Effect of Mn substitution on the oxidation/adsorption abilities of iron(III) oxyhydroxides

In this study, divalent manganese ions [Mn(II)] were substituted a part of divalent iron ions [Fe(II)] present in Fe oxyhydroxides to prepare novel composites (Mn@Feox). The composites were prepared by (1) simultaneous hydrolysis of Fe(II) and Mn(II), and (2) rapid oxidation with H₂O₂. The resulting Mn@Feox prepared with different molar ratios of Fe and Mn was characterized and evaluated for their abilities to adsorb arsenic species [As(III) and As(V)] in aqueous solution. X-ray diffraction and field emission transmission electron microscope analyses revealed Mn@Feox has a δ-(Fe_1−x, Mn_x)OOH-like structure with their mineralogical properties resembling those of feroxyhyte (δ-FeOOH). The increase in Mn substitution in Mn@Feox enhanced the oxidative ability to oxidize As(III) to As(V), but it decreased the adsorption capacity for both arsenic species. The optimal Mn/Fe molar ratio that could endow oxidation and magnetic capabilities to the composite without significantly compromising As adsorption capability was determined to be 0.1 (0.1Mn@Feox). The adsorption of As(III) on 0.1Mn@Feox was weakly influenced by pH change while As(V) adsorption showed high dependence on pH, achieving nearly complete removal at pH < 5.7 but gradual decrease at pH > 5.7. The adsorption kinetics and isotherms of As(III) and As(V) showed good conformity to pseudo-second-order kinetics model and Freundlich model, respectively.