Water Confined in Hydrophobic Cup-Stacked Carbon Nanotubes beyond Surface-Tension Dominance.

Water confined in carbon nanotubes (CNTs) can exhibit distinctly different behaviors from the bulk. We report transmission electron microscopy (TEM) observation of water phases inside hydrophobic cup-stacked CNTs exposed to high vacuum. Unexpectedly, we observed stable water morphologies beyond surface-tension dominance, including nanometer thin free water films, complex water-bubble structures, and zigzag-shaped liquid-gas interface. The menisci of the water phases are complex and inflected, where we measured the contact angles on the CNT inner wall to be 68-104°. The superstability of the suspended ultrathin water films is attributed to the strong hydrogen-bonded network among water molecules and adsorption of water molecules on the cup-structured inner wall. The complex water-bubble structure is a result of the stability of free water films and interfacial nanobubbles, and the zigzag edge of the liquid-gas interface is explained by the pinning effect. These experimental findings provide valuable knowledge for the research on fluids under nanoscale confinement.