Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

• Published in: Nature communications Vol. 12; no. 1; pp. 6390 - 9
• Main Authors: Zhang, Yu, Dong, Long-Zhang, Li, Shan, Huang, Xin, Chang, Jia-Nan, Wang, Jian-Hui, Zhou, Jie, Li, Shun-Li, Lan, Ya-Qian
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 04.11.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/299/886; 639/638/161/886; 639/638/911; Active sites; Adsorption; Carbon dioxide; Catalysis; Catalysts; Climate change; Coordination; Copper; Crystal structure; Crystallinity; Electrochemistry; Energy; Energy conversion; Graphene; Humanities and Social Sciences; Hydrocarbons; Investigations; Ligands; Metal-organic frameworks; Methane; multidisciplinary; Nitrogen; Oxygen; Pore size; Science; Science (multidisciplinary); Selectivity; Transmission electron microscopy
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-26724-8

The electrochemical CO 2 reduction to high-value-added chemicals is one of the most promising and challenging research in the energy conversion field. An efficient ECR catalyst based on a Cu-based conductive metal-organic framework (Cu-DBC) is dedicated to producing CH 4 with superior activity and selectivity, showing a Faradaic efficiency of CH 4 as high as ~80% and a large current density of −203 mA cm −2 at −0.9 V vs. RHE. The further investigation based on theoretical calculations and experimental results indicates the Cu-DBC with oxygen-coordinated Cu sites exhibits higher selectivity and activity over the other two crystalline ECR catalysts with nitrogen-coordinated Cu sites due to the lower energy barriers of Cu-O 4 sites during ECR process. This work unravels the strong dependence of ECR selectivity on the Cu site coordination environment in crystalline porous catalysts, and provides a platform for constructing highly selective ECR catalysts. Crystalline porous catalysts with single Cu sites are dedicated to exploring the dependence of CO 2 electroreduction selectivity on the coordination environment of catalytic sites. The conductive MOF Cu-DBC with oxygen-coordinated Cu sites shows a high Faradaic efficiency ~80% of CO 2 -to-CH 4 .