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

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─N4 moieties couple with atomic Co─N4 sites on the surface of polyhedral carbon. Density functional theory calculations reveal that face‐to‐face laminated construction of Fe─N4 and Co─N4 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. An oxygen reduction electrocatalyst is designed by introducing Co atom to regulate FePc. FePc containing Fe─N4 moieties is coupled with a single‐atom Co catalyst featuring Co─N4 sites, resulting in a face‐to‐face laminated arrangement of Fe─N4 and Co─N4 within the hybrid catalyst. Such an oxygen reduction electrocatalyst revealed exceptional ORR performance and assembled both liquid‐state and solid‐state zinc–air batteries, which exhibit an enormous power density.