Sampled-Current Voltammetry at Microdisk Electrodes: Kinetic Information from Pseudo Steady State Voltammograms

In sampled-current voltammetry (SCV), current transients acquired after stepping the potential along the redox wave of interest are sampled at a fixed time to produce a sigmoidal current–potential curve akin to a pseudo steady state voltammogram. Repeating the sampling for different times yields a family of sampled-current voltammograms, one for each time scale. The concept has been used to describe the current–time-potential relationship at planar electrodes but rarely employed as an electroanalytical method except in normal pulse voltammetry where the chronoamperograms are sampled once to produce a single voltammogram. Here we combine the unique properties of microdisk electrodes with SCV and report a simple protocol to analyze and compare the microdisk sampled-current voltammograms irrespective of sampling time. This is particularly useful for microelectrodes where cyclic voltammograms change shape as the mass transport regime evolves from planar diffusion at short times to hemispherical diffusion at long times. We also combine microdisk sampled-current voltammetry (MSCV) with a conditioning waveform to produce voltammograms where each data point is recorded with the same electrode history and demonstrate that the waveform is crucial to obtaining reliable sampled-current voltammograms below 100 ms. To facilitate qualitative analysis of the voltammograms, we convert the current–potential data recorded at different time scales into a unique sigmoidal curve, which clearly highlights kinetic complications. To quantitatively model the MSCVs, we derive an analytical expression which accounts for the diffusion regime and kinetic parameters. The procedure is validated with the reduction of Ru­(NH₃)₆³⁺, a model one electron outer sphere process, and applied to the derivation of the kinetic parameters for the reduction of Fe³⁺ on Pt microdisks. The methodology reported here is easily implemented on computer controlled electrochemical workstations as a new electroanalytical method to exploit the unique properties of microelectrodes, in particular at short times.