Potential modulated attenuated total reflectance (PM-ATR) spectroscopy has been employed to study charge transfer processes in Prussian blue (PB) films deposited on indium tin oxide (ITO) electrodes. PM-ATR is a planar waveguide-based spectroelectrochemical technique in which the optical response of an electroactive film is measured as a function of applied potential and modulation frequency. The multiple internal reflection geometry of PM-ATR provides a significant sensitivity advantage over the single external reflectance geometry that has been employed in most prior electroreflectance studies. The apparent electron transfer rate of PB on ITO obtained using PM-ATR was compared to that obtained with conventional cyclic voltammetry; the respective rates, 0.33 ± 0.15 s-1 (n = 3) and 0.71 ± 0.37 s-1 (n = 10), are in good agreement.
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