Importance of Ligand Effects Breaking the Scaling Relation for Core–Shell Oxygen Reduction Catalysts

Abstract Tremendous recent efforts have been made toward developing highly active oxygen reduction reaction (ORR) catalysts with a minimized usage of noble metal Pt by using Pt alloys and core–Pt shell structures. A main computational framework for such a goal has been the search for a new material with the *OH binding slightly weaker than Pt based on the conventional volcano relation of ORR activity versus *OH binding energy. In this work, by using carbides and nitrides as core materials, we demonstrate that the conventional scaling relation between *OH and *O can be completely broken owing to a significant ligand–Pt orbital interactions in the core–Pt shell structure, and in such cases, the usual catalyst design strategy of tuning the *OH binding energy of Pt to a weaker leg of the volcano can mislead the prediction. In these cases, one needs to consider all reaction intermediates to a…