Engineering Catalytic Active Sites on Cobalt Oxide Surface for Enhanced Oxygen Electrocatalysis

Abstract Tuning the catalytic active sites plays a crucial role in developing low cost and highly durable oxygen electrode catalysts with precious metal‐competitive activity. In an attempt to engineer the active sites in Co 3 O 4 spinel for oxygen electrocatalysis in alkaline electrolyte, herein, controllable synthesis of surface‐tailored Co 3 O 4 nanocrystals including nanocube (NC), nanotruncated octahedron (NTO), and nanopolyhedron (NP) anchored on nitrogen‐doped reduced graphene oxide (N‐rGO), through a facile and template‐free hydrothermal strategy, is provided. The as‐synthesized Co 3 O 4 NC, NTO, and NP nanostructures are predominantly enclosed by {001}, {001} + {111}, and {112} crystal planes, which expose different surface atomic configurations of Co 2+ and Co 3+ active sites. Electrochemical results indicate that the unusual {112} plane enclosed Co 3 O 4 NP on rGO with abundant Co 3+ sites exhibit superior bifunctional activity for oxygen reduction and evolution reactions, as well as enhanced metal–air battery performance in comparison with other counterparts. Experimental and theoretical simulation studies demonstrate that the surface atomic arrangement of Co 2+ /Co 3+ active sites, especially the existence of octahedrally coordinated Co 3+ sites, optimizes the adsorption, activation, and desorption features of oxygen species. This work paves the way to obtain highly active, durable, and cost‐effective electrocatalysts for practical clean energy devices through regulating the surface atomic configuration and catalytic active sites.