Preferentially Engineering FeN4 Edge Sites onto Graphitic Nanosheets for Highly Active and Durable Oxygen Electrocatalysis in Rechargeable Zn–Air Batteries

Abstract Single‐atom FeN 4 sites at the edges of carbon substrates are considered more active for oxygen electrocatalysis than those in plane; however, the conventional high‐temperature pyrolysis process does not allow for precisely engineering the location of the active site down to atomic level. Enlightened by theoretical prediction, herein, a self‐sacrificed templating approach is developed to obtain edge‐enriched FeN 4 sites integrated in the highly graphitic nanosheet architecture. The in situ formed Fe clusters are intentionally introduced to catalyze the growth of graphitic carbon, induce porous structure formation, and most importantly, facilitate the preferential anchoring of FeN 4 to its close approximation. Due to these attributes, the as‐resulted catalyst (denoted as Fe/N‐G‐SAC) demonstrates unprecedented catalytic activity and stability for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) by showing an impressive half‐wave potential of 0.89 V for the ORR and a small overpotential of 370 mV at 10 mA cm −2 for the OER. Moreover, the Fe/N‐G‐SAC cathode displays encouraging performance in a rechargeable Zn–air battery prototype with a low charge–discharge voltage gap of 0.78 V and long‐term cyclability for over 240 cycles, outperforming the noble metal benchmarks.