Unraveling the configuration-activity relationship and synergistic enhancement mechanism (such as real active center, electron spin-state, and d-orbital energy level) for triatomic catalysts, as well as their intrinsically bifunctional oxygen electrocatalysis, is a great challenge. Here we present a triatomic catalyst (TAC) with a trinuclear active structure that displays extraordinary oxygen electrocatalysis for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), greatly outperforming the counterpart of single-atom and diatomic catalysts. The aqueous Zn-air battery (ZAB) equipped with a TAC-based cathode exhibits extraordinary rechargeable stability and ultrarobust cycling performance (1970 h/3940 cycles at 2 mA cm-2, 125 h/250 cycles at 10 mA cm-2 with negligible voltage decay), and the quasi-solid-state ZAB displays outstanding rechargeability and low-temperature adaptability (300 h/1800 cycles at 2 mA cm-2 at -60 °C), outperforming other state-of-the-art ZABs. The experimental and theoretical analyses reveal the symmetry-breaking CoN4 configuration under incorporation of neighboring metal atoms (Fe and Cu), which leads to d-orbital modulation, a low-shift d band center, weakened binding strength to the oxygen intermediates, and decreased energy barrier for bifunctional oxygen electrocatalysis. This rational tricoordination design as well as an in-depth mechanism analysis indicate that hetero-TACs can be promisingly applied in various electrocatalysis applications.
Keywords: Oxygen evolution reaction; Oxygen reduction reaction; Symmetry-breaking center; Triatomic site catalysts; Zn-air battery; d-orbital modulation.