Surface enhanced Raman scattering in electrochemical systems: The complex roles of surface roughness

A series of experiments designed to elucidate the presence and properties of large-scale and atomic-scale roughness produced on Ag electrodes with electrochemical oxidation-reduction cycle (ORC) pretreatments are presented. This report reviews surface enhanced Raman scattering (SERS) and scanning electron microscopic (SEM) characterization of Ag electrodes roughened with controlled-rate ORCs, and presents new results for the laser-induced thermal decay of SERS as a probe of Ag surface active sites and differential reflectance spectroscopy of electrochemically roughened Ag electrodes. These results are interpreted in terms of the presence and properties of both large-scale and atomic-scale roughness on these surfaces.