Cyclic Voltammograms at Coplanar and Shallow Recessed Microdisk Electrode Arrays: Guidelines for Design and Experiment

Although microdisk electrode arrays (MEAs) have been extensively used for more than three decades, the existing rules do not provide an unambiguous formula for the calculation of the minimum interelectrode distance (d) necessary for steady-state current response. With the aim of formulating generally applicable guidelines for design and experiment with MEAs, cyclic voltammograms were simulated for coplanar and shallow recessed microdisk electrode arrays with various interelectrode distances and dimensionless scan rates (V). The dimensionless scan rate (V) is a function of the radius (a) of the individual electrodes in the array, the diffusion coefficient (D) of the analyte, and the potential scan rate (v). The cyclic voltammograms at microdisk electrode arrays are grouped into five categories corresponding to the contributions of linear and radial diffusion to the overall responses. These categories are illustrated in a zone diagram based on the effect of V and d on the shape of cyclic voltammograms. The zone diagram reveals the minimum d and a cluster of linked d and V values that are incident to sigmoidal wave responses. For shallow recessed microdisk electrode arrays, the zones representing hemispherical diffusion are larger than that for coplanar arrays. The minimum d necessary for hemispherical diffusion becomes smaller as recess depth increases. With the zone diagram, one can predict the type of the cyclic voltammograms that can be expected for different microelectrode array geometries and experimental conditions. The fitting between simulation and experimental data validates our conclusions.