In situ copper faceting enables efficient CO2/CO electrolysis

Kaili Yao; Jun Li; Adnan Ozden; Haibin Wang; Ning Sun; Pengyu Liu; Wen Zhong; Wei Zhou; Jieshu Zhou; Xi Wang; Hanqi Liu; Yongchang Liu; Songhua Chen; Yongfeng Hu; Ziyun Wang; David Sinton; Hongyan Liang

doi:10.1038/s41467-024-45538-y

In situ copper faceting enables efficient CO₂/CO electrolysis

Nat Commun. 2024 Feb 26;15(1):1749. doi: 10.1038/s41467-024-45538-y.

Authors

Kaili Yao^#^{1

2}, Jun Li^#³, Adnan Ozden^#⁴, Haibin Wang^#¹, Ning Sun⁵, Pengyu Liu⁵, Wen Zhong⁵, Wei Zhou⁶, Jieshu Zhou¹, Xi Wang¹, Hanqi Liu⁵, Yongchang Liu^{1

7}, Songhua Chen⁸, Yongfeng Hu⁹, Ziyun Wang¹⁰, David Sinton¹¹, Hongyan Liang¹²

Affiliations

¹ School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China.
² Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming, 650500, China.
³ Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, and Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China. lijun001@sjtu.edu.cn.
⁴ Department of Mechanical and Industrial Engineering, University of Toronto, 5 King's College Road, Toronto, ON, M5S 3G8, Canada.
⁵ Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, and Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁶ School of Science, Tianjin University, Tianjin, 300350, China.
⁷ State Key Lab of Hydraulic Engineering Simulation and Safety, School of Materials Science and Engineering, Tianjin University, Tianjin, 300354, China.
⁸ College of Chemistry and Material Science, Longyan University, Longyan, 364012, China.
⁹ Sinopec Shanghai Research Institute of Petrochemical Technology, Shanghai, 201208, China.
¹⁰ School of Chemical Sciences, The University of Auckland, Auckland, 1010, New Zealand.
¹¹ Department of Mechanical and Industrial Engineering, University of Toronto, 5 King's College Road, Toronto, ON, M5S 3G8, Canada. sinton@mie.utoronto.ca.
¹² School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China. hongyan.liang@tju.edu.cn.

^# Contributed equally.

Abstract

The copper (Cu)-catalyzed electrochemical CO₂ reduction provides a route for the synthesis of multicarbon (C₂₊) products. However, the thermodynamically favorable Cu surface (i.e. Cu(111)) energetically favors single-carbon production, leading to low energy efficiency and low production rates for C₂₊ products. Here we introduce in situ copper faceting from electrochemical reduction to enable preferential exposure of Cu(100) facets. During the precatalyst evolution, a phosphate ligand slows the reduction of Cu and assists the generation and co-adsorption of CO and hydroxide ions, steering the surface reconstruction to Cu (100). The resulting Cu catalyst enables current densities of > 500 mA cm^-2 and Faradaic efficiencies of >83% towards C₂₊ products from both CO₂ reduction and CO reduction. When run at 500 mA cm^-2 for 150 hours, the catalyst maintains a 37% full-cell energy efficiency and a 95% single-pass carbon efficiency throughout.