H-Induced Restructuring on Cu(111) Triggers CO Electroreduction in an Acidic Electrolyte.

ABSTRACT

In acidic conditions, the electroreduction of CO or CO2 (noted CO(2)RR) on metal surfaces is conventionally hindered by intense competition with the hydrogen evolution reaction (HER). In this study, we present first-principles calculations of a mechanism wherein the formation of H-induced Cu adatoms on Cu(111) serves as a pivotal trigger for CORR in acidic environments. Through an analysis of the grand canonical surface state population, we elucidate that these newly formed adatoms create an array of active sites essential for both CO adsorption and subsequent reduction. Our ensemble-based kinetic models unveil the role of adatoms, enhancing the HER while simultaneously initiating CORR. Notably, the cumulative activity of the HER and CORR is contingent upon the combination of various surface states, with their individual contributions varying based on the electrode potential and pH. The interplay between surface state dynamics and electrochemical activity sheds new light on the potential-dependent nature of the active site and reaction kinetics governing CORR on Cu(111) in acidic media.