Fe-catalyzed photoreduction of Cr(VI) with dicarboxylic acid (C₂–C₅): divergent reaction pathways

Reduction of carcinogenic hexavalent chromium (Cr(VI)) by ferrous iron (Fe(II)) to essentially nontoxic trivalent chromium (Cr(III)) is a simple and effective method for Cr(VI) decontamination. In this study, the photoreduction efficacy of Cr(VI) in acidic Fe(III)/Fe(II) solutions was examined in the presence of dicarboxylic acids (DCA) (i.e. oxalic acid (Oxal), malonic acid (Mal), succinic acid (Suc), and glutaric acid (Glu)). Rates of Cr(VI) reduction under UV irradiation depend on the photochemistry of Fe(III)/Fe(II) complexes with DCA, following the order of Oxal > Suc ≈ Glu > Mal. Fe(III)-oxalato complexes are favorable for transforming Cr(VI) due to the formation of relative abundance of Fe(II) and reductive radicals such as (Formula presented.) , (Formula presented.) after photoreaction, whereas Fe(III)-Mal complexes upon UV irradiation generate the lowest amount of Fe(II) among all the Fe-DCA complexes, and thus have poor capacity for Cr(VI) reduction. The effects of Suc and Glu on the Cr(VI) reduction are insignificant since the Fe(III)-OH complexes are still the main Fe(III) species due to their weak chelating abilities with Fe(III). This work has important implications for selecting the favorable ligands of Fe(III) for light-induced Cr(VI) transformation and designing the methods for treating wastewater with low-molecular-weight acids and Cr(VI).