Direct observation of 2-dimensional ices on different surfaces near room temperature without confinement

Abstract

Water–solid interfaces play important roles in a wide range of fields, including atmospheric science, geochemistry, electrochemistry, and food science. Herein, we report simulation evidence of 2-dimensional (2D) ice formation on various surfaces and the dependence of the 2D crystalline structure on the hydrophobicity and morphology of the underlying surface. Contrary to the prevailing view that nanoscale confinement is necessary for the 2D liquid-to-bilayer ice transition, we find that the liquid-to-bilayer hexagonal ice (BHI) transition can occur either on a model smooth surface or on model fcc-crystal surfaces with indices of (100), (110), and (111) near room temperature. We identify a critical parameter that characterizes the water–surface interaction, above which the BHI can form on the surface. This critical parameter increases as the temperature increases. Even at temperatures above the freezing temperature of bulk ice (Ih), we find that BHI can also form on a superhydrophilic surface due to the strong water–surface interaction. The tendency toward the formation of BHI without confinement reflects a proper water–surface interaction that can compensate for the entropy loss during the freezing transition. Furthermore, phase diagrams of 2D ice formation are described on the plane of the adsorption energy versus the fcc lattice constant (Eads–afcc), where 4 monolayer square-like ices are also identified on the fcc model surfaces with distinct water–surface interactions.