Abstract
Adsorption of ions at the solid - aqueous interface is the primary mechanism in fast biological processes to very slow geological transformations. Despite, little is known about role of ion charge, hydration energy and hydration structure on competitive adsorption of ions, their structure and coverage at the interface. In this report, we investigate the structure and adsorption behavior of monovalent (Rb(+) and Na(+)) and divalent (Sr(2+) and Mg(2+)) cations ranging from 0-4.5 M of bulk concentrations on the muscovite mica surface. Divalent ions have stronger adsorption strength compared to monovalent ions due higher charge. However, we observed counter-intuitive behavior of lesser adsorption of divalent cations compared to monovalent cations. Our detailed analysis reveals that hydration structure of divalent cations hinders their adsorption. Both, Na(+) and Rb(+) ions exhibits similar adsorption behavior, however, the adsorption mechanism of Na(+) ions is different from Rb(+) ions in terms of redistribution of the water molecules in their hydration shell. In addition, we observed surface mediated RbCl salting out behavior, which is absent in Na(+) and divalent ions. We observed direct correlation in hydration energy of cations and their adsorption behavior. The obtained understanding will have tremendous impact in super-capacitors, nanotribology, colloidal chemistry and water purifications.