Abstract
A new form of Fourier transformed square wave voltammetry (FT-SWV) is proposed to simplify and accelerate the electron transfer kinetics evaluation procedures for surface-confined redox systems. Even harmonic frequencies, which are derived from the nonlinear Faradaic response, will arise in the power spectrum after Fourier transformation of the current response of FT-SWV. The profile of the even harmonic power spectra is bell-shaped and shows a maximum at a certain frequency. The electrode kinetics-dependent maximum and the corresponding frequency are equivalent to the so-called "quasi-reversible maximum" and "critical frequency" (fmax) in traditional SWV, respectively. The critical frequency can be regarded as a frequency that is synchronized to the electron transfer rate constant (k(0)). As a result, it can serve as a probe of k(0) by means of a very simple equation, k(0) = kmax fmax. Compared with traditional cyclic voltammetry, square wave voltammetry, alternating current voltammetry, and several other voltammetric techniques, this method exhibits great advantages for its simplicity, rapidity, and sensitivity.
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