In this paper, the adsorption of cyanide and its combination with zinc sulfate on the surface of sphalerite (110) was studied by density functional theory (DFT), and its configurational relationship was analyzed by coordination chemistry. The calculation results show that the adsorption configuration stability of CN⁻ is stronger than that of Zn(CN)₂; the chemical bond of Zn(OH)₂ is less covalent. The three adsorption modes all make the surface of sphalerite lose more electrons, thereby weakening the reactivity of S and Zn atoms on the sphalerite surface. During the CN⁻ adsorption process, both the 3d and 4p orbital peak energy levels of Zn decrease, indicating the strong inhibitory effect of CN⁻. Coordination chemistry also shows that CN⁻ matches the Zn ion orbital in sphalerite and the π electron pair on the Zn ion can easily interact with the empty π orbital on CN⁻ to form π-backbonding.

In industrial manufacturing, pyrrhotite(Fe_1−xS), once depressed, is commonly activated for flotation. However, the replacement of CuSO₄ is necessary due to the need for exact control over the dosage during the activation of pyrrhotite, which can pose challenges in industrial settings. This research introduces the use of FeSO₄ for the first time to efficiently activate pyrrhotite. The impact of two different activators on pyrrhotite was examined through microflotation experiments and density functional theory (DFT) calculations. Microflotation experiments confirmed that as the CuSO₄ dosage increased from 0 to 8 × 10⁻⁴ mol/L, the recovery of pyrrhotite initially increased slightly from 71.27% to 87.65% but then sharply decreased to 16.47%. Conversely, when the FeSO₄ dosage was increased from 0 to 8 × 10⁻⁴ mol/L, pyrrhotite’s recovery rose from 71.27% to 82.37%. These results indicate a higher sensitivity of CuSO₄ to dosage variations, suggesting that minor alterations in dosage can significantly impact its efficacy under certain experimental conditions. In contrast, FeSO₄ might demonstrate reduced sensitivity to changes in dosage, leading to more consistent performance. Fe ions can chemically adsorb onto the surface of pyrrhotite (001), creating a stable chemical bond, thereby markedly activating pyrrhotite. The addition of butyl xanthate (BX), coupled with the action of Fe²⁺ on activated pyrrhotite, results in the formation of four Fe-S bonds on Fe²⁺. The proximity of their atomic distances contributes to the development of a stable double-chelate structure. The S 3p orbital on BX hybridizes with the Fe 3d orbital on pyrrhotite, but the hybrid effect of Fe²⁺ activation is stronger than that of nonactivation. In addition, the Fe-S bond formed by the addition of activated Fe²⁺ has a higher Mulliken population, more charge overlap, and stronger covalent bonds. Therefore, Fe²⁺ is an excellent, efficient, and stable pyrrhotite activator.