Inverted Region in Electrochemical Reduction of CO2 Induced by Potential-Dependent Pauli Repulsion

Abstract

Electrochemical CO₂ reduction reaction (eCO₂RR) is of great significance to energy and environmental engineering, while fundamental questions remain regarding its mechanisms. Herein, we formulate a fundamental understanding of the interplay between the applied potential (U) and kinetics of CO₂ activation in eCO₂RR on Cu surfaces. We find that the nature of the CO₂ activation mechanism in eCO₂RR varies with U, and it is the sequential electron-proton transfer (SEPT) mechanism dominant at the working U but switched to the concerted proton-electron transfer (CPET) mechanism at highly negative U. We then identify that the barrier of the electron-transfer step in the SEPT mechanism exhibits an inverted region as U decreases, which originates from the rapidly rising Pauli repulsion in the physisorption of CO₂ with decreasing U. We further demonstrate catalyst designs that effectively suppress the adverse effect of Pauli repulsion. This fundamental understanding may be general for the electrochemical reduction reactions of closed-shell molecules.