Oscillations and Complex Dynamical Bifurcations in Electrochemical Systems

Koper, Marc T. M.

doi:10.1002/9780470141519.ch2

Cited by 151 publications

(118 citation statements)

References 159 publications

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“…2b (top panel), HCOOH oxidation in acidic media exhibits two anodic peaks in the positive-going scan (peak p1 and peak p2), while a single oxidation peak is observed with shoulders at both positive and negative side in the negative-going scan (a single peak with a shoulder at the low potential side is observed at higher HCOOH concentrations [6,13,14,51,57])). The interpretation of the complex voltammetric features has been the subject of discussion, because the origins of the two anodic peaks in the positive-going scan are the key issues for understanding electrochemical oscillations observed during HCOOH oxidation [51,53,58,59]. …”

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The effect of pH on the electrocatalytic oxidation of formic acid/formate on platinum: A mechanistic study by surface-enhanced infrared spectroscopy coupled with cyclic voltammetry

Joo

Uchida

Cuesta

et al. 2014

Electrochimica Acta

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132

127

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Please cite this article as: J. Joo, T. Uchida, A. Cuesta, M.T.M. Koper, M. Osawa , The effect of pH on the electrocatalytic oxidation of formic acid/formate on platinum: A mechanistic study by surface-enhanced infrared spectroscopy coupled with cyclic voltammetry, Electrochimica Acta (2014), http://dx.doi.org/10. 1016/j.electacta.2014.02.040 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe electrocatalytic oxidation of formic acid (HCOOH) and formate (HCOO − ) to CO 2 on platinum has been studied over a wide range of pH (0-12) by surface-enhanced infrared absorption spectroscopy (SEIRAS) coupled with cyclic voltammetry. The peak current of HCOOH/HCOO − oxidation exhibits a volcano-shaped pH dependence peaked at a pH close to the pK a of HCOOH (3.75). The experimental result is reasonably explained by a simple kinetic model that HCOO − oxidation is the dominant reaction route over the whole pH range.HCOOH is oxidized after being converted to HCOO − via the acid-base equilibrium. The ascending part of the volcano plot at pH < 4 is ascribed mostly to the increase of the molar ratio of HCOO − , while the descending part at pH > 4 is ascribed to the suppression of HCOO − oxidation by adsorbed OH or oxidation of the electrode surface. In acidic media, HCOOH is

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confidence: 99%

The effect of pH on the electrocatalytic oxidation of formic acid/formate on platinum: A mechanistic study by surface-enhanced infrared spectroscopy coupled with cyclic voltammetry

Joo

Uchida

Cuesta

et al. 2014

Electrochimica Acta

Self Cite

132

127

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“…Oscillatory phenomena and other nonlinear phenomena such as bistability and spatiotemporal patterns are frequently observed in metal and alloy electrodissolutionpassivation processes (Hudson & Tsotsis, 1994;Koper, 1996a;Krischer, 1999;Krischer, 2003b). Current oscillations during the Fe electrodissolution-passivation in acid solutions were reported as early as 1828 (Fechner, 1828).…”

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Oscillatory Phenomena as a Probe to Study Pitting Corrosion of Iron in Halide-Containing Sulfuric Acid Solutions

Sazou¹,

Pavlidou²,

Diamantopoulou³

et al. 2012

Pitting Corrosion

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“…Since most (electro)chemists are thus not familiar with nonlinear dynamics, it is useful to introduce here some of the basic concepts [1][2][3][4][5][6][7][8][9], in order to facilitate the reading of the contributions to this topical issue. If similar dynamic phenomena occur in different systems, they must have common mechanistic basis.…”

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“…Interfacial electrochemical systems have of course their specific features which contribute to the source of instabilities, also of the entire electric circuit [3][4][5][6][7][8][9]. One of them can be the non-monotonic dependence between the current and the electrode potential, caused by, e.g., passivation of the electrode surface or an adsorption of an inhibitor in certain potential range.…”

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confidence: 99%

“…Now, if there is an additional source of slow negative feedback, coming, e.g., from a relatively slow diffusion transport of the reacting particles from the system's bulk to the electrode surface, the steady-states may undergo continuous destabilization and sustained oscillatory variations of the current can then emerge, showing in such a case their strict correlation with bistability. Under appropriate conditions and for more sophisticated system's characteristics, involving the so-called hidden N-shaped negative resistance (HN-NDR) [5], also oscillations of the electrode potential can occur upon polarization of the electrode with constant current. Now, let us consider inhomogeneous systems in which concentration or potential gradients exist and hence induce transport phenomena, like diffusion or migration.…”

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