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Universal Algorithm for Simulating and Evaluating Cyclic Voltammetry at Macroporous Electrodes by Considering Random Arrays of Microelectrodes.

ABSTRACT: An algorithm for the simulation and evaluation of cyclic voltammetry (CV) at macroporous electrodes such as felts, foams, and layered structures is presented. By considering 1D, 2D, and 3D arrays of electrode sheets, cylindrical microelectrodes, hollow-cylindrical microelectrodes, and hollow-spherical microelectrodes the internal diffusion domains of the macroporous structures are approximated. A universal algorithm providing the time-dependent surface concentrations of the electrochemically active species, required for simulating cyclic voltammetry responses of the individual planar, cylindrical, and spherical microelectrodes, is presented as well. An essential ingredient of the algorithm, which is based on Laplace integral transformation techniques, is the use of a modified Talbot contour for the inverse Laplace transformation. It is demonstrated that first-order homogeneous chemical kinetics preceding and/or following the electrochemical reaction and electrochemically active species with non-equal diffusion coefficients can be included in all diffusion models as well. The proposed theory is supported by experimental data acquired for a reference reaction, the oxidation of [Fe(CN)₆ ]^4- at platinum electrodes as well as for a technically relevant reaction, the oxidation of VO₂ ⁺ at carbon felt electrodes. Based on our calculation strategy, we provide a powerful open source tool for simulating and evaluating CV data implemented into a Python graphical user interface (GUI).

SUBMITTER: Tichter T

PROVIDER: S-EPMC7078989 | biostudies-literature |

REPOSITORIES: biostudies-literature

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