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.
Pettit
C M
CM
Department of Physics, Clarkson University, Potsdam, New York 13699-5820, USA.
Goonetilleke
P C
PC
Sulyma
C M
CM
Roy
D
D
D006046:Gold / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D013057:Spectrum Analysis
D006046:Gold