Synergistic Fe–Ni dual-atom sites on hollow carbon enabling high-performance rechargeable zinc–air batteries

The advancement of rechargeable zinc-air batteries (ZABs) hinges critically on the development of efficient and durable bifunctional oxygen electrocatalysts. Herein, we report an atomically dispersed Fe-Ni bifunctional catalyst loaded on a hollow carbon framework (FeNi-hCN) through a density difference-assisted strategy. This unique architecture, leveraging the synergistic interplay between Fe and Ni atoms and the advantageous properties of the hollow carbon support, endows the catalyst with exceptional bifunctional oxygen electrocatalytic activity: a half-wave potential (<i>E</i> _1/2) of 0.91 V for the oxygen reduction reaction (ORR) and overpotential of only 330 mV at 10 mA cm^-2 for the oxygen evolution reaction (OER). Remarkably, the catalyst demonstrates outstanding stability, retaining its activity after 100 000 accelerated degradation test (ADT) cycles and 240 hours of continuous OER operation. When deployed as the air cathode in aqueous ZABs, this catalyst achieves a high peak power density of 212 mW cm^-2 and stable cycling for 560 hours, outperforming a Pt/C + RuO₂ combination. Density functional theory (DFT) calculations elucidate that the Fe-Ni dual sites synergistically lower the adsorption energy of the critical *OOH intermediate, thereby reducing the overall energy barriers for both ORR and OER pathways. This density difference-assisted method also works for other MOFs like UiO-66 and HKUST-1, enabling diverse high-performance carbon-supported catalysts.