Enhanced Ion Adsorption on Mineral Nanoparticles.

Classical molecular dynamics simulation was used to study the adsorption of Na+, Ca2+, Ba2+, and Cl- ions on gibbsite edge (1 0 0), basal (0 0 1), and nanoparticle (NP) surfaces. The gibbsite NP consists of both basal and edge surfaces. Simulation results indicate that Na+ and Cl- ions adsorb on both (1 0 0) and (0 0 1) surfaces as inner-sphere species (i.e., no water molecules between an ion and the surface). Outer-sphere Cl- ions (i.e., one water molecule between an ion and the surface) were also found on these surfaces. On the (1 0 0) edge, Ca2+ ions adsorb as inner-sphere and outer-sphere complexes, whereas on the (0 0 1) surface, outer-sphere Ca2+ ions are the dominant species. Ba2+ ions were found as inner-sphere and outer-sphere complexes on both surfaces. Calculated ion surface coverages indicate that, for all ions, surface coverages are always higher on the basal surface compared to those on the edge surface. More importantly, surface coverages for cations on the gibbsite NP are always higher than those calculated for the (1 0 0) and (0 0 1) surfaces. This enhanced ion adsorption behavior for the NP is due to the significant number of inner-sphere cations found at NP corners. Outer-sphere cations do not contribute to the enhanced surface coverage. In addition, there is no ion adsorption enhancement observed for the Cl- ion. Our work provides a molecular-scale understanding of the relative significance of ion adsorption onto gibbsite basal versus edge surfaces and demonstrates the corner effect on ion adsorption on NPs.