Unlocking Durable High-Power Zn-Air Batteries: {Fe3O} Molecular Furnace-Forged Dual-Site Catalysts Enabling Synergistic Oxygen Reduction in Alkaline Media.

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 (Fe3C/Fe-NC1050) by in situ domain-confined complexation of ZIF-8(Zn) using {Fe3O} as a core metal-oxo cluster. The unique flexible ligand-carboxylate group of {Fe3O} 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 Fe3C (110) crystal plane modulates the electronic structure of neighboring Fe-N4 active sites, thus reducing the adsorption energy of key step O2→*OOH and endowing the material with excellent methanol resistance and stability. Structural characterization and theoretical calculations reveal that the synergistic interaction between {Fe3O} 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.