Molecular Hydrophobicity Signature in Charged Bidimensional Clay Materials

The unraveling of the hydrophobicity/hydrophilicity molecular signature of nanometric bidimensional confined systems represents a challenging task with repercussions in environmental transport processes. Swelling clay minerals represent an ideal model system, as hydrophobicity can be modified during material synthesis by substituting hydroxyls by fluorine in the structure, without additional surface treatment. This following work presents a combined approach, integrating experimental inelastic neutron scattering spectroscopy and ab initio molecular dynamics simulations, with the objective of advancing our understanding of the role of surface hydroxylation/fluorination and the extent of confinement on water properties. From computed structures, the analysis of molecular hydrophobicity/hydrophilicity signature was investigated in detail through water–cation–surface interactions. The results elucidate the influence of fluorination on interlayer species, thereby tracing the impact of the surface on the diminished number of water molecules in such a sample. It is notable that the strong cation–water interaction can overcome the disruptive influence of fluorine, thereby maintaining comparable water hydration shells around cations and resulting in an almost identical bidimensional confinement geometry for both hydroxylated and fluorinated specimens. The analysis of the hydrogen-bond network revealed a significant reorganization of the water molecules due to fluorination. Our results suggest that a quantitative molecular signature of hydrophobicity/hydrophilicity can be derived from the analysis of the formation of cavities in the confined fluid. This new finding represents a robust approach for generalizing the hydrophobicity/hydrophilicity character for a wide variety of bidimensional systems while proposing a framework for the design of new materials with controlled water properties.