Nanoparticulate nickel sulfides formed in low temperature aqueous solutions

The nature of the nickel sulfides formed in low temperature aqueous solutions is not well-understood. The material has some intrinsic interest to mineralogy, geochemistry and materials science as well as to biogeochemisty, especially as a possible catalyst involved in the origin and early evolution of life. We synthesized Ni sulfide under anoxic conditions at 25 C: (1) chemically, by the addition of 50 mL of 0.1 M NiSO4Æ7H2O to 100 mL of 0.05M Na2SÆ9H2O; (2) electrochemically, with a Ni foil and H2S gas. At pH 6 5, millerite (b-NiS) was produced electrochemically and NiS mixtures, including heazlewoodite (Ni3S2) and polydymite (Ni3S4), were obtained chemically. At pH >11, a- NiS was obtained from the chemical reaction. At pH 6–9, the product produced only two broad peaks (d = ca. 2.7 and 1.8 ) with conventional and synchrotron XRPD which could be assigned to a number of Ni sulfides. It has previously been referred to as ‘‘amorphous NiS’’ Jeong and Manthiram, 2001. Eight SAED reflections were collected which identified the material as godlevskite, orthorhombic NiS. HRTEM shows that the godlevskite particles are ca. 30 nm in diameter and plate-like. SAXS analyses show that the material is 6–8.5 nm thick. Godlevskite is structurally related to makinawite, tetragonal FeS, and is found naturally in similar parageneses-associated with the monosulfide solid solution products of high temperature nickel ores. Mackinawite is the black FeS precipitate from the reaction between Fe(II) and S(-II) in aqueous solution. It appears that, geochemically, godlevskite is the Ni analogue of mackinawite.