Influence of Co:Fe:Ni ratio on cobalt Pentlandite?s electronic structure and surface speciation

X-ray photoemission spectroscopy (XPS) was used to investigate the electronic structure and oxidation state of transition metals in synthetic cobalt pentlandites (Fe,Co,Ni)9S8 with measured stoichiometries of Fe4.85Ni4.64S8, Co0.13Fe4.68Ni4.71S8, Co2.73Fe3.18Ni3.16S8, Co5.80Fe1.63Ni1.59S8 and Co8.70S8. The addition of cobalt was found to decrease the bond length and hence decrease the unit cell dimensions of the cobalt pentlandite crystal structure by up to 0.18 angstrom. High resolution XPS S 2p spectra show increases in the binding energies of bulk 5-coordinated (162.1 eV) and surface 3-coordinated (160.9 eV) sulfur (approximate to 0.2 eV) with increasing Co concentration and decreasing bond lengths. As the Co concentration increases, variation in metal site occupation decreases, resulting in smaller S 2p FWHMs due to a dominant single Co-S state rather than mixed Fe-S, Ni-S and Co-S states with similar binding energies. The S 2p high binding energy tail, previously identified as a S 3p- Fe 3d ligand to metal transfer in Fe chalcogenides, shows a marked decrease in intensity as the concentration of Co increases, that is attributed to a decreased probability of ligand-to-metal charge transfer as the eg orbitals are filled. The transition metal XPS 2p spectra were modelled using CTM4XAS to investigate metal site occupation and ligand-to-metal charge transfer. Fe, Co, and Ni were all best simulated using a tetrahedral symmetry and 2+ oxidation state, their 2p3/2 and 2p1/2 peaks occurred at 706.9 and 719.9 eV, 778.2 and 793.1 eV, and 852.8 and 870.0 eV, respectively. A negative charge transfer energy confirms the high binding energy tail results from S3p-Fe3d ligand to metal charge transfer. This increased understanding of the pentlandite electronic structure will provide a basis for the refinement of mineral processing techniques and allow for a reduced environmental impact from limited efficiency.

Automated summary

X-ray photoemission spectroscopy was used to investigate the electronic structure and oxidation state of synthetic cobalt pentlandites. The addition of cobalt decreased the bond length and unit cell dimensions of the crystal structure, while increasing the binding energies of sulfur atoms. Modeling the XPS spectra confirmed the metal site occupation and ligand-to-metal charge transfer processes. This study provides insights for improving mineral processing techniques and reducing environmental impact.