Role of Quinone Intermediates as Electron Shuttles in Fenton and Photoassisted Fenton Oxidations of Aromatic Compounds

Abstract

Fenton and related reactions are potentially useful oxidation processes for destroying toxic organic compounds in water. In these reactions, H 2 O 2 is combined with Fe(II) or Fe(III) in the presence or absence of light to generate hydroxyl radicals (HO • ). A relatively neglected area of research is the influence of organic species on the reactivity of iron, and hence on the rate or course of the reaction. This study examined the oxidation of phenol (2 mM) by Fenton systems in the dark (Fe 3+ /H 2 O 2, Fe 2+ /H 2 O 2, and mixed Fe 3+ /Fe 2+ /H 2 O 2 systems) and under UV/visible light (Fe 3+ /H 2 O 2 / h ν). Reactions were conducted at an initial pH of 2.8, with H 2 O 2 in excess and iron in catalytic concentrations. In all cases, the reactions display autocatalysis. In dark reactions, the lag phase decreases (a) with increasing total iron concentration, [Fe] T; (b) as initial [Fe 2+ ] increases when [Fe] T is held constant; (c) in proportion to the amount of hydroquinone (1,4- or 1,2-) added; and (d) in proportion to the amount of quinones (1,4-benzoquinone or 5-hydroxy-1,4-naphthoquinone [juglone]) added. The hydroquinones reduce Fe 3+ to Fe 2+ . An important result is the finding that quinones serve as electron-transfer catalysts between dihydroxycyclohexadienyl radical the HO • adduct of phenol and Fe 3+ by way of a semiquinone radical. This conclusion is supported by simulations with a kinetic model employing known and proposed steps. In irradiated solutions, the lag phase decreases with decreasing wavelength (480−300 nm; 10 nm band-pass). A cause of light initiation, especially above ∼410 nm where photolysis of Fe 3+ and/or H 2 O 2 is negligible, is direct photolysis of quinones to HO • and semiquinone radicals, which subsequently reduce Fe 3+ and re-form the quinone. Thus, quinones play an important catalytic role in Fenton oxidation of aromatic compounds.