Aqueous-solution/solid interfaces are ubiquitous in modern manufacturing environments as well as in our living environment, and studies of such interfaces are an active area of science and engineering research. An important area is the study of liquid/solid interfaces under active electrochemical control, which has many immediate technological implications, for example, corrosion/passivation of metals and energy storage in batteries and ultracapacitors. The central phenomenon of electrochemistry is the charge transfer at the interface, and the region of interest is usually wider than a single atomic layer, ranging from a monolayer to thousands of angstroms, extending into both phases.
Despite the technological and environmental importance of liquid/solid interfaces, the atomic level understanding of such interfaces had been very much hampered by the absence of nondestructive, in situ experimental techniques. The situation has changed somewhat in recent decades with the development of the largely ex situ ultrahigh vacuum (UHV) surface science, modern spectroscopic techniques, and modern surface microscopy.
However in situ experiments of electrochemical interfaces are difficult, stemming from the special nature of these interfaces. These are so-called buried interfaces in which the solid electrode surface is covered by a relatively thick liquid layer. For this reason, the probe we use in the structural investigation must satisfy simultaneously two conditions: (1) the technique must be surface/interface sensitive, and (2) absorption of the probe in the liquid phase must be sufficiently small for penetration to and from the interface of interest without significant intensity loss.