Molecular Fe─N4 Moieties Coupled with Atomic Co─N4 Sites Toward Improved Oxygen Reduction Performance

Abstract Research on high‐efficiency and cost‐efficient catalysts for oxygen reduction reaction (ORR) is still a vital but challenging issue for commercializing metal–air batteries. Herein, a single‐molecule/atom hybrid catalyst is developed to boost the ORR, in which iron phthalocyanine molecules containing molecular Fe─N 4 moieties couple with atomic Co─N 4 sites on the surface of polyhedral carbon. Density functional theory calculations reveal that face‐to‐face laminated construction of Fe─N 4 and Co─N 4 in the hybrid catalyst can effectively modulate the electronic structure of active iron atoms and reduce the energy barrier of the rate‐determining step for ORR. As a result, this hybrid catalyst demonstrates excellent ORR performance, featuring a half‐wave potential of 0.904 V, a peak power density of 238.3 mW cm −2 for zinc–air battery, and outstanding electrocatalytic stability. This work offers a distinctive and robust molecular/atomic engineering approach to creating efficient electrocatalysts, advancing the fields of metal–air batteries.