Specific Ion Effects at Two Single-Crystal Planes of Sapphire

Abstract

Experimental results on specific ion effects at the c- and r- single-crystal planes of sapphire obtained by zeta-potential measurements at pH 5.8 are reported. Both crystal planes have negative electrokinetic charge at pH 5.8 and their intrinsic isoelectric points are found close to pH 4. The water structure "making" surface (i.e., r-plane, based on surface diffraction and surface complexation modeling) causes cation specificity in the order Li(+) > Na(+) > K(+) > Rb(+) > Cs(+) in chloride systems while no anion sensitivity occurs in sodium systems (Cl(-), NO3(-), and BrO3(-)) as expected. The cation series concurs with the simple idea of structure making ions being adsorbed more strongly on structure making surfaces and also concurs with the sequence found for particulate alumina for the cation series in nitrate systems. On the structure breaking basal plane (i.e., c-plane, again based on surface diffraction and surface complexation modeling), no cation specific effects are observed in chloride systems, but the structure breaking properties are retrieved in the cation series in nitrate systems. Surprisingly, anion specificity is observed on sapphire-c. Furthermore, the chloride ion shows unexpected behavior that suggests chloride adsorption onto the negatively charged surface. Based on these experimental observations in conjunction with generic results from published MD simulations, the c-plane sapphire aqueous electrolyte interface is a nonpolar surface with negative charge. The nonpolarity finds repercussions in the weak water ordering and the observed ion specific effects. The low isoelectric points of the cuts cannot be explained by the respective surface chemistries of the ideal surfaces. Relation to "inert" surfaces and concomitant dominance of hydroxide ion adsorption is a possible explanation for the low isoelectric points of both cuts. The reported ion specific effects occur at concentrations below 10 mM. Overall, the results support the idea that ion specific effects are largely governed by surface hydration.