RESUMO
Room-temperature ionic liquids (RTILs) are new materials with fundamental importance for energy storage and active lubrication. They are unusual liquids, which challenge the classical frameworks of electrolytes, whose behaviour at electrified interfaces remains elusive, with exotic responses relevant to their electrochemical activity. Using tuning-fork-based atomic force microscope nanorheological measurements, we explore here the properties of confined RTILs, unveiling a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to capillary freezing in confinement. This threshold is related to the metallic nature of the confining materials, with more metallic surfaces facilitating freezing. This behaviour is interpreted in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces. Our findings provide fresh views on the properties of confined RTIL with implications for their properties inside nanoporous metallic structures, and suggests applications to tune nanoscale lubrication with phase-changing RTILs, by varying the nature and patterning of the substrate, and application of active polarization.
RESUMO
Carbon materials have unveiled outstanding properties as membranes for water transport, both in 1D carbon nanotube and between 2D graphene layers. In the ultimate confinement, water properties however strongly deviate from the continuum, showing exotic properties with numerous counterparts in fields ranging from nanotribology to biology. Here, by means of molecular dynamics, we show a self-organized inhomogeneous structure of water confined between graphene sheets, whereby the very strong localization of water defeats the energy cost for bending the graphene sheets. This leads to a two-dimensional water droplet accompanied by localized graphene ripples, which we call "dripplon." Additional osmotic effects originating in dissolved impurities are shown to further stabilize the dripplon. Our analysis also reveals a counterintuitive superfast dynamics of the dripplons, comparable to that of individual water molecules. They move like a (nano-) ruck in a rug, with water molecules and carbon atoms exchanging rapidly across the dripplon interface.