A surface strategy boosting the ethylene selectivity for CO2 reduction and in situ mechanistic insights

Yinchao Yao; Tong Shi; Wenxing Chen; Jiehua Wu; Yunying Fan; Yichun Liu; Liang Cao; Zhuo Chen

doi:10.1038/s41467-024-45704-2

A surface strategy boosting the ethylene selectivity for CO₂ reduction and in situ mechanistic insights

Nat Commun. 2024 Feb 10;15(1):1257. doi: 10.1038/s41467-024-45704-2.

Authors

Yinchao Yao^#¹, Tong Shi^#^{2

3}, Wenxing Chen¹, Jiehua Wu⁴, Yunying Fan⁵, Yichun Liu⁵, Liang Cao⁶, Zhuo Chen⁷

Affiliations

¹ Energy & Catalysis Center, Department of Materials Physics and Chemistry, School of Materials Science and Engineering, Beijing Institute of Technology, 100081, Beijing, PR China.
² Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou, 310058, Zhejiang, PR China.
³ Inner Mongolia Key Laboratory of Chemistry and Physics of Rare Earth Materials, Department of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, PR China.
⁴ SINOPEC (Beijing) Research Institute of Chemical Industry Co., Ltd, 100013, Beijing, PR China.
⁵ School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, 650093, PR China.
⁶ Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou, 310058, Zhejiang, PR China. liangcao@zju.edu.cn.
⁷ Energy & Catalysis Center, Department of Materials Physics and Chemistry, School of Materials Science and Engineering, Beijing Institute of Technology, 100081, Beijing, PR China. zchen@bit.edu.cn.

^# Contributed equally.

Abstract

Electrochemical reduction of carbon dioxide into ethylene, as opposed to traditional industrial methods, represents a more environmentally friendly and promising technical approach. However, achieving high activity of ethylene remains a huge challenge due to the numerous possible reaction pathways. Here, we construct a hierarchical nanoelectrode composed of CuO treated with dodecanethiol to achieve elevated ethylene activity with a Faradaic efficiency reaching 79.5%. Through on in situ investigations, it is observed that dodecanethiol modification not only facilitates CO₂ transfer and enhances *CO coverage on the catalyst surfaces, but also stabilizes Cu(100) facet. Density functional theory calculations of activation energy barriers of the asymmetrical C-C coupling between *CO and *CHO further support that the greatly increased selectivity of ethylene is attributed to the thiol-stabilized Cu(100). Our findings not only provide an effective strategy to design and construct Cu-based catalysts for highly selective CO₂ to ethylene, but also offer deep insights into the mechanism of CO₂ to ethylene.