Tailored sp²-C─F Bonding for Reversible Oxygen-Peroxide Electrocatalysis

Rechargeable zinc-air batteries are fundamentally limited by the sluggishness of four-electron (4e^-) oxygen electrocatalysis and by bifunctional catalysts that rarely combine high activity with long-term durability, resulting in substantial polarization and poor reversibility. Replacing this chemistry with O₂-H₂O₂ interconversion offers a compelling alternative, because two-electron (2e^-) oxygen electrocatalysis features intrinsically more reversible pathways and faster kinetics. Herein, fluorine-doped graphene is established as a programmable electrocatalytic platform for O₂-H₂O₂ interconversion, where tailored sp²-C─F bonding acts as a precise electronic lever to regulate OOH* intermediate binding and thereby steer O₂-H₂O₂ redox selectivity and kinetics. By controlling fluorine incorporation, the local electronic environment of graphene is delicately engineered without sacrificing electrical conductivity. The optimized catalyst exhibits outstanding bifunctional activity for 2e^- oxygen reduction reaction (2e^- -ORR) and peroxide oxidation reaction (POR), translating into rechargeable zinc-based batteries with high power output and robust long-term durability. Mechanistic studies reveal that sp²-C─F bonding induces localized electrostatic polarization at neighboring carbon sites, selectively stabilizing OOH* intermediates, lowering the kinetic barrier for 2e^--ORR, and concurrently facilitating POR while minimizing parasitic reactions. These findings demonstrate a fundamental structure-property principle linking fluorine-induced polarization with O₂-H₂O₂ redox kinetics, and position fluorinated carbon frameworks as a versatile foundation for next-generation reversible energy storage.