Combining Impedance Spectroscopy with Cyclic Voltammetry: Measurement and Analysis of Kinetic Parameters for Faradaic and Nonfaradaic Reactions on Thin-Film Gold

The technique of time-resolved impedance spectroscopy can be combined with dc cyclic voltammetry (CV) to study mechanisms and kinetics of electrochemical reactions at solid-liquid interfaces. Utilization of these techniques in a combined framework, however, is based on a number of specific considerations of measurement procedures and data analysis. The present work discusses certain essential elements of this topic, focusing primarily on the analysis of time-resolved impedance spectra where interdependent dc and ac effects of parallel faradaic and nonfaradaic reactions are present under potentiodynamic conditions. A thin gold film is used as a model experimental system where oxidation and reduction of the sample surface is voltage-controlled both in the presence and in the absence of specifically adsorbing Cl- ions in neutral background electrolytes of NaF. Impedance spectra are recorded under transient conditions of CV, and kinetic parameters based on electrode-equivalent circuit models are obtained as functions of CV scans.