Directional Formation of Reactive Oxygen Species via a Non‐Redox Catalysis Strategy that Bypasses Electron Transfer Process

Abstract A broad range of chemical transformations driven by catalytic processes necessitates the electron transfer between catalyst and substrate. The redox cycle limitation arising from the inequivalent electron donation and acceptance of the involved catalysts, however, generally leads to their deactivation, causing substantial economic losses and environmental risks. Here, a “non‐redox catalysis” strategy is provided, wherein the catalytic units are constructed by atomic Fe and B as dual active sites to create tensile force and electric field, which allows directional self‐decomposition of peroxymonosulfate (PMS) molecules through internal electron transfer to form singlet oxygen, bypassing the need of electron transfer between catalyst and PMS. The proposed catalytic approach with non‐redox cycling of catalyst contributes to excellent stability of the active centers while the generated reactive oxygen species find high efficiency in long‐term catalytic pollutant degradation and selective organic oxidation synthesis in aqueous phase. This work offers a new avenue for directional substrate conversion, which holds promise to advance the design of alternative catalytic pathways for sustainable energy conversion and valuable chemical production.