Graphitic-like Hexagonal Phase of Alkali Halides in Quasi-Two-Dimensional Confined Space under Ambient Conditions

The discovery of specific matter phases with abnormal physical properties in low-dimensional systems and/or on particular substrates, such as the hexagonal phase of ice and two-dimensional (2D) CaCl with an abnormal valence state, continuously reveals more fundamental mechanisms of the nature. Alkali halides, represented by NaCl, are one of the most common compounds and usually thought to be well-understood. In the past decades, many theoretical studies suggested the existence of one particular phase, that is, the graphitic-like hexagonal phase of alkali halides at high pressure or in low-dimension states, with the expectation of improved properties of this matter phase but lacking experimental evidence due to severe technical challenges. Here, by optimized cryo-electron microscopy, we report the direct atomic-resolution observation and in situ characterization of the prevalent and stable graphitic-like alkali halide hexagonal phases, which were spontaneously formed by unsaturated NaCl and LiCl solution, respectively, in the quasi-2D confined space between reduced graphene oxide layers under ambient conditions. Combined with a control experiment, density functional theory calculations, and previous theoretical studies, we believe that a delicate balance among the cation-π interaction of the solute and substrate, electrostatic interactions of anions and cations, solute-solvent interactions, and thermodynamics under confinement synergistically results in the formation of such hexagonal crystalline phases. These findings highlight the effects of the substrate and the confined space on the formation of specific matter phases and provide a universal scheme for the preparation of special graphitic-like hexagonal phases of alkali halides.