Atomically Dispersed Fe/N4 and Ni/N4 Sites on Separate‐Sides of Porous Carbon Nanosheets with Janus Structure for Selective Oxygen Electrocatalysis

Abstract Dual single atoms catalysts have promising application in bifunctional electrocatalysis due to their synergistic effect. However, how to balance the competition between rate‐limiting steps (RDSs) of reversible oxygen reduction and oxygen evolution reaction (OER) and fully expose the active centers by reasonable structure design remain enormous challenges. Herein, Fe/N 4 and Ni/N 4 sites separated on different sides of the carbon nanosheets with Janus structure (FeNi jns /NC) is synthesized by layer‐by‐layer assembly method. Experiments and calculations reveal that the side of Fe/N 4 is beneficial to oxygen reduction reaction (ORR) and the Ni/N 4 side is preferred to OER. Such Janus structure can take full advantage of two separate‐sides of carbon nanosheets and balance the competition of RDSs during ORR and OER. FeNi jns /NC possesses superior ORR and OER activity with ORR half‐wave potential of 0.92 V and OER overpotential of 440 mV at J = 10 mA cm −2 . Benefiting from the excellent bifunctional activities, FeNi jns /NC assembled aqueous Zn–air battery (ZAB) demonstrates better maximum power density, and long‐term stability (140 h) than Pt/C+RuO 2 catalyst. It also reveals superior flexibility and stability in solid‐state ZAB. This work brings a novel perspective for rational design and understanding of the catalytic mechanisms of dual single atom catalysts.