Abstract

AbstractThe compositing strategy offers great potential in designing bifunctional oxygen electrocatalysts for Zn–air batteries. Recent reports reveal that the couple of RuO2, serving as a benchmark oxygen evolution reaction (OER) catalyst, with other oxygen reduction reaction (ORR) catalysts is a wise choice to build highly efficient bifunctional electrocatalysts. However, the design criteria for ORR and OER activities of RuO2‐based composite catalysts are still unclear. Herein, a series of transition metal (Fe, Co, Mn, and Ni)‐doped spinel oxides are designed to support RuO2 nanorods for exploring the reaction mechanism. Through advanced technology, it is considered that increasing the content and binding energy of Co3+ and enhancing the oxidation state of Ru4+ is an efficient strategy to promote ORR and OER activities for RuO2/Co‐based spinel oxide composite catalysts. It is found that coupling Mn‐doping Co3O4 (CMO) supports with RuO2 can induce the highest catalytic activities in ORR/OER and excellent performance in rechargeable Zn–air batteries. Operando electrochemical impedance spectroscopy and theoretical calculation further prove the synergistic effect between RuO2 and CMO supports originated from the oxygen overflow to overcome the large barrier for oxygen desorption on RuO2 during OER and oxygen adsorption on CMO supports during ORR.

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