Ultrahigh Vacuum Surface Analytical Methods in Electrochemical Studies of Single-Crystal Surfaces

摘要

A complete understanding of a given electrochemical reaction needs to take intoaccount all the physical and chemical interactions that arise between an electrified surface and the constituents of the electrolytic environment. Such interactions will depend upon the parameters which control the properties of the electrode-solution interface; these include solvent, electrolyte, electrode potential, reactant concentration, crystallographic orientation, and surface electronic structure. The traditional approach to the study of the electrode-solution interface is based upon a thermodynamic analysis of the interfacial response to perturbations in terms of current-charge-potential measurements. Analysis of results from such measurements have relied on phenomenological methods which incorporate, to varying levels of approximation, the macroscopic interfacial parameters, devoid of atomic-level specificity. The need for an atomic-level perspective of electrochemical processes is now well established. While it is true that a great deal is now known about heterogeneous processes at gas-solid interfaces, it should be noted that barely two decades ago, these fields were beset by problems remarkably similar to those today. jg p.2.