Nonlinear frequency response of electrochemical methanol oxidation kinetics: A theoretical analysis

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  • Max Planck Institute for Dynamics of Complex Technical Systems
  • Otto-von-Guericke University Magdeburg
  • University of Belgrade
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Original languageEnglish
Pages (from-to)B1279-B1289
JournalJournal of the Electrochemical Society
Volume2010
Issue number157
Publication statusPublished - 2010
Externally publishedYes

Abstract

In this theoretical contribution, nonlinear frequency response analysis was applied for the investigation of electrochemical methanol oxidation. This technique expresses the input-output behavior of any weakly nonlinear system with the help of the Volterra series expansion and generalized Fourier transform into so-called higher order frequency response functions. These functions contain the system's nonlinear fingerprint. They can be derived analytically from a nonlinear model. These functions can be obtained experimentally from the measurement of higher harmonics induced by a high amplitude sinusoidal perturbation of the system of interest. Frequency response functions up to the second order have been derived analytically for four different model varieties describing the kinetics of the electrochemical methanol oxidation. The first-order frequency response function corresponds to the reciprocal value of the well-known electrochemical impedance, which represents the linear part of the frequency response. This function does not contain sufficient information for discrimination between the different kinetic models. In contrast, the symmetrical second-order frequency response functions H2(ω, ω) show differences in shape, which substantiate the availability of the theoretical prerequisites for model discrimination. A detailed parametric study for all four model variants has been performed. The results show that the basic features of the shapes of the H2(ω, ω) amplitude spectra corresponding to the four models remain unique. The ubiquitousness of the qualitative differences between the competing models, for the whole set of parameters chosen for our analysis, suggests that the aforementioned amplitude spectra contain sufficient information for an unequivocal model discrimination.

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Cite this

Nonlinear frequency response of electrochemical methanol oxidation kinetics: A theoretical analysis. / Bensmann, Boris; Petkovska, Menka; Vidaković-Koch, Tanja et al.
In: Journal of the Electrochemical Society, Vol. 2010, No. 157, 2010, p. B1279-B1289.

Research output: Contribution to journalArticleResearchpeer review

Bensmann B, Petkovska M, Vidaković-Koch T, Hanke-Rauschenbach R, Sundmacher K. Nonlinear frequency response of electrochemical methanol oxidation kinetics: A theoretical analysis. Journal of the Electrochemical Society. 2010;2010(157):B1279-B1289. doi: 10.1149/1.3446836
Bensmann, Boris ; Petkovska, Menka ; Vidaković-Koch, Tanja et al. / Nonlinear frequency response of electrochemical methanol oxidation kinetics : A theoretical analysis. In: Journal of the Electrochemical Society. 2010 ; Vol. 2010, No. 157. pp. B1279-B1289.
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AU - Bensmann, Boris

AU - Petkovska, Menka

AU - Vidaković-Koch, Tanja

AU - Hanke-Rauschenbach, Richard

AU - Sundmacher, Kai

N1 - Copyright: Copyright 2010 Elsevier B.V., All rights reserved.

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