title: Large-amplitude Fourier transformed high-harmonic alternating current cyclic voltammetry: kinetic discrimination of interfering Faradaic processes at glassy carbon and at boron-doped diamond electrodes.
abstract: Significant advantages of Fourier transformed large-amplitude ac higher (second to eighth) harmonics relative to responses obtained with conventional small-amplitude ac or dc cyclic voltammetric methods have been demonstrated with respect to (i) the suppression of capacitive background currents, (ii) the separation of the reversible reduction of [Ru(NH(3))(6)](3+) from the overlapping irreversible oxygen reduction process under conditions where aerobic oxygen remains present in the electrochemical cell, and (iii) the kinetic resolution of the reversible [Ru(NH(3))(6)](3+/2+) process in mixtures of [Fe(CN)(6)](3-) and [Ru(NH(3))(6)](3+) at appropriately treated boron-doped diamond electrodes, even when highly unfavorable [Fe(CN)(6)](3-) to [Ru(NH(3))(6)](3+) concentration ratios are employed. Theoretical support for the basis of kinetic discrimination in large-amplitude higher harmonic ac cyclic voltammetry is provided.
authors.affiliation: School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
authors.forename: Jie
authors.initials: J
authors.lastname: Zhang
authors.forename: Si-Xuan
authors.initials: SX
authors.lastname: Guo
authors.forename: Alan M
authors.initials: AM
authors.lastname: Bond
authors.forename: Frank
authors.initials: F
authors.lastname: Marken