First-principles Calculation of In and Ag, Cu Replacing Zn in Sphalerite

Sphalerite has been recognized as the most important carrier of critical metal of Indium (In) due to that In mainly exists in the sphalerite lattice by isomorphic substitution. There are two significant replacing schemes for In entry into sphalerite, these are, Ag++In3+→2Zn2+ and Cu++In3+→2Zn2+. In order to understand the reaction process and constraints of the two substitution schemes, this paper uses first-principles methods to calculate In and Ag, Cu replacing Zn in sphalerite. According to the substitution schemes of Ag++In3+→2Zn2+ and Cu++In3+→2Zn2+, two doped sphalerite systems of Zn30InAgS32 and Zn30InCuS32 were constructed using 2×2×2 supercell model of sphalerite. Firstly, the pressure is controlled to 30MPa, and the temperature is set from 20-40MPa to simulate the response of the two doped sphalerite systems to temperature; Then, the control temperature was unchanged to 600K, and the pressure was set from 20-40MPa to investigate the pressure control of the two doped sphalerite systems. The lattice parameters, substitution energy, electronic structure, and population analysis of the designed models before and after replacement have been critically compared. The main conclusions can be drawn that it is more stable for In to enter sphalerite via the coupled substitution scheme Cu++In3+→2Zn2+, and the conditions that the two substitution schemes most likely to occur are 650K and 40MPa. This study not only reveals the physical and chemical properties of In-rich sphalerite formed by the two reaction processes of Ag++In3+→2Zn2+ and Cu++In3+→2Zn2+, but also has a certain enlightenment effect on the search for indium in sphalerite, and promotes the application of first principles in mineralization analysis.