Promoting CO2 methanation via ligand-stabilized metal oxide clusters as hydrogen-donating motifs

Yuhang Li; Aoni Xu; Yanwei Lum; Xue Wang; Sung-Fu Hung; Bin Chen; Ziyun Wang; Yi Xu; Fengwang Li; Jehad Abed; Jianan Erick Huang; Armin Sedighian Rasouli; Joshua Wicks; Laxmi Kishore Sagar; Tao Peng; Alexander H Ip; David Sinton; Hao Jiang; Chunzhong Li; Edward H Sargent

doi:10.1038/s41467-020-20004-7

Promoting CO₂ methanation via ligand-stabilized metal oxide clusters as hydrogen-donating motifs

Nat Commun. 2020 Dec 3;11(1):6190. doi: 10.1038/s41467-020-20004-7.

Authors

Yuhang Li^{1

2}, Aoni Xu¹, Yanwei Lum¹, Xue Wang¹, Sung-Fu Hung¹, Bin Chen¹, Ziyun Wang¹, Yi Xu³, Fengwang Li¹, Jehad Abed^{1

4}, Jianan Erick Huang¹, Armin Sedighian Rasouli¹, Joshua Wicks¹, Laxmi Kishore Sagar¹, Tao Peng¹, Alexander H Ip¹, David Sinton³, Hao Jiang^{2

5}, Chunzhong Li^{6

7}, Edward H Sargent⁸

Affiliations

¹ Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON, M5S 1A4, Canada.
² Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
³ Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, ON, M5S 3G8, Canada.
⁴ Department of Materials Science and Engineering, University of Toronto, Toronto, ON, M5S 3E4, Canada.
⁵ School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China.
⁶ Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China. czli@ecust.edu.cn.
⁷ School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China. czli@ecust.edu.cn.
⁸ Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON, M5S 1A4, Canada. ted.sargent@utoronto.ca.

Abstract

Electroreduction uses renewable energy to upgrade carbon dioxide to value-added chemicals and fuels. Renewable methane synthesized using such a route stands to be readily deployed using existing infrastructure for the distribution and utilization of natural gas. Here we design a suite of ligand-stabilized metal oxide clusters and find that these modulate carbon dioxide reduction pathways on a copper catalyst, enabling thereby a record activity for methane electroproduction. Density functional theory calculations show adsorbed hydrogen donation from clusters to copper active sites for the *CO hydrogenation pathway towards *CHO. We promote this effect via control over cluster size and composition and demonstrate the effect on metal oxides including cobalt(II), molybdenum(VI), tungsten(VI), nickel(II) and palladium(II) oxides. We report a carbon dioxide-to-methane faradaic efficiency of 60% at a partial current density to methane of 135 milliampere per square centimetre. We showcase operation over 18 h that retains a faradaic efficiency exceeding 55%.