Oversolubility in the microvicinity of solid-solution interfaces

Water-solid interactions at the macroscopic level (beyond tens of nanometers) are often viewed as the coexistence of two bulk phases with a sharp interface in many areas spanning from biology to (geo) chemistry and various technological fields (membranes, microfluidics, coatings, etc.). Here we present experimental evidence indicating that such a view may be a significant oversimplification. High-resolution infrared and Raman experiments were performed in a 60-20 mu m(2) quartz cavity, synthetically created and initially filled with demineralized water. The IR mapping (3 x 3 mu m(2) beam size) performed using the SOLEIL synchrotron radiation source displays two important features: (i) the presence of a dangling free-OH component, a signature of hydrophobic inner walls; (ii) a shift of the OH-stretching band which essentially makes the 3200 cm(-1) sub-band predominate over the usual main component at around 3400 cm(-1). Raman maps confirmed these signatures (though less marked than IR's) and afforded a refined spatial distribution of this interfacial signal. This spatial resolution, statistically treated, results in a puzzling image of a 1-3 mu m thick marked-liquid layer along the entire liquid-solid interface. The common view is then challenged by this strong evidence that a mu m-thick layer analogous to an interphase forms at the solid-liquid interface. The thermodynamic counterpart of the vibrational shifts amounts to around +1 kJ mol(-1) at the interface with a rapidly decreasing signature towards the cavity centre, meaning that vicinal water may form a reactive layer, of micrometer thickness, expected to have an elevated melting point, a depressed boiling temperature, and enhanced solvent properties.