Issue

Vol. 15 (2023)

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

https://doi.org/10.1007/s40820-023-01188-1
Minhan Li
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
Fangzhou Zhang
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
Min Kuang
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
Yuanyuan Ma
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
Ting Liao
School of Mechanical, Medical and Process Engineering, School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4001, Australia
Ziqi Sun
School of Mechanical, Medical and Process Engineering, School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4001, Australia
Wei Luo
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
Wan Jiang
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
Jianping Yang
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

Corresponding Author: Jianping Yang

jianpingyang@dhu.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 238

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.


Highlights:
1 The Cu-doped graphitic carbon nitride (g-C3N4) material is synthesized by an in situ thermal polymerization strategy, through which the atomic dispersion and coordination structure of Cu on g-C3N4 are realized by regulating the doping level of Cu.
2 High Faraday efficiency of CH4 of 49.04% and a maximum CH4/C2H4 ratio up to 35.03 are achieved for the first time on g-C3N4-supported Cu single-atom catalyst.
3 Structure–activity relationship analysis based on experimental and theoretical studies demonstrates the well-defined Cu single atoms coordinated with N atoms in the nitrogen cavity of g-C3N4 are active sites for CO2-to-CH4.

Keywords

CO2RR Cu single-atom catalyst g-C3N4 Methane CH4/C2H4 ratio
Li, Minhan, Fangzhou Zhang, Min Kuang, Yuanyuan Ma, Ting Liao, Ziqi Sun, Wei Luo, Wan Jiang, and Jianping Yang. 2023. “Atomic Cu Sites Engineering Enables Efficient CO2 Electroreduction to Methane With High CH4/C2H4 Ratio”. Nano-Micro Letters 15 (October):238. https://doi.org/10.1007/s40820-023-01188-1.
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