Harnessing the Synergistic Interplay between Atomic‐scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance

Defect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt‐based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni‐doped vacancy‐rich Pt nanoparticles anchored on nitrogen‐doped graphene (Vac‐NiPt NPs/NG) with a low Pt loading of 3.5 wt.% and a Ni/Pt ratio of 0.038:1. Physical characterizations confirmed the presence of abundant atomic‐scale vacancies in the Pt NPs induces long‐range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic‐scale vacancies mainly contributed the tolerance performances towards CO and CH3OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic‐scale vacancies and ligand effect, as‐prepared Vac‐NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal‐based nanomaterials.