Advanced Oxidation Process Based on the Cr(III)/Cr(VI) Redox Cycle

Oxidative degradation of aqueous organic pollutants, using 4-chlorophenol (4-CP) as a main model substrate, was achieved with the concurrent H(2)O(2)-mediated transformation of Cr(III) to Cr(VI). The Fenton-like oxidation of 4-CP is initiated by the reaction between the aquo-complex of Cr(III) and H(2)O(2), which generates HO(•) along with the stepwise oxidation of Cr(III) to Cr(VI). The Cr(III)/H(2)O(2) system is inactive in acidic condition, but exhibits maximum oxidative capacity at neutral and near-alkaline pH. Since we previously reported that Cr(VI) can also activate H(2)O(2) to efficiently generate HO(•), the dual role of H(2)O(2) as an oxidant of Cr(III) and a reductant of Cr(VI) can be utilized to establish a redox cycle of Cr(III)-Cr(VI)-Cr(III). As a result, HO(•) can be generated using both Cr(III)/H(2)O(2) and Cr(VI)/H(2)O(2) reactions, either concurrently or sequentially. The formation of HO(•) was confirmed by monitoring the production of p-hydroxybenzoic acid from [benzoic acid + HO(•)] as a probe reaction and by quenching the degradation of 4-CP in the presence of methanol as a HO(•) scavenger. The oxidation rate of 4-CP in the Cr(III)/H(2)O(2) solution was highly influenced by pH, which is ascribed to the hydrolysis of Cr(III)(H(2)O)(n) into Cr(III)(H(2)O)(n-m)(OH)(m) and the subsequent condensation to oligomers. The present study proposes that the Cr(III)/H(2)O(2) combined with Cr(VI)/H(2)O(2) process is a viable advanced oxidation process that operates over a wide pH range using the reusable redox cycle of Cr(III) and Cr(VI).