A DFT study on the effect of lattice impurities on the electronic structures and floatability of sphalerite

The electronic structures of bulk sphalerite containing 14 typical kinds of impurities were studied by density-functional theory (DFT). The calculated results show that the presence of Cd, Hg, Ga, Ge, In, Ag, Sn, Pb and Sb could increase the lattice parameter of sphalerite. Ag, Sn, Pb, Sb, Cd and Hg impurities narrowed the band-gap and increased the conductivity of sphalerite. Moreover, Mn, Fe, Ga, In, Sn and Sb impurities changed the semiconductor type of sphalerite from p-type to n-type. All of the impurities except Cd and Hg made the Fermi level shift to higher energy and led to the occurrence of an impurity state in the forbidden band.Analysis of the frontier molecular orbital showed that the impurities Mn, Fe, Cu, Ge, Sn, Pb and Sb contributed greatly to the highest occupied molecular orbital (HOMO) and greatly influence the nucleophilicity of sphalerite. On the other hand, the impurities of Fe, Cu, Co, Ni, Cd and Ga greatly contributed to the lowest unoccupied molecular orbital (LUMO) and greatly affected the electrophilicity of sphalerite. The interactions of O2 and xanthate with sphalerite are discussed. Results suggest that Mn, Fe, Ni, Cu, Sn and Pb impurities favored the oxidization of sphalerite; however, the impurities of Cd, Hg, Ga and In had the opposite effect. Impurities of Mn, Fe, Co, Ni, Cu, Hg and Pb could enhance the reactivity of xanthate with sphalerite.