Abstract
The voltammetry of various well-characterized aqueous and nonaqueous electrochemical systems has been studied at platinum and gold disk electrodes under illumination from a 10 Hz pulsed Nd:YAG laser frequency doubled to operate at 532 nm. A simple Nernst diffusion layer model is established to quantify the slight enhancement in mass transport observed as a function of laser intensity in the thermoelastic region where light energy absorbed by the metal is insufficient to cause localized melting or vaporization but does lead to a partial thinning of the diffusion layer thickness through surface heating/vibration. This leads to sigmoidal shaped voltammograms whilst maintaining a clean, reproducible electrode surface. Above the ablation threshold, the minimum laser intensity required to cause electrode damage, atomic force microscopy (AFM) is used to probe the nature of the surface damage and its relationship to the laser intensity. The Nernst-diffusion model is verified by means of potential step chronoamperometric measurements in water and acetonitrile where good agreement with theory is seen for transport across a diffusion layer of a thickness corresponding to that inferred from steady-state voltammetry. Applications of the laser activation technique are illustrated by three systems found to be passivating in aqueous media; the two electron reduction of toluidine blue dye, iodide oxidation and the oxidation of ferrocyanide in the presence of the blood protein, fibrinogen. In all cases clean, reproducible and quantitative voltammetry is seen in contrast to that observed in the absence of laser activation, demonstrating the excellent surface-cleaning effects of LAV.
Published Version
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