A Superior Bifunctional Electrocatalyst in Which Directional Electron Transfer Occurs Between a Co/Ni Alloy and Fe─N─C Support

Abstract Stable, efficient, and economical bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are needed for rechargeable Zn–air batteries. In this study, a directional electron transfer pathway is exploited in a spatial heterojunction of Co y Ni x @Fe─N─C heterogeneous catalyst for effective bifunctional electrolysis (OER/ORR). Thereinto, the Co/Ni alloy is strongly coupled to the Fe─N─C support through Co/Ni─N bonds. DFT calculations and experimental findings confirm that Co/Ni─N bonds play a bridging role in the directional electron transfer from Co/Ni alloy to the Fe─N─C support, increasing the content of pyridinic nitrogen in the ORR‐active support. In addition, the discovered directional electron transfer mechanism enhances both the ORR/OER activity and the durability of the catalyst. The Co 0.66 Ni 0.34 @Fe─N─C with the optimal Ni/Co ratio exhibits satisfying bifunctional electrocatalytic performance, requiring an ORR half‐wave potential of 0.90 V and an OER overpotential of 317 mV at 10 mA cm −2 in alkaline electrolytes. The assembled rechargeable zinc–air batteries (ZABs) incorporating Co 0.66 Ni 0.34 @Fe─N─C cathode exhibits a charge–discharge voltage gap comparable to the Pt/C||IrO 2 assembly and high robustness for over 60 h at 20 mA cm −2 .