Ferryl Ion in the Photo-Fenton Process at Acidic pH: Occurrence, Fate, and Implications

Fenton processes produce reactive species that can oxidize organic compounds in natural and engineered systems. While it is well-documented that Fenton reactions produce hydroxyl radical (HO•) under acidic conditions, we demonstrated the generation of ferryl ion (FeIVO2+) in the UV/Fe(III) and UV/Fe(III)/H2O2 systems at pH 2.8 using methyl phenyl sulfoxide (PMSO) as the probe compound. Moreover, we clarified that FeIVO2+ is parallelly formed via the oxidation of Fe(III) by HO• and the O–O homolysis of [FeIII–OOH]2+ in the photo-Fenton process. The rate constant for the reaction between HO• and Fe3+ measured by laser flash photolysis was 4.41 × 107 M–1 s–1. The rate constant and quantum yield for thermal and photo O–O homolysis of [FeIII–OOH]2+ complex were 1.4 × 10–2 s–1 and 0.3, respectively, which were determined by fitting PMSO2 formation. While FeIVO2+ forms predominantly through the reaction between HO• and Fe3+ in the absence of H2O2, the relative contribution of [FeIII–OOH]2+ O–O homolysis to FeIVO2+ formation highly depends on the molar ratio of [H2O2]0/[Fe(III)]0, the level of HO• scavenging, and incident irradiance in the UV/Fe(III)/H2O2 system. Accordingly, an optimized kinetic model was developed by incorporating FeIVO2+-involved reactions into the conventional photo-Fenton model, which can accurately predict Fe(II) formation and contaminant decay in the UV/Fe(III) and UV/Fe(III)/H2O2 systems. Our study illuminated the underlying formation mechanism of reactive oxidative species in the photo-Fenton process and highlighted the role of FeIVO2+ evolution in modulating the iron cycle and pollutant abatement therein.