Theoretical Study of Electrocatalytic CO2 Reduction Mechanism on Typical MXenes under Realistic Conditions

MXenes are a revolutionary class of two-dimensional materials that have been recently demonstrated to exhibit promising capability of electrocatalytic CO2 reduction reaction (CO2RR) in theory and experiment. In electrocatalytic reactions, the active phases, the mechanism, and the performance can be greatly influenced by electrochemical conditions such as applied electrode potential, pH, and electrolyte. Therefore, in this first-principles study, the stable surface structures of three typical MXenes (V2C, Mo2C, and Ti3C2) with variation of electrocatalytic conditions were determined by the Pourbaix phase diagrams. Additionally, the reaction mechanism for CO2RR toward C1 products was investigated based on the thermal dynamically stable phases. The computation revealed that surfaces of all three MXenes are dominated by H* termination throughout the practical CO2RR electrochemical condition ranges. Meanwhile, the bicarbonate ions, which serve as the major electrolyte in CO2RR, show thermal dynamic unfavorability to adsorb on the surfaces. Among the three types of MXenes, V2CH exhibits higher activity in generating CO and HCOOH through the CO2RR, while Mo2CH exhibits higher activity in producing HCHO, CH3OH, and CH4. This comprehensive study provides crucial insights into the mechanism of electrocatalytic CO2RR on MXenes under realistic electrochemical conditions.