Dual-Frequency Alternating Current Designer Waveform for Reliable Voltammetric Determination of Electrode Kinetics Approaching the Reversible Limit.
作者： Jiezhen Li , Cameron L. Bentley , Alan M. Bond , Jie Zhang
DOI: 10.1021/ACS.ANALCHEM.5B04354
关键词: Electrode 、 Chemistry 、 Voltammetry 、 Diffusion 、 Waveform 、 Sine wave 、 Analytical chemistry 、 Alternating current 、 Amplitude 、 Direct current
摘要: Alternating current (ac) voltammetry provides access to faster electrode kinetics than direct (dc) methods. However, difficulties in ac and other methods arise when the heterogeneous electron-transfer rate constant (k0) approaches reversible limit, because voltammetric characteristics become insensitive kinetics. Thus, this near-reversible regime, even small uncertainties associated with bulk concentration (C), diffusion coefficient (D), area (A), uncompensated resistance (Ru) can lead significant systematic error determination of k0. In study, we have introduced a kinetically sensitive dual-frequency designer waveform into Fourier-transformed large-amplitude alternating (FTAC) method that is made up two sine waves having same amplitude but different frequencies (e.g., 37 615 Hz) superimposed onto dc ramp quantify close-to-reversible Fc0/+ process (Fc = ferrocene) nonhaloaluminate ionic li...
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