In the flotation process, surface–reagent
reactions occur
on water precovered surfaces; therefore, investigation on the mineral–water
interactions is essential in such systems. In the present study, the
importance of surface vacancies was scrutinized by simulating water–surface
complexes up to multilayer water molecules on the defective ZnS (110)
surface using density functional theory. We restricted our attention
to the ZnS surfaces with single sulfur, single zinc, and double neighboring
congruent vacancies. Our simulation results revealed that the absence
of Zn or S atoms on the surface layer has a different effect on the
local surface wettability: while removing a S atom increases the hydrophobicity,
removing a Zn atom increases the hydrophilicity around the defect
site. The presence of double neighboring congruent vacancies further
stabilized the water adsorption, whereas, by removing one Zn atom
and one S atom, respectively, from surface upper and downward hills,
water was dissociatively adsorbed on the ZnS surface. However, increasing
the number of water molecules in a system altered the adsorption configuration
and energies, indicating that considering an isolated water molecule
cannot reflect the real surface circumstances at the water–surface
interface. In general, in the ZnS system, surface reconstruction occurs
through molecular adsorption of water on the surface by forming the
Zn–O bond. Our surface analysis revealed that the level of
hydrophilicity of the ZnS surface is higher when the number of undercoordinated
S atoms on the surface is increased.