Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction

Jian Jin; Joshua Wicks; Qiuhong Min; Jun Li; Yongfeng Hu; Jingyuan Ma; Yu Wang; Zheng Jiang; Yi Xu; Ruihu Lu; Gangzheng Si; Panagiotis Papangelakis; Mohsen Shakouri; Qunfeng Xiao; Pengfei Ou; Xue Wang; Zhu Chen; Wei Zhang; Kesong Yu; Jiayang Song; Xiaohang Jiang; Peng Qiu; Yuanhao Lou; Dan Wu; Yu Mao; Adnan Ozden; Chundong Wang; Bao Yu Xia; Xiaobing Hu; Vinayak P Dravid; Yun-Mui Yiu; Tsun-Kong Sham; Ziyun Wang; David Sinton; Liqiang Mai; Edward H Sargent; Yuanjie Pang

doi:10.1038/s41586-023-05918-8

Constrained C₂ adsorbate orientation enables CO-to-acetate electroreduction

Nature. 2023 May;617(7962):724-729. doi: 10.1038/s41586-023-05918-8. Epub 2023 May 3.

Authors

Jian Jin^#^{1

2}, Joshua Wicks^#³, Qiuhong Min^#¹, Jun Li^#⁴, Yongfeng Hu⁵, Jingyuan Ma^{6

7}, Yu Wang^{6

7}, Zheng Jiang^{6

7}, Yi Xu⁸, Ruihu Lu^{1

9}, Gangzheng Si¹, Panagiotis Papangelakis⁸, Mohsen Shakouri¹⁰, Qunfeng Xiao¹⁰, Pengfei Ou³, Xue Wang³, Zhu Chen³, Wei Zhang¹¹, Kesong Yu¹¹, Jiayang Song¹, Xiaohang Jiang¹, Peng Qiu¹, Yuanhao Lou¹, Dan Wu¹, Yu Mao⁹, Adnan Ozden⁸, Chundong Wang¹, Bao Yu Xia¹², Xiaobing Hu^{13

14}, Vinayak P Dravid^{13

14}, Yun-Mui Yiu¹⁵, Tsun-Kong Sham¹⁵, Ziyun Wang⁹, David Sinton⁸, Liqiang Mai¹⁶, Edward H Sargent^{17

18

19}, Yuanjie Pang²⁰

Affiliations

¹ School of Optical and Electronic Information, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, China.
² School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan, China.
³ Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada.
⁴ Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, China.
⁵ Department of Chemical & Biological Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada.
⁶ Shanghai Synchrotron Radiation Facility, Zhangjiang National Lab, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China.
⁷ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China.
⁸ Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada.
⁹ School of Chemical Sciences, The University of Auckland, Auckland, New Zealand.
¹⁰ Canadian Light Source, Inc., University of Saskatchewan, Saskatoon, Saskatchewan, Canada.
¹¹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, China.
¹² Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, China.
¹³ Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA.
¹⁴ The NUANCE Center, Northwestern University, Evanston, IL, USA.
¹⁵ Department of Chemistry, Western University, London, ON, Canada.
¹⁶ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, China. mlq518@whut.edu.cn.
¹⁷ Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada. ted.sargent@utoronto.ca.
¹⁸ Department of Chemistry, Northwestern University, Evanston, IL, USA. ted.sargent@utoronto.ca.
¹⁹ Department of Electrical and Computer Engineering, Northwestern University, Evanston, IL, USA. ted.sargent@utoronto.ca.
²⁰ School of Optical and Electronic Information, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, China. yuanjie_pang@hust.edu.cn.

^# Contributed equally.

PMID: 37138081
DOI: 10.1038/s41586-023-05918-8

Abstract

The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture^1,2. Copper (Cu) is relied on today for carbon-carbon coupling, in which it produces mixtures of more than ten C₂₊ chemicals^3-6: a long-standing challenge lies in achieving selectivity to a single principal C₂₊ product^7-9. Acetate is one such C₂ compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes¹⁰-chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10 atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C₂₊ product¹¹.