ab initio study of Mn-based systems for oxidative degradation

Organic contaminants can be removed from water/wastewater by oxidative degradation using oxidants such as manganese oxides and/or aqueous manganese ions. The Mn species show a wide range of activity, which is related to the oxidation state of Mn. Here, we use ab initio molecular dynamics simulations to address Mn oxidation states in these systems. We first develop a correlation between Mn partial atomic charge and the oxidation state based on results of 31 simulations on known Mn aqueous complexes. The results collapse to a master curve; the dependence of partial atomic charge on oxidation state weakens with increasing oxidation state, which concurs with a previously proposed feedback effect. This correlation is then used to address oxidation states in Mn systems used as oxidants. Simulations of MnO₂ polymorphs immersed in water give average oxidation states (AOS) in excellent agreement with experimental results, in that β-MnO₂ has the highest AOS, α-MnO₂ has an intermediate AOS, and δ-MnO₂ has the lowest AOS. Furthermore, the oxidation state varies substantially with the atom's environment, and these structures include Mn(III) and Mn(V) species that are expected to be active. In regard to the MnO₄⁻/HSO₃⁻/O₂ system that has been shown to be a highly effective oxidant, we propose a novel Mn complex that could give rise to the oxidative activity, where Mn(III) is stabilized by sulfite and dissolved O₂ ligands. Our simulations also show that the O₂ would be activated to O₂²⁻ in this complex under acidic conditions, and could lead to the formation of OH radicals that serve as oxidants.