Engineering Symmetry-Breaking Centers and d-Orbital Modulation in Triatomic Catalysts for Zinc-Air Batteries

作者：Junjie Zhong, Zhanhao Liang, Ning Liu, Yucui Xiang, Bo Yan, Fangyuan Zhu, Xi Xie, Xuchun Gui, Li‐Yong Gan, Hong Bin Yang, Dingshan Yu, Zhiping Zeng, Guowei Yang · 发表于：ACS Nano · 年份：2024 · DOI：10.1021/acsnano.3c08839 · 被引用次数：35 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Advanced Photocatalysis Techniques

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 CoN 4 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 electrocataly...