Highly Selective Electrochemical Reduction of CO2 into Methane on Nanotwinned Cu

Jin Cai; Qing Zhao; Wei-You Hsu; Chungseok Choi; Yang Liu; John Mark P Martirez; Chih Chen; Jin Huang; Emily A Carter; Yu Huang

doi:10.1021/jacs.3c00847

Highly Selective Electrochemical Reduction of CO₂ into Methane on Nanotwinned Cu

J Am Chem Soc. 2023 Apr 26;145(16):9136-9143. doi: 10.1021/jacs.3c00847. Epub 2023 Apr 18.

Authors

Jin Cai¹, Qing Zhao², Wei-You Hsu³, Chungseok Choi¹, Yang Liu¹, John Mark P Martirez⁴, Chih Chen³, Jin Huang¹, Emily A Carter^{2

4}, Yu Huang^{1

5}

Affiliations

¹ Department of Materials Science and Engineering, University of California, Los Angeles, Los Angeles, California 90095-1595, United States.
² Department of Mechanical and Aerospace Engineering and the Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544-5263, United States.
³ Department of Materials Science and Engineering, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan, ROC.
⁴ Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, California 90095-1592, United States.
⁵ California NanoSystems Institute, University of California, Los Angeles, Los Angeles, California 90095, United States.

Abstract

The electrochemical carbon dioxide reduction reaction (CO₂RR) is a promising route to close the carbon cycle by reducing CO₂ into valuable fuels and chemicals. Electrocatalysts with high selectivity toward a single product are economically desirable yet challenging to achieve. Herein, we demonstrated a highly (111)-oriented Cu foil electrocatalyst with dense twin boundaries (TB) (tw-Cu) that showed a high Faradaic efficiency of 86.1 ± 5.3% toward CH₄ at -1.2 ± 0.02 V vs the reversible hydrogen electrode. Theoretical studies suggested that tw-Cu can significantly lower the reduction barrier for the rate-determining hydrogenation of CO compared to planar Cu(111) under working conditions, which suppressed the competing C-C coupling, leading to the experimentally observed high CH₄ selectivity.