Electrochemistry and DFT study of galvanic interaction on the surface of monoclinic pyrrhotite (0 0 1) and galena (1 0 0)

The electrochemical interaction between galena and monoclinic pyrrhotite was investigated to examine its impact on the physical and chemical properties of the mineral micro-surface. This investigation employed techniques such as electrochemistry, metal ion stripping, X-ray photoelectron spectroscopy, and quantum chemistry. The electrochemical test results demonstrate that the galena surface in the electro-couple system exhibits a lower electrostatic potential and higher electrochemical activity compared to the monoclinic pyrrhotite surface, rendering it more susceptible to oxidation dissolution. Monoclinic pyrrhotite significantly amplifies the corrosion rate of the galena surface. Mulliken charge population calculations indicate that electrons are consistently transferred from galena to monoclinic pyrrhotite, with the number of electron transfers on the mineral surface increasing as the interaction distance decreases. The analysis of state density revealed a shift in the surface state density of galena towards lower energy levels, resulting in decreased reactivity and increased difficulty for the reagent to adsorb onto the mineral surface. Conversely, monoclinic pyrrhotite exhibited an opposite trend. The X-ray photoelectron spectroscopy (XPS) test results indicate that galvanic interaction leads to the formation of hydrophilic substances, PbS_xO_y and Pb(OH)₂, on the surface of galena. Additionally, the surface of monoclinic pyrrhotite not only adsorbs Pb²⁺ but also undergoes S⁰ formation, thereby augmenting its hydrophobic nature.