In situ constructing Co/Co-Ox/Co-Nx diverse active sites on hollow porous carbon spheres derived from Co-MOF for efficient bifunctional electrocatalysis in rechargeable Zn-air

Earth-rich, durable, and efficient bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is vitally important for the wide application of zinc-air batteries in the future. However, due to the single active site, traditional commercial benchmark catalysts typically exhibit selective activity in only one of the two reactions (ORR or OER), making it difficult to meet the dual functional catalytic requirements. Developing efficient oxygen electrocatalysts that achieve diverse active sites on a single catalyst and understanding their internal synergistic reaction activity remain a challenge. Herein, spherical hollow porous carbon matrix composites (s-Co/CoNC) with the coexistence of diverse intrinsic active sites including Co-Nx and Co-Ox species and metal Co nanoparticles were prepared by pyrolysis with oxygen-enriched Co-MOFs as precursor in the presence of melamine. Owing to the combined advantages of the catalyst including the great specific surface area, good conductivity, abundant diverse intrinsic active sites towards ORR and OER, and the electronic interaction among active sites and the optimized the adsorption/desorption process of oxygen species at the catalyst surface, s-Co/CoNC exhibits desirable electrocatalytic activity for both ORR and OER with an ORR half-wave potential of 0.81 V, an OER potential of 1.53 V(vs. RHE at 10 mA cm−2), providing a small reversible potential difference of 0.72 V, superior to the commercial noble-metal catalysts and the most reported cobalt based ORR/OER catalysts. The assembled s-Co/CoC-based rechargeable Zn-air batteries possess high peak power density of 101.7 mW cm−2. This work provides a significant strategy for constructing high-performance dual functional catalysts for secondary Zn-air batteries.