Boron‐Activated Single‐Metal‐Site Catalysts Break Adsorption‐Energy Scaling Relations for Robust Bifunctional Oxygen Catalysis

Abstract The electrocatalytic oxygen evolution and reduction reaction (OER/ORR) catalysts are paramount to many renewable energy technologies. Atomically‐dispersed transition‐metal catalysts are compelling alternatives to current dominant noble‐metal catalysts, yet they often show inadequate activity for OER and insufficient durability in practical battery operations. Here, we show a rational methodology that enables single‐metal‐site catalyst to break universal adsorption‐energy scaling limitations for both OER/ORR and push bifunctional catalytic performance of transition‐metal‐dominated catalysts to unprecedented level. Other than metal–nitrogen coordination, the newly‐designed catalyst (namely metal‐C‐B) stabilizes atomic metals on B‐doped carbon via metal–carbon coordination and afford favorable electronic engineering. The optimized Co‐C‐B catalyst in base exhibits a record‐low OER overpotential of 172 mV at 10 mA cm −2 and a superior ORR half‐wave potential of 0.87 V with robust stability over 500 h of continuous OER or ORR, which endows a rechargeable Zn–air battery with over 6755 charge/discharge cycles. The delivered mass activities of 33941 A g metal −1 for OER and 15873 A g metal −1 for ORR are respectively ∼112/80‐fold higher than those of commercial noble‐metal counterparts. Atomically‐dispersed CoC 4 Bᵪ moieties were theoretically identified as unique bifunctional active centers, breaking usual scaling relations of intermediates adsorption and boosting inherent OER/ORR activities simultaneously beyond theoretical limitations for single metal site.