Electrochemical and Spectroscopic Data supported by Computational Models for Exploring the Metal- and Ligand-Based Oxidation of Mackinawite Nanoparticles

Supporting information to our study, where under anaerobic conditions, ferrous iron reacts with sulfide producing FeS precipitate, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases such as gregite or pyrite. The dataset provide information about the chemical speciation of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Nanoparticulate FeS was found to get oxidized to a Fe³⁺ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7) and in a concomitant oxidation step, polysulfides are proposed to give a material described as Fe²⁺_(1−3x)Fe³⁺_(2x)S^2-_(1-y)(S_n^2-)_y. The thermodynamic differences between ligand- and metal-based oxidation processes from density functional theory can be used to describe one- and two-electron electronic and structural transformations. These findings together point to the existence of a previously unknown, metastable FeS phase located between FeS and greigite (Fe²⁺Fe³⁺₂S^2-₄) along a metal oxidation path, and Fe²⁺S^2- and pyrite (Fe²⁺S₂^2-) along a ligand oxidation path, respectively.