Unfolding Chemical Diversity: Co-Sublimation in 2D Metal–Organic Networks for the Oxygen Reduction Reaction

In this study, we employ density functional theory to analyze the electrocatalytic activity toward the oxygen reduction reaction (ORR) of FeTPyP/Au(111) self-assembled monolayers (SAMs) and their bimetallic-organic counterpart, FeTPyP + Co/Au(111), synthesized via Co atom sublimation. Our investigation focuses on elucidating the mechanistic roles of various metal active sites, thereby establishing a correlation between the local chemical environment and the electronic properties of the active metal centers. We find that the FeTPyP + Co/Au(111) system exhibits sites with a more balanced adsorption behavior for ORR intermediates compared to FeTPyP/Au(111), which leads us to conclude that the former demonstrates enhanced ORR catalytic activity. Additionally, we introduce a methodology for rapid evaluation of the ORR performance based on the electronic structure of the metal active sites.