Tailoring Hetero-diatomic Sites via Prefabricated Intermetallic Arrangement for Enhanced Oxygen Reduction Reaction in Zinc–Air Batteries

Heteronuclear dual-atom catalysts (DACs) have attracted considerable interest due to their synergistic effects. However, controlling the spatial distribution of bimetallic atoms and developing a comprehensive theoretical framework remain challenging. Here, we systematically investigate long-range-coupled FeM DACs using density functional theory (DFT) calculations to identify hetero-FeZn sites with optimal local electron density and geometry. We introduce a strategy to create precisely ordered sites on hierarchically porous nitrogen-doped carbon (FeZn-NC). Establishing a heterogeneous intermetallic precursor promotes the desired atomic pairs through microstructural inheritance. DFT and experiments confirm synergistic FeN 4 –ZnN 4 interactions induce asymmetric charge distributions that balance oxygen intermediate adsorption/desorption. Consequently, FeZn-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.91 V and a mass activity of 32.52 A mg –1 . Moreover, it achieves high discharge performance and excellent durability exceeding 1300 h in zinc–air batteries (ZABs). More importantly, this prefabricated bimetallic spacing strategy demonstrates versatility for preparing various diatomic sites.