Coherent nanoscale cobalt/cobalt oxide heterostructures embedded in porous carbon for the oxygen reduction reaction

Cost-effective and efficient electrocatalysts for the oxygen reduction reaction (ORR) are crucial for fuel cells and metal-air batteries. Herein, we report the facile synthesis of a Co/CoO/Co₃O₄ heterostructure embedded in a porous carbon matrix by refluxing and annealing. This composite exhibits several structural merits for catalyzing the ORR: (1) the existence of metallic Co and graphitic carbon enhanced the electrical conduction; (2) the porous, loose carbon network facilitated the electrolyte permeation and mass transport; (3) more importantly, the nanosized coherent CoO/Co₃O₄ heterojunctions with structural defects and oxygen vacancies enhanced the charge transport/separation at the interface and adsorption affinity to O₂, thus promoting the ORR kinetics and lowering the reaction barrier. Consequently, the composite electrode manifests high electrocatalytic activity, attaining a current density of 6.7 mA cm^-2 at -0.8 V (vs. Ag/AgCl), which is superior to pure CoO nanoparticles (4.7 mA cm^-2), and has good methanol tolerance. The present strategy based on heterostructure and vacancy engineering may pave the way for the exploration of more advanced, low-cost electrocatalysts for electrochemical reduction and evolution processes.