An efficient strategy to screen dual TM atoms modified MoSe2 surface for electroreduction CO2 to C2 product: a first-principles study

Abstract

Electrochemical reduction of carbon dioxide into valuable C2 products offers a promising avenue for artificial carbon cycling, but the efficiency remains a challenge. Here, the potential candidates of the CO2 reduction catalysis based on double transition metal atoms modified MoSe2 (TMmTMn@MoSe2 with TMm/n=Sc ∼ Zn) surfaces are systematically investigated by density functional theory. Through a rigorous three-step screening strategy based on structural stability, balanced CO2 adsorption, and C–C coupling energy barrier, ninety-five percent of the TMmTMn@MoSe2 can be extracted, leaving only Cu2@MoSe2, TiCo@MoSe2, and TiFe@MoSe2 as the promising candidates. Further examination shows a donation-feedback mechanism governed the CO2 adsorption. Globally, it is evident that C–C coupling primarily occurs via the CO dimerization pathway. Particularly, among the optimal candidates, TiCo@MoSe2 exhibited the best kinetic equilibrium throughout the reaction cycle, characterized by a moderate C–C coupling barrier of 0.60 eV and a very low subsequent hydrogenation barrier of 0.34 eV. Electron structure analysis reveals that an anomalous upward shift of the d-level in the TiCo system facilitates the effective return of electrons to the non-bonding orbitals of CO, thereby promoting excellent bond formation. These findings suggests that the screen process is an efficient strategy to obtain the catalysis for CO2 reduction to C2 product.