Gas molecules sandwiched in hydration layers at graphite/water interfaces

Hydration structures are ubiquitous at solid/liquid interfaces and play a key role in various physicochemical and biological phenomena. Recently, it has been reported that dissolved gas molecules attracted to hydrophobic surfaces form adsorbed gas layers. Although a hydration structure and adsorbed gas layers coexist on the surface, the relationships between them remain unknown. In this study, we investigated a highly ordered pyrolytic graphite/pure water interface with and without adsorbed gas layers using frequency-modulation atomic force microscopy. We penetrated the adsorbed gas layers with the strong load force of the AFM tip and thereby obtained the frequency shift curves inside them. By comparing the curves with those measured on a bare HOPG surface, we found that the adsorbed gas layers were located at regions where the molecular density of water was low and were sandwiched between hydration layers with high water density. Moreover, the distance between adjacent hydration layers was larger than that predicted by simulations and was the same with and without the adsorbed gas layers. We propose that gas molecules on the hydrophobic surface interact with the hydration structure before forming the adsorbed gas layers, and extend the distance between hydration layers.