Atomic Cu Sites Engineering Enables Efficient CO2 Electroreduction to Methane with High CH4/C2H4 Ratio

Minhan Li; Fangzhou Zhang; Min Kuang; Yuanyuan Ma; Ting Liao; Ziqi Sun; Wei Luo; Wan Jiang; Jianping Yang

doi:10.1007/s40820-023-01188-1

Atomic Cu Sites Engineering Enables Efficient CO₂ Electroreduction to Methane with High CH₄/C₂H₄ Ratio

Nanomicro Lett. 2023 Oct 26;15(1):238. doi: 10.1007/s40820-023-01188-1.

Authors

Minhan Li^#^{1

2}, Fangzhou Zhang^#¹, Min Kuang¹, Yuanyuan Ma³, Ting Liao⁴, Ziqi Sun⁴, Wei Luo¹, Wan Jiang¹, Jianping Yang⁵

Affiliations

¹ Institute of Functional Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, People's Republic of China.
² College of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450001, People's Republic of China.
³ Institute of Functional Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, People's Republic of China. yyma@dhu.edu.cn.
⁴ School of Mechanical, Medical and Process Engineering, School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4001, Australia.
⁵ Institute of Functional Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, People's Republic of China. jianpingyang@dhu.edu.cn.

^# Contributed equally.

Abstract

Electrochemical reduction of CO₂ into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO₂ capture and utilization, resulting from their high catalytic activity and selectivity. The mobility and accessibility of active sites in Cu-based catalysts significantly hinder the development of efficient Cu-based catalysts for CO₂ electrochemical reduction reaction (CO₂RR). Herein, a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride (g-C₃N₄) as the active sites for CO₂-to-CH₄ conversion in CO₂RR. By regulating the coordination and density of Cu sites in g-C₃N₄, an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH₄ Faraday efficiency of 49.04% and produces the products with a high CH₄/C₂H₄ ratio over 9. This work provides the first experimental study on g-C₃N₄-supported single Cu atom catalyst for efficient CH₄ production from CO₂RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO₂RR by engineering Cu active sites in 2D materials with porous crystal structures.

Keywords: CH4/C2H4 ratio; CO2RR; Cu single-atom catalyst; Methane; g-C3N4.