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Square Wave Voltcoulometry of Spatially Confined Electroactive Species
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DOI：10.1002/cmtd.70142.png)
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Abstract
En 中文
Finite diffusion (FD) cells, that is, those with spatial restrictions in the electrolyte solution layer adjacent to the electrodes that affect the overall mass transport, are becoming a very attractive situation due to the increasing applications to many relevant fields, such as electrochemical sensing or electric energy conversion and storage. In the case of electrode processes with fast kinetics, voltcoulometric techniques are very sensitive techniques to characterize the Faradaic processes taking place. In the case of FD devices in the thin-layer limit, the application of square wave voltcoulometry (SWVC) to redox probes in solution leads to a response identical to that obtained for surface confined electroactive species forming a monolayer. In practice, this implies the use of low square wave frequencies, typically below 1.0 Hz, for diffusion field lengths below 50 microns. Moreover, for these small frequencies and high square wave amplitudes, it is possible to observe the complete Faradaic conversion of the redox probes and calculate in a very simple way the amount of electroactive species (through the application of Faraday's law) or the thickness of the electrolyte solution layer that defines the thin-layer setup (for a known value of the concentration).
Keywords:
calibration-free methods
Faraday's law
finite diffusion
square wave
thin-layer voltammetry
voltcoulometry
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