A “Pre‐Division Metal Clusters” Strategy to Mediate Efficient Dual‐Active Sites ORR Catalyst for Ultralong Rechargeable Zn‐Air Battery

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal‐air batteries, catalysts with dual‐active centers have stood out. Here, a “pre‐division metal clusters” strategy is firstly conceived to fabricate a N,S‐dual doped honeycomb‐like carbon matrix inlaid with CoN4 sites and wrapped Co2P nanoclusters as dual‐active centers (Co2P/CoN4@NSC‐500). A crystalline {CoII2} coordination cluster divided by periphery second organic layers is well‐designed to realize delocalized dispersion before calcination. The optimal Co2P/CoN4@NSC‐500 executes excellent 4e− ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn‐air battery (ZAB) assembled by Co2P/CoN4@NSC‐500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm−2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices. A “pre‐division metal clusters” strategy is first conceived to fabricate dual‐active center catalysts (Co2P/CoN4@NSC‐500) with dispersed CoN4 and Co2P sites. The optimal catalyst executes superior ORR activity and was applied in ultralong Zn‐air batteries surpassing the benchmark 20 % Pt/C. Theoretical calculations demonstrate that the dual‐active sites synergistically quicken the formation of the *OOH intermediate, greatly boosting the performance.