3D Hollow Hierarchical Porous Carbon with Fe‐N4‐OH Single‐Atom Sites for High‐Performance Zn‐Air Batteries

The development of innovative and efficient Fe-N-C catalysts is crucial for the widespread application of zinc-air batteries (ZABs), where the inherent oxygen reduction reaction (ORR) activity of Fe single-atom sites needs to be optimized to meet the practical application. Herein, a three-dimensional (3D) hollow hierarchical porous electrocatalyst (ZIF8@FePMPDA-920) rich in asymmetric Fe-N₄ -OH moieties as the single atomic sites is reported. The Fe center is in a penta-coordinated geometry with four N atoms and one O atom to form Fe-N₄ -OH configuration. Compared to conventional Fe-N₄ configuration, this unique structure can weaken the adsorption of intermediates by reducing the electron density of the Fe center for oxygen binding, which decreases the energy barrier of the rate-determining steps (RDS) to accelerate the ORR and oxygen evolution reaction (OER) processes for ZABs. The rechargeable liquid ZABs (LZABs) equipped with ZIF8@FePMPDA-920 display a high power density of 123.11 mW cm^-2 and a long cycle life (300 h). The relevant flexible all-solid-state ZABs (FASSZABs) also display outstanding foldability and cyclical stability. This work provides a new perspective for the structural design of single-atom catalysts in the energy conversion and storage areas.