Practical Guide to Large Amplitude Fourier-Transformed Alternating Current Voltammetry─What, How, and Why

Fourier-transformed alternating current voltammetry (FTacV) is a technique utilizing a combination of a periodic (frequently sinusoidal) oscillation superimposed onto a staircase or linear potential ramp. The advanced utilization of a large amplitude sine wave induces substantial nonlinear current responses. Subsequent filter processing (via Fourier-transformation, band selection, followed by inverse Fourier-transformation) generates a series of harmonics in which rapid electron transfer processes may be separated from non-Faradaic and competing electron transfer processes with slower kinetics. Thus, FTacV enables the isolation of current associated with redox processes under experimental conditions that would not generate meaningful data using direct current voltammetry (dcV). In this study, the enhanced experimental sensitivity and selectivity of FTacV versus dcV are illustrated in measurements that (i) separate the Faradaic current from background current contributions, (ii) use a low (5 μM) concentration of analyte (exemplified with ferrocene), and (iii) enable discrimination of the reversible [Ru(NH₃)₆]^3+/2+ electron-transfer process from the irreversible reduction of oxygen under a standard atmosphere, negating the requirement for inert gas conditions. The simple, homebuilt check-cell described ensures that modern instruments can be checked for their ability to perform valid FTacV experiments. Detailed analysis methods and open-source data sets that accompany this work are intended to facilitate other researchers in the integration of FTacV into their everyday electrochemical methodological toolkit.