Real-Time FTIR Spectroscopy as a Quantitative Kinetic Probe of Competing Electrooxidation Pathways for Small Organic Molecules

Article abstract of DOI:10.1021/j100325a004

The application of real-time FTIR spectroscopy to probe quantitative kinetics and mechanisms of competing electrochemical patways on a voltammetric time scale is illustrated for the electrooxidation of ethanol, ethylene glycol, and glycolaldehyde in 0.1 M HClO4 at platinum.A simple procedure is outlined whereby the required ratio of molar absorptivities in the thin-layer cavity and bulk solution ε_eff/ε_b, can be evaluated.This approach enables the proportion of CO2 and partial oxidation products formed during voltammetric sweeps to be determined reliably and the role of adsorbed CO and other chemisorbed fragments in the electrocatalytic mechanisms to be evaluated.