Two rhombic ice phases from aqueous salt solutions under graphene confinement

Water exhibits rich ice phases depending upon its respective formation conditions, and in particular, the two-dimensional ice with nonhexagonal symmetry adsorbed on solids relates to the exceptional arrangement of water molecules. Despite extensive reporting of two-dimensional ice on various solid surfaces, the geometry and thermodynamics of ice formation from an aqueous salt solution are still unknown. In this Letter, we show the formation of single- and two-phase mixed two-dimensional rhombic ice from aqueous salt solutions with different concentrations under strong compressed confinement of graphene at ambient temperature by using classical molecular dynamics simulations and first-principles calculations. The two rhombic ice phases exhibit identical geometry and thermodynamic properties, but different projections of the oxygen atoms against solid surface symmetry, where they relate to the stable and metastable arrangements of water molecules confined between two graphene layers. A single-phase rhombic ice would grow from the confined saturated aqueous solutions since the previously stable rhombic molecular arrangement becomes an unstable high-energy state by introducing salt ions nearby. Our result reveals different rhombic ice phases growing from pure water and aqueous solutions, highlighting the deciding role of salt ions in the ice formation process due to their common presence in liquids.