Effects of Co(II) ion exchange, Ni(II)- and V(V)-doping on the transformation behaviors of Cr(III) on hexagonal turbostratic birnessite-water interfaces

Natural birnessite-like minerals are commonly enriched in various transitional metals (TMs), which greatly modify the mineral structure and properties. However few studies are yet conducted systematically on the effects of TM doping on birnessite reactivity towards Cr(III) oxidation. In the present study, the transformation behaviors of Cr(III) on Co-, Ni-, V-containing birnessites were investigated. Co and Ni doping generally decrease the mineral crystalline sizes and hydrodynamic sizes (DH) while V-doping greatly decreases the crystalline sizes but not the DH, owing to particle aggregation. Co and Ni firstly decrease and then increase the mineral zeta potentials (ζ) at pH4 while V decreases ζ. Electrochemical specific capacitances for Co-containing birnessites are gradually reduced, while those for Ni-doped birnessites are slightly reduced and for V-doped birnessites increased, which have a positively linear relationship with the amounts of Cr(III) oxidized by these samples. Cr(III) removal efficiencies from solution by these Co-, Ni- and V-containing birnessites are 26–51%, ∼62–72% and ∼96–100%, respectively, compared to ∼92% by pure birnessite. Cr(III) oxidation kinetics analysis demonstrates the gradual decrease of Mn(IV) and concurrent increase of Mn(III) and the adsorption of mainly Cr(III) on mineral surfaces. A negatively linear relationship exists between birnessite lateral sizes and the proportions of Mn(IV/III) consumed to oxidize Cr(III). Apparent initial Cr(III) oxidation rate (kobs) for Co-containing birnessites are greatly reduced, while those for Ni-doped samples moderately decreased and for V-doped samples first increased and then decreased. A positively or negatively linear relationship exists between kobs or the amount of Mn(II) released and the mineral Mn(IV) content respectively. Cr(III) oxidation probably initiates from layer edge sites of Ni-doped birnessites but the vacancies of Co- and V-containing birnessites. These results provide insights into the reaction mechanisms of Cr(III) with natural birnessite-like minerals.