ATR-IR spectroscopic study of antimonate adsorption to iron oxide.

Antimonate ions adsorb to iron oxides in mining contexts, but the nature of the adsorbed antimonate species has not frequently been investigated. In this study, ATR-IR spectroscopy was used to reveal that the adsorption of Sb(OH)6- ion from aqueous solutions onto an amorphous iron oxide particle film is accompanied by changes in the Sb(OH)6- spectrum and the loss of OH stretching absorptions from iron oxide surface hydroxyl groups. These spectral changes upon adsorption imply an inner-sphere surface interaction with the formation of Sb-O-Fe bonds as well as some outer-sphere adsorption. The corresponding results from solutions of antimonate in D2O confirm that chemisorption occurs. The dependence of antimonate adsorption on pH in the range from 8 to 3 follows that expected for anions on iron oxide considering its pH-dependent surface charge, with the greatest amount of adsorbed antimonate at pH 3. The study of adsorption/desorption kinetics showed a more rapid desorption of adsorbed antimonate under alkaline conditions. This trend is expected from the pH dependence of the antimonate charge and iron oxide surface charge, but it might be partly due to the fact that high pH favors hydrolysis of antimonate oligomers formed on the iron oxide surface from adsorption under acidic conditions.