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CN-121976223-A - Method and device for electrocatalytic reduction of carbon dioxide under near-equilibrium potential condition

CN121976223ACN 121976223 ACN121976223 ACN 121976223ACN-121976223-A

Abstract

The invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and particularly relates to a method and a device for electrocatalytic carbon dioxide reduction under the condition of normal temperature and normal pressure near equilibrium potential. Monoatomic layer Cu, ag, bi, sn, co metal, or monoatomic layer PdCu, cuAg, pdAg alloy was used as a catalyst. The invention also discloses a preparation method of the required monoatomic layer catalyst, and an electrolytic cell and a primary cell based on the reduction method, and the invention utilizes the characteristic that the monoatomic layer catalyst is endowed with a high-energy special state in the initial stage, namely the synthesis process, and the surface of the catalyst is rich in a large amount of residual electrons, and the characteristic can promote the efficient conversion of carbon dioxide into a CO intermediate under the condition of approaching an equilibrium potential, and effectively weaken the mutual repulsive interaction of the CO intermediate, thereby promoting dimerization of the CO intermediate and realizing electrocatalytic CO 2 reduction under the condition of approaching the equilibrium potential at normal temperature and normal pressure.

Inventors

  • DING WEI
  • Zheng Tangfei

Assignees

  • 重庆大学

Dates

Publication Date
20260505
Application Date
20251215

Claims (10)

  1. 1. A method for electrocatalytic carbon dioxide reduction at near equilibrium potential conditions, comprising: monoatomic layer Cu, ag, bi, sn, co, pd metal, or monoatomic layer PdCu, cuAg, pdAg alloy was used as a catalyst.
  2. 2. The method of claim 1, wherein the preparation of the desired monoatomic layer catalyst comprises: Dispersing sodium montmorillonite and a metal precursor in a solution, wherein the mass ratio of the sodium montmorillonite to the metal in the metal precursor is 1-5:1-5; Reacting for 3 hours at a pressure of less than 15 mbar ℃ and a temperature of 50 ℃ to obtain solid powder; Placing the powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃ min -1 under Ar/H 2 atmosphere, preserving heat for 2 hours for high-temperature reduction, and grinding after the product is cooled to room temperature under atmosphere protection; placing the ground product into HF solution, ultrasonic etching, standing, removing supernatant after layering, adding precipitate into HF solution, repeating the above etching process, centrifuging and washing the etched product, and vacuum drying the washed product to obtain monoatomic layer catalyst.
  3. 3. The method of claim 2, wherein the mass ratio of sodium-based montmorillonite to metal in the metal precursor is 1:1.
  4. 4. The method of claim 2, wherein the metal precursor comprises one or more of copper sulfate, copper nitrate, copper acetylacetonate, copper acetate, copper perchlorate, palladium chloride, palladium sulfate, palladium nitrate, palladium acetylacetonate, silver nitrate, silver perchlorate, silver acetate, bismuth nitrate, bismuth sulfate, tin chloride, stannous sulfate, stannous fluoroborate, tin tetrachloride, sodium stannate, cobalt nitrate, cobalt chloride.
  5. 5. The method of claim 1, comprising preparing the monoatomic layer catalyst as a gas diffusion electrode and using it as a working electrode for electrocatalytic CO 2 reduction.
  6. 6. An electrolytic cell comprising a cathode and an anode, the anode employing a gas diffusion electrode coated with an anode catalyst having hydrogen oxidation reaction activity, characterized in that the cathode employs a gas diffusion electrode coated with the catalyst as claimed in claim 1.
  7. 7. The electrolytic cell of claim 6 wherein the anode catalyst is a Pt/C catalyst or PtRu/C catalyst.
  8. 8. The electrolytic cell according to claim 6, wherein the cell comprises four chambers, a cathode gas chamber, a cathode liquid chamber, an anode gas chamber and an anode liquid chamber, and a solar cell panel is provided as a power source.
  9. 9. A CO 2 -H 2 cell comprising a gas diffusion electrode coated with an anode catalyst having hydrogen oxidation activity and a monoatomic layer catalyst.
  10. 10. The CO 2 -H 2 cell as defined in claim 9, wherein the anode catalyst is a Pt/C catalyst or a PtRu/C catalyst.

