One‐Step Pyrolysis Construction of Bimetallic Atom‐Cluster Sites for Boosting Bifunctional Catalytic Activity in Zn‐Air Batteries

Abstract Due to their unique advantages, single atoms and clusters of transition metals are expected to achieve a breakthrough in catalytic activity, but large‐scale production of active materials remains a challenge. In this work, a simple solvent‐free one‐step annealing method is developed and applied to construct diatomic and cluster active sites in activated carbon by utilizing the strong anchoring ability of phenanthroline to metal ions, which can be scaled for mass productions. Benefiting from the synergy between the different metals, the obtained sub‐nano‐bimetallic atom‐cluster catalysts (FeNi AC ‐NC) exhibit high oxygen reduction reactions (ORR) activity ( E 1/2 = 0.936 V vs. RHE) and a small ORR/oxygen evolution reaction (OER) potential gap of only 0.594 V. An in‐house pouch Zn‐air battery is assembled using an FeNi AC ‐NC catalyst, which demonstrates a stability of 1000 h, outperforming previous reports. The existence of clusters and their effects on catalytic activity is analyzed by density functional theory calculations to reveal the chemistry of nano‐bimetallic atom‐cluster catalysts.