Structure, Properties, and Phase Transformations of Water Nanoconfined between Brucite-like Layers: The Role of Wall Surface Polarity

The interaction of water with confining surfaces is primarily governed by the wetting properties of the wall material—in particular, whether it is hydrophobic or hydrophilic. The hydrophobicity or hydrophilicity itself is determined primarily by the atomic structure and polarity of the surface groups. In the present work, we used molecular dynamics to study the structure and properties of nanoscale water layers confined between layered metal hydroxide surfaces with a brucite-like structure. The influence of the surface polarity of the confining material on the properties of nanoconfined water was studied in the pressure range of 0.1–10 GPa. This pressure range is relevant for many geodynamic phenomena, hydrocarbon recovery, contact spots of tribological systems, and heterogeneous materials under extreme mechanical loading. Two phase transitions were identified in water confined within 2 nm wide slit-shaped nanopores: (1) at p(1) = 3.3–3.4 GPa, the liquid transforms to a solid phase with a hexagonal close-packed (HCP) crystal structure, and (2) at p(2) = 6.7–7.1 GPa, a further transformation to face-centered cubic (FCC) crystals occurs. It was found that the behavior of the confined water radically changes when the partial charges (and, therefore, the surface polarity) are reduced. In this case, water transforms directly from the liquid phase to an FCC-like phase at 3.2–3.3 GPa. Numerical simulations enabled determination of the amount of hydrogen bonding and diffusivity of nanoconfined water, as well as the relationship between pressure and volumetric strain.