ABSTRACT
In a natural environment, Fe(ii) adsorbed onto the surfaces of natural particles to form various surface complex species can influence the transformation of contaminants. The reductive reactivity of the [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples are close correlated with the surrounding conditions. In this study, we investigated the effects of Si(iv) on the reductive reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples adsorbed onto γ-Al2O3. Experiments were conducted under different conditions to investigate the effects of Si(iv) on the reactivity of [[triple bond, length as m-dash]Fe(iii)]/[[triple bond, length as m-dash]Fe(ii)] couples for 2-nitrophenol (2-NP, selected as the model pollutant) reduction in γ-Al2O3 suspensions. Kinetics results revealed that chemical adsorption is the rate limiting step in Fe(ii) and Si(iv) adsorption processes and the reduction of 2-NP is an endothermic reaction. The linear correlations between the reduced peak oxidation potential (E p) (versus SCE) and 2-NP reduction rate (ln k), and between the adsorbed Fe(ii) density (ρ Fe(II)) and ln k, illustrated that E p and ρ Fe(II) are two key factors in the inhibiting effects of Si(iv) on the reductive reactivity of Fe(iii)/Fe(ii) couples on γ-Al2O3. The results of Fe K-edge X-ray absorption spectroscopy revealed that the increase of Si(iv) concentration resulted in the gradual change in the composition of the adsorbed Fe species from pure [triple bond, length as m-dash]AlOFe+ (γ-Al2O3 surface-bound Fe(ii) species with higher reductive reactivity) to a mixture of [triple bond, length as m-dash]AlOFe+ and [triple bond, length as m-dash]SiOFe+ (SiO2 surface-bound Fe(ii) species with lower reductive reactivity), leading to the decrease in ρ Fe(II), the positive shift in E p, the increase in activation energy (E a), and consequently the decrease in the reduction rate (ln k) of 2-NP.
