducing overall energy efficiency. The problem can be effectively solved by adopting the acidic electrolyte to carry out the electroreduction CO 2 reaction, but the competitive electrolytic water hydrogen evolution reaction in the acidic environment is easier to occur, so that the efficiency of converting CO 2 into a high-added-value C 2+ product is reduced, and therefore, the realization of electroreduction of CO 2 into high-added-value chemicals under the industrial current density in the acidic environment still faces a great challenge. The copper-based catalyst has the capability of deeply reducing CO 2 into hydrocarbon products, has moderate adsorption energy on most carbon-containing intermediates, and is widely applied to the reaction of electric reduction CO 2. However, since the CO 2 molecule is a linear structure, the initial activation process is very difficult, while the electro-reduction CO 2 reaction is a multi-step proton-coupled electron transfer process, the reaction kinetics are slow, resulting in a single copper-based catalyst that is less selective for the formation of a specific C 2+ product, and therefore, it is very necessary to develop a copper-based catalyst that can effectively activate the CO 2 molecule and convert it to a high value-added C 2+ product with high efficiency. At present, the doping of the copper-based catalyst by the second component metal is one of effective means for modifying the copper-based catalyst, for example, chinese patent literature of publication No. CN118727045A discloses a rare earth doped nano-porous copper-based catalyst, a preparation method and application thereof, and as rare earth elements have unique electron orbits, excellent electron transfer capability is shown, the rare earth elements are introduced into the copper-based catalyst with a nano-porous structure, so that the Faraday efficiency of a C 2+ product can be remarkably improved, competitive hydrogen evolution reaction is effectively inhibited, and the stability is improved. Carbon-carbon (C-C) coupling is often considered as a critical reaction step in determining the rate of formation of C 2+ products, however, the problems of CO desorption and high energy barrier of C-C coupling reactions, which greatly limit the reaction kinetics. Therefore, enhancing adsorption of CO and lowering the reaction energy barrier of C-C coupling are effective methods of increasing the rate of formation of CO (COCOH) key intermediates. In recent years, a strategy of modifying the surface of an electrode material by utilizing organic molecules is a direct and effective modification method, and can regulate and control the concentration of a reactant on the surface of a catalyst and adjust the adsorption strength of a reaction intermediate to improve performance, so that the method is widely studied. The Chinese patent document of publication No. CN117070980A discloses an alkaline ionic liquid functionalized copper and application thereof in preparing a multi-carbon product by electrocatalytic CO 2 reduction, wherein the performance of the electric reduction CO 2 is remarkably improved by introducing the alkaline ionic liquid to perform surface functionalization modification of a copper electrode, and the Faraday efficiency of the C 2+ product is more than 70 percent and is remarkably superior to that of an unmodified copper electrode. Despite the advances in the synthesis of high value-added C 2+ products from electroreduced CO 2, achieving high current density, high selectivity electroreduced CO 2 under acidic conditions still faces challenges, especially the efficient targeted synthesis of a single C 2+ product remains to be explored further. Disclos