Insufficient bifunctional activity of electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the major obstruction to the application of rechargeable metal-air batteries. The primary reason is the mutual constraint of ORR and OER mechanism, involving the same oxygen-containing intermediates and demonstrating the scaling limitations of the adsorption energies. Herein, it is reported a high-valence Ir single atom anchored on manganese oxide (IrSA-MnOx) bifunctional catalyst showing independent pathways for ORR and OER, i.e., associated 4e- pathway on high-valence Ir site for ORR and a novel chemical-activated concerted mechanism for OER, where a distinct spontaneous chemical activation process triggers direct O─O coupling. The IrSA-MnOx therefore delivers outstanding bifunctional activities with remarkably low potential difference (0.635 V) between OER potential at 10 mA cm-2 and ORR half-wave potential in alkaline solution. This work breaks the scaling limitations and provides a new avenue to design efficient and multifunctional electrocatalysts.
Keywords: Ir single‐atom; bifunctional electrocatalysis; manganese oxide; reaction mechanism; zinc–air battery.
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