Atomically Dispersed Fe2 and Ni Sites for Efficient and Durable Oxygen Electrocatalysis

Developing highly efficient, cost‐effective, and robust electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is paramount for the large‐scale commercialization of renewable fuel cells and rechargeable metal‐air batteries. Herein, a new ternary‐atom catalyst that is composed of paired Fe sites and single Ni sites (as Fe2‐N6 and Ni‐N4) coordinated onto hollow nitrogen‐doped carbon microspheres is developed. The as‐synthesized catalyst exhibits remarkable activities toward both the ORR and OER in an alkaline media, with superior performances to those of the control materials that contain only Fe2‐N6 or Ni‐N4 sites. Density functional theory calculations and in situ infrared (IR) spectroscopic studies clearly reveal that the Fe2‐N6 centers are the active sites for both ORR and OER, and their electrocatalytic activities are synergistically enhanced through optimization of their d‐band centers by the Ni‐N4 sites. This ternary‐atom catalyst may be a promising, alternative, sustainable catalyst to commercially used Pt‐ and Ru‐based catalysts to drive both ORR and OER in rechargeable zinc‐air batteries and other related applications.