Understanding the Synergistic Effects of Cobalt Single Atoms and Small Nanoparticles: Enhancing Oxygen Reduction Reaction Catalytic Activity and Stability for Zinc‐Air Batteries.

The development of earth‐abundant oxygen reduction reaction (ORR) catalysts with high catalytic activity and good stability for practical metal‐air batteries remains an enormous challenge. Herein, a highly efficient and durable ORR catalyst is reported, which consists of atomically dispersed Co single atoms (Co‐SAs) in the form of Co‐N4 moieties and small Co nanoparticles (Co‐SNPs) co‐anchored on nitrogen‐doped porous carbon nanocage (Co‐SAs/SNPs@NC). Benefiting from the synergistic effect of Co‐SAs and Co‐SNPs as well as the enhanced anticorrosion capability of the carbon matrix brought by its improved graphitization degree, the resultant Co‐SAs/SNPs@NC catalyst exhibits outstanding ORR activity and remarkable stability in alkaline media, outperforming Co‐SAs‐based catalyst (Co‐SAs@NC), and benchmark Pt/C catalyst. Density functional theory calculations reveal that the strong interaction between Co‐SNPs and Co‐N4 sites can increase the valence state of the active Co atoms in Co‐SAs/SNPs@NC and moderate the adsorption free energy of ORR intermediates, thus facilitating the reduction of O2. Moreover, the practical zinc‐air battery assembled with Co‐SAs/SNPs@NC catalyst demonstrates a maximum power density of 223.5 mW cm–2, a high specific capacity of 742 W h kg–1 at 50 mA cm–2 and a superior cycling stability. [ABSTRACT FROM AUTHOR]