Water at the nanoscale: From filling or dewetting hydrophobic pores and carbon nanotubes to “sliding” on graphene

Abstract

In this work, we study the effect of nanoconfinement on the hydration properties of model hydrophobic pores and carbon nanotubes, determining their wetting propensity and the conditions for geometrically induced dehydration. By employing a recently introduced water structural index, we aim at two main goals: (1) to accurately quantify the local hydrophobicity and predict the drying transitions in such systems, and (2) to provide a molecular rationalization of the wetting process. In this sense, we will further discuss the number and strength of the interactions required by the water molecules to promote wetting. In the case of graphene-like surfaces, an explanation for their unexpectedly significant hydrophilicity will also be provided. On the one hand, the structural index will show that the net attraction to the dense carbon network that a water molecule experiences through several simultaneous weak interactions is sufficient to give rise to hydrophilic behavior. On the other hand, we will show that an additional effect is also at play: the hydrating water molecule is retained on the surface by a smooth exchange of such simultaneous weak interactions, as if “sliding” on graphene.