Universal Principle to Describe Reactivity and Selectivity of CO<sub>2</sub> Electroreduction on Transition Metals and Single-Atom Catalysts
Xin Guan, Chenxu Zhao, Xin Liu, Shanping Liu, Wang Gao, Qing Jiang
Abstract
The correlation between catalysts’ intrinsic electronic structures and their reactivity and selectivity is essential for the design of advanced catalysts. We propose a universal principle to describe the CH4, CO, HCOOH, and H2 formation of CO2 electroreduction reaction (CO2RR), in which the intermediates are also active in several other reactions, over transition metals (TMs) and single-atom catalysts (SACs). Our results demonstrate that the catalytic activity of TMs and SACs toward CO2RR, denoted as onset potential and current density, which were previously understood with the adsorption strength of key intermediates, are strongly correlated with the intrinsic properties, namely the valence-electron number and electronegativity of active centers. Moreover, we uncover the local-environment effect of SACs on the adsorption properties of CO*, COOH*, H*, and HCOO*. Our scheme rationalizes a series of experimental observations including the trends in reactivity and selectivity of CO2RR and allows quick screening of advanced catalysts for CO2RR.