Atom‐Scale Charge Reorganization for MOF‐Driven Electrocatalytic Switching

Abstract Achieving dynamic and reversible control over electrocatalytic reactions underpins the chemistry of next‐generation energy devices. This work reveals a unique mechanism, atom‐scale charge reorganization within a deliberately engineered metal‐organic framework (MOF), that enables electrocatalytic switching during dioxygen redox processes. By precisely modulating atomic‐level electronic structures, oxidation states and localized charge distributions through interfaces with nitrogen‐rich supports, this work realizes a switchable bifunctional catalytic pathway that lowers the oxygen evolution (OER) and reduction (ORR) voltage gap to an exceptionally low 0.77 V. Notably, this modulation facilitates a mechanistic transition from a two‐ to a four‐electron pathway during ORR, significantly enhancing reaction efficiency. This charge‐driven reorganization mechanism translates into a high‐performance rechargeable air battery, delivering superior power density, cycling stability, and energy efficiency over 100 h of continuous operation, surpassing noble metal‐based systems. This work introduces localized charge reorganization as a powerful design principle for reconfigurable and high‐efficiency MOF‐based electrocatalysts in next‐generation energy devices.