In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction

作者：Meihuan Liu, Jing Zhang, Hui Su, Yaling Jiang, Wanlin Zhou, Chenyu Yang, Shuowen Bo, Jun Pan, Qinghua Liu · 发表于：Nature Communications · 年份：2024 · DOI：10.1038/s41467-024-45990-w · 被引用次数：264 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Fuel Cells and Related Materials

Abstract Single-atom catalysts, especially those with metal−N 4 moieties, hold great promise for facilitating the oxygen reduction reaction. However, the symmetrical distribution of electrons within the metal−N 4 moiety results in unsatisfactory adsorption strength of intermediates, thereby limiting their performance improvements. Herein, we present atomically coordination-regulated Co single-atom catalysts that comprise a symmetry-broken Cl−Co−N 4 moiety, which serves to break the symmetrical electron distribution. In situ characterizations reveal the dynamic evolution of the symmetry-broken Cl−Co−N 4 moiety into a coordination-reduced Cl−Co−N 2 structure, effectively optimizing the 3 d electron filling of Co sites toward a reduced d -band electron occupancy ( d 5.8 → d 5.28 ) under reaction conditions for a fast four-electron oxygen reduction reaction process. As a result, the coordination-regulated Co single-atom catalysts deliver a large half-potential of 0.93 V and a mass activity of 5480 A g metal −1 . Importantly, a Zn-air battery using the coordination-regulated Co single-atom catalysts as the cathode also exhibits a large power density and excellent stability.