Unlocking Durable High‐Power Zn‐Air Batteries: {Fe ₃ O} Molecular Furnace‐Forged Dual‐Site Catalysts Enabling Synergistic Oxygen Reduction in Alkaline Media

Abstract

ABSTRACT Atomic‐level precision metal‐oxo clusters serve as a unique bridge linking single atoms and nanoparticles. Their highly ordered, quasi‐molecular structure effectively promotes electron transfer and optimizes charge deposition kinetics, thereby significantly enhancing the catalytic activity and stability of electrochemical oxygen reduction reactions. Here, we constructed a single‐atom‐nanoparticle dual‐engine catalyst (Fe 3 C/Fe‐NC 1050 ) by in situ domain‐confined complexation of ZIF‐8(Zn) using {Fe 3 O} as a core metal‐oxo cluster. The unique flexible ligand‐carboxylate group of {Fe 3 O} clusters provide a protective barrier for the metal atoms distribution during pyrolysis, work in synergy with the ZIF‐8 framework to provide a conductive substrate. The precisely exposed Fe 3 C (110) crystal plane modulates the electronic structure of neighboring Fe‐N 4 active sites, thus reducing the adsorption energy of key step O 2 →*OOH and endowing the material with excellent methanol resistance and stability. Structural characterization and theoretical calculations reveal that the synergistic interaction between {Fe 3 O} clusters and the carbon substrate provides a stable conductive network and active sites, achieving a maximum power density of 249.0 mW cm −2 in alkaline zinc‐air batteries and demonstrates exceptionally long cycle life of 700 h at the current density of 2.0 mA cm −2 . This design provides crucial insights for the nanoengineering of metal‐oxo clusters and atomic‐scale design of catalysts.