Defective Fe 3 O 4- x Few-Atom Clusters Anchored on Nitrogen-Doped Carbon as Efficient Oxygen Reduction Electrocatalysts for High-Performance Zinc-Air Batteries.

It remains a challenge to develop cost-effective, high-performance oxygen electrocatalysts for rechargeable metal-air batteries. Herein, zinc-mediated zeolitic imidazolate frameworks are exploited as the template and nitrogen and carbon sources, onto which is deposited a Fe 3 O 4 layer by plasma-enhanced atomic layer deposition. Controlled pyrolysis at 1000 °C leads to the formation of high density of Fe 3 O 4- x few-atom clusters with abundant oxygen vacancies deposited on an N-doped graphitic carbon framework. The resulting nanocomposite (Fe 3 O 4- x /NC-1000) exhibits a markedly enhanced electrocatalytic performance toward oxygen reduction reaction in alkaline media, with a remarkable half-wave potential of +0.930 V versus reversible hydrogen electrode, long-term stability, and strong tolerance against methanol poisoning, in comparison to samples prepared at other temperatures and even commercial Pt/C. Notably, with Fe 3 O 4- x /NC-1000 as the cathode catalyst, a zinc-air battery delivers a high power density of 158 mW cm -2 and excellent durability at 5 mA cm -2 with stable 2000 charge-discharge cycles over 600 h. This is ascribed to the ready accessibility of the Fe 3 O 4- x catalytic active sites, and enhanced electrical conductivity, oxygen adsorption, and electron-transfer kinetics by surface oxygen vacancies. Further contributions may arise from the highly conductive and stable N-doped graphitic carbon frameworks.