Tailored sp ² ‐C─F Bonding for Reversible Oxygen‐Peroxide Electrocatalysis

ABSTRACT

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 O ₂ –H ₂ O ₂ 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 O ₂ ‐H ₂ O ₂ interconversion, where tailored sp ² ‐C─F bonding acts as a precise electronic lever to regulate OOH* intermediate binding and thereby steer O ₂ –H ₂ O ₂ 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 sp ² ‐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 O ₂ –H ₂ O ₂ redox kinetics, and position fluorinated carbon frameworks as a versatile foundation for next‐generation reversible energy storage.