Thin layer sonoelectrochemistry: Impact on slow heterogeneous electron transfer

Abstract

In thin layer sonoelectrochemistry (TLS), constructive interference is established in a thin layer of electrolyte with a low power, ultrasonic quartz crystal oscillator (QCO). No cavitation, no temperature increase, and no impacts on mass transport are observed. In this first report of TLS experiments without cavitation, voltammetric morphologies are not disrupted. Interfacial electron transfer for three transition metal species are evaluated with established cyclic voltammetric diagnostics. For Ru(bpy)32+ with inherently fast (reversible) interfacial electron transfer, voltammograms are unchanged on sonication at 41 kHz. For Fe3＋ with slow heterogeneous electron transfer, interfacial rate increases with sonication, where increases in rate persist without diminution for minutes postsonication. For a cobalt phenanthroline probe, changes in voltammetric morphology at higher QCO intensity are consistent with chemical changes of ligand loss. Constructive interference in TLS imparts sound pressure to the electrode solution interface to increase electron transfer rates without mass transport disruption. TLS may provide means to electrocatalyze interfacial rates.