Enhanced Fe IV ═O Generation via Peroxymonosulfate Activation by an Edge‐Site Engineered Single‐Atom Iron Catalyst

Abstract As an oxidant, the ferryl‐oxo complex (Fe IV ═O) offers excellent reactivity and selectivity for degrading recalcitrant organic contaminants. However, enhancing Fe IV ═O generation on heterogeneous surfaces remains challenging because the underlying formation mechanism is poorly understood. This study introduces edge defects onto a single‐atom Fe catalyst (FeNC‐edge) to promote Fe IV ═O generation via peroxymonosulfate (PMS) activation. In the presence of PMS, the FeNC‐edge catalyst at a low dose (20 mg L −1 , equivalent to 0.14 mg L −1 Fe) exhibits unprecedented activity for organic contaminant degradation. Electrochemical analysis, in situ Raman spectroscopy, and Fe IV ═O probe experiments confirm that Fe IV ═O generation is enhanced on the surface of FeNC‐edge. Density functional theory calculations reveal that the introduced edge sites concentrate electron density on active …