Search for: All records

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 − reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n (Fe 2+ S 2− ) (s) was found to oxidize to a Fe 3+ containing FeS phase at −0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2− and polysulfide (S n 2− ) species, with its composition described as Fe 2+ 1−3 x Fe 3+ 2 x S 2− 1− y (S n 2− ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2− 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2− ). 

Thioesters are important intermediates in both synthetic organic and biosynthetic reaction pathways. Here we show that thioesters can be synthesized in an aqueous reaction between thioacetate and thiols. The reaction can be coupled to a second reaction between sulfide and either ferrous or ferric iron, which drives the reaction forward. We furthermore demonstrate that sulfide released during thioester formation can be used in the synthesis of peptide bound [Fe–S] clusters, which like thioesters, are ancient components of metabolism. Together our results reveal a primordial linkage between high-energy ester formation and redox chemistry.