Description

Method and device for electrocatalytic reduction of carbon dioxide under near-equilibrium potential condition Technical Field The invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and particularly relates to a method and a device for electrocatalytic carbon dioxide reduction under the condition of normal temperature and normal pressure near equilibrium potential. Background Development of a carbon dioxide electrocatalytic reduction catalyst with high selectivity, new and high energy efficiency is important to pushing a carbon dioxide conversion technology. The carbon dioxide molecule itself is chemically inert with a c=o bond dissociation energy as high as 803 kJ mol -1 and its reduction process involves multiple electron, multi-step reactions during which multiple intermediates of different chemisorbed species are formed, resulting in reduced reaction selectivity and yield. Among the numerous metal catalyst species, cu-based catalysts exhibit excellent potential for efficient conversion of CO 2 to multi-carbon products due to their specific binding energy to CO intermediates. Document [ ANGEWANDTE INTERNATIONAL EDITION CHEMIE, 2022, e202209629] reports that by means of one-step pyrolysis of metal-organic frameworks, cuO x @ C catalysts were designed with a faradaic efficiency of electrocatalytic reduction of CO 2 to ethanol of up to 46% at-1.0V (relative reversible hydrogen electrode, RHE) voltage. document [ ANGEWANDTE INTERNATIONAL EDITION CHEMIE, 2022, e202209268] reports that constructing K-doped Cu 2 Se nanoplatelet arrays on foam Cu substrates achieves 70.3% faraday efficiency at-0.8V REH by modulating the interaction between Cu active sites and reaction intermediates. On this basis, literature [ ANGEWANDTE INTERNATIONAL EDITION CHEMIE, 2022, e202205909] devised catalysts of Cu δ⁺ active species rich in electrons, exhibiting higher selectivity to ethanol at-0.3V RHE. From the thermodynamic point of view, the theoretical equilibrium potential for the production of ethanol by electrocatalytic carbon dioxide reduction is only +0.09V RHE, which is more positive than the potential for the production of CO, HCOOH, CH 4 and C 2H4 products. Thus, it is expected to further reduce the overpotential required for the reaction, thereby achieving higher selectivity and faraday efficiency. Disclosure of Invention The invention aims to solve the problems of high overpotential, poor selectivity and the like of the existing electrocatalytic CO 2, and provides a method for electrocatalytic CO 2 reduction with high selectivity and high Faraday efficiency under the condition of near-equilibrium potential. The purpose of the invention is realized in the following way: A method of electrocatalytic carbon dioxide reduction at near equilibrium potential conditions, comprising: monoatomic layer Cu, ag, bi, sn, co, pd metal, or monoatomic layer PdCu, cuAg, pdAg alloy was used as a catalyst. Further, the preparation process of the required monoatomic layer catalyst comprises the following steps: Dispersing sodium montmorillonite and a metal precursor in a solution, wherein the mass ratio of the sodium montmorillonite to the metal in the metal precursor is 1-5:1-5; Reacting for 3 hours at a pressure of less than 15 mbar ℃ and a temperature of 50 ℃ to obtain solid powder; Placing the powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃ min -1 under Ar/H 2 atmosphere, preserving heat for 2 hours for high-temperature reduction, and grinding after the product is cooled to room temperature under atmosphere protection; placing the ground product into HF solution, ultrasonic etching, standing, removing supernatant after layering, adding precipitate into HF solution, repeating the above etching process, centrifuging and washing the etched product, and vacuum drying the washed product to obtain monoatomic layer catalyst. Further, the mass ratio of the sodium montmorillonite to the metal in the metal precursor is 1:1. Further, the metal precursor includes one or more of sulfate of copper, nitrate of copper, copper acetylacetonate, copper acetate, copper perchlorate, palladium chloride, sulfate of palladium, nitrate of palladium, palladium acetylacetonate, silver nitrate, silver perchlorate, silver acetate, bismuth nitrate, sulfate of bismuth, tin chloride, stannous sulfate, stannous fluoroborate, stannic chloride, sodium stannate, cobalt nitrate, cobalt chloride. Further, it includes a gas diffusion electrode prepared from the monoatomic layer catalyst and used as a working electrode for electrocatalytic CO 2 reduction. The invention also discloses an electrolytic cell comprising a cathode and an anode, the anode being a gas diffusion electrode coated with an anode catalyst having hydrogen oxidation activity, characterized in that the cathode is a gas diffusion electrode coated with a catalyst as described in claim 1. Further, the anode catalyst is a Pt/C catalyst or a PtRu/C c