Peroxide Directingthe Iron Cycling for Tailored Generationof Active Oxidants in Aqueous Fenton Reactions

The diverse electron transfer between iron and peroxides endows Fenton and related reactions with versatility in generating multiple active oxidants, underpinning their important contribution to environmental remediation. The type of active oxidant generated can be tailored by the structure of peroxides, yet the underlying mechanism remains to be uncovered. Herein, taking the reaction of Fe(III)–picolinate (Fe^III–PICA) with peroxides as an examplary case, we provide a detailed structure–activity analysis to clarify this issue. Experimental results show that the reaction of Fe^III–PICA with H₂O₂, <i>tert</i>-butyl hydroperoxide, and isopropyl hydroperoxide initiates the Haber–Weiss cycle to generate radicals exclusively, whereas the reaction with peroxymonosulfate, peracetic acid, and <i>m</i>-chloroperoxybenzoic acid generates Fe(IV). Theoretical calculations reveal that the peroxide-dependent generation of active oxidants is attributed to the selectivity in the lysis of the PICA–Fe^III–OOR intermediate, which serves as a rate-limiting step in Fenton reactions. The inductive effect of R dynamically modulates the strength of Fe–O/O–O bonding and the stability of cleavage products to favor Fe–O homolysis of PICA–Fe^III–OOR toward Fe(III)/Fe(II) cycling. Conversely, the coordination of R to Fe(III) stabilizes transition states to favor O–O homolysis for Fe(III)/Fe(IV) cycling. These findings are believed to shed new light on the pathway selectivity of iron cycling in aqueous Fenton reactions.