Generation of FeIV=O and its Contribution to Fenton‐Like Reactions on a Single‐Atom Iron−N−C Catalyst

Generating Fe^IV =O on single-atom catalysts by Fenton-like reaction has been established for water treatment; however, the Fe^IV =O generation pathway and oxidation behavior remain obscure. Employing an Fe-N-C catalyst with a typical Fe-N₄ moiety to activate peroxymonosulfate (PMS), we demonstrate that generating Fe^IV =O is mediated by an Fe-N-C-PMS* complex-a well-recognized nonradical species for induction of electron-transfer oxidation-and we determined that adjacent Fe sites with a specific Fe₁ -Fe₁ distance are required. After the Fe atoms with an Fe₁ -Fe₁ distance <4 Å are PMS-saturated, Fe-N-C-PMS* formed on Fe sites with an Fe₁ -Fe₁ distance of 4-5 Å can coordinate with the adjacent Fe^II -N₄ , forming an inter-complex with enhanced charge transfer to produce Fe^IV =O. Fe^IV =O enables the Fenton-like system to efficiently oxidize various pollutants in a substrate-specific, pH-tolerant, and sustainable manner, where its prominent contribution manifests for pollutants with higher one-electron oxidation potential.