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 (Sr2+ and Mg2+) 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.
Highlights
The findings of this work, i.e. molecular understanding of adsorption of ions at the mineral-water interface, mechanism and role of hydration energy, have profound applications in toxic element contaminants in aquifers and surface water, plant nutrient supply and effectiveness of water purification method, where maximum ions adsorption on adsorbent is desirable
The obtained understanding would help in the better design of these adsorbate materials
Our analysis finds that higher concentration of elecrolyte is not always desirable, rather hydration structure plays the crucial role
Summary
The findings of this work, i.e. molecular understanding of adsorption of ions at the mineral-water interface, mechanism and role of hydration energy, have profound applications in toxic element contaminants in aquifers and surface water, plant nutrient supply and effectiveness of water purification method, where maximum ions adsorption on adsorbent is desirable. The obtained understanding would help in the better design of these adsorbate materials. The findings have implications in super-capacitors, where ion adsorption on charged surfaces from electrolyte solution dictates their energy storage capacity. Our analysis finds that higher concentration of elecrolyte is not always desirable, rather hydration structure plays the crucial role
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