Synchronized current oscillations of formic acid electro-oxidation in a microchip-based dual-electrode flow cell

Kiss, István Z.; Munjal, Neil; Martin, R. Scott

doi:10.1016/j.electacta.2009.02.094

Cited by 20 publications

(23 citation statements)

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“…In a previous study, oscillatory electrooxidation of formic acid on Pt [19-21] was investigated in a micro-chip based microfluidic electrode flow cell. [22] The fluidic component of the chip, made of poly(dimethylsiloxane) (PDMS) with soft lithography [23], was reversibly sealed to a glass round with 100 μm wide Pt band electrode. The main dynamical features of current oscillations that had been observed in macro-cells[19-21] were reproduced in the microfabricated electrochemical cell.…”

Section: Introductionmentioning

confidence: 99%

“…The main dynamical features of current oscillations that had been observed in macro-cells[19-21] were reproduced in the microfabricated electrochemical cell. [22] The previous experimental design enables the investigation of the dynamical behavior of electrochemical reactions on a thin noble metal (Pt, Pd, Au) band electrode with well-defined control of flow of the electrolyte in a manner where the size of the electrode can be easily varied.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical oscillations of nickel electrodissolution in an epoxy-based microchip flow cell

Cioffi

Martin

Kiss

2011

Journal of Electroanalytical Chemistry

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We investigate the nonlinear dynamics of transpassive electrodissolution of nickel in sulfuric acid in an epoxy-based microchip flow cell. We observed bistability, smooth, relaxation, and period-2 waveform current oscillations with external resistance attached to the electrode in the microfabricated electrochemical cell with 0.05 mm diameter Ni wire under potentiostatic control. Experiments with 1mm × 0.1 mm Ni electrode show spontaneous oscillations without attached external resistance; similar surface area electrode in macrocell does not exhibit spontaneous oscillations. Combined experimental and numerical studies show that spontaneous oscillation with the on-chip fabricated electrochemical cell occurs because of the unusually large ohmic potential drop due to the constrained current in the narrow flow channel. This large IR potential drop is expected to have an important role in destabilizing negative differential resistance electrochemical (e.g., metal dissolution and electrocatalytic) systems in on-chip integrated microfludic flow cells. The proposed experimental setup can be extendend to multi-electrode configurations; the epoxy-based substrate procedure thus holds promise in electroanalytical applications that require collector-generator multi-electrodes wires with various electrode sizes, compositions, and spacings as well as controlled flow conditions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrochemical oscillations of nickel electrodissolution in an epoxy-based microchip flow cell

Cioffi

Martin

Kiss

2011

Journal of Electroanalytical Chemistry

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“…9,10 When concentrations (or reaction rates) in these units exhibit oscillatory behavior, the interactions can produce a wide array of synchronization related behaviors, e.g., periodic 4,11,12 and chaotic 13,14 synchronization, oscillator death, [15][16][17][18][19][20] collective synchronization, [21][22][23] dynamical clustering, [24][25][26] and quorum transition. 27 The synchronization behaviors have been observed in BelousovZhabotinsky (BZ) reaction, 3,4,12,13,15,28,29 pH oscillators, 30 and biochemical reaction 31 in coupled continuously fed, stirred tank reactors (CSTRs), in metal dissolution 21,24,25,[32][33][34][35][36][37] and electrocatalytic [38][39][40] reactions in electrochemical systems, in CO oxidation on heterogeneous catalysts, 41,42 and in BZ beads, 22,23,26,…”

Section: Introductionmentioning

confidence: 99%

Dynamics of electrochemical oscillators with electrode size disparity: asymmetrical coupling and anomalous phase synchronization

Wickramasinghe

Mrugacz

Kiss

2011

Phys. Chem. Chem. Phys.

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Experiments are carried out in dual electrode oscillatory Ni electrodissolution in which the two electrodes have different surface areas. The transition to phase synchronization is analyzed as asymmetrical coupling strength, induced by placing a cross resistance between the electrodes, is varied. It is shown that because of nonisochronicity (phase shear, i.e., strong dependence of period on amplitude) of the oscillators, anomalous phase synchronization effects can be observed: advanced/delayed synchronization and, to a lesser extent, frequency difference enhancement. The type of synchronization is strongly affected by the underlying heterogeneities of the oscillators; in the experiments with a slow driver (large surface area) electrode the synchronization is advanced, with a fast driver electrode the synchronization is delayed with respect to symmetrical coupling. The findings thus reveal that the interplay of asymmetrical coupling with the types of inherent heterogeneities plays an important role for the interpretation of size effects in the dynamical behavior of a nonlinear chemical reaction.

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“…5.4 of volume I, there was described the oscillatory oxidation of formic acid/formate ions and its electrochemical mechanism. Recently, a novel approach to the studies of the role of coupling in the electrooxidation of formic acid on Pt electrodes was described by Kiss et al [7] who have applied a microchip-based dual-electrode flow cell, with microfluidic flow control ( Fig. 3.8).…”

Section: Coupling In the Oscillatory Oxidation Of Formic Acidmentioning

confidence: 99%

Cooperative Dynamics of Coupled and Forced Oscillators

Orlik

2012

Self-Organization in Electrochemical Systems II

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The formation of dissipative patterns on electrode surfaces is related to various kinds of spatial couplings that interact with the electrochemical process in a way dependent, among others, on the geometrical arrangement of the electrodes and the operational mode of the electrochemical experiments. A natural development of the concept of individual reaction sites engaged into such couplings is the case of coupled oscillators. It is thus not surprising that the treatment of coupling of the individual oscillators and spatiotemporal phenomena in a single oscillator may have common points. The analysis of such complex systems allows to understand better the general mechanisms underlying the spatiotemporal phenomena, including the coupling that exist between oscillators in living systems, e.g., in the biological cell membranes.The coupling of chemical or electrochemical oscillators can lead to either more complex or simpler oscillatory regimes, in the latter case including even ceasing of the oscillations. A special variant of such coupling can be realized through the external perturbation of a single oscillator or of a set of them.Karantonis and Nakabayashi [1] have analyzed the case of coupling of two limit cycle electrochemical oscillators, described by only two dynamical variables. In this work the diffusive coupling in one dynamical variable is considered which, under appropriate conditions, can lead to dephasing of the oscillators. This particular problem is related to the suggestion by Kuramoto [2] that chemical spatiotemporal chaos might arise where diffusive coupling leads to dephasing. The problem is important since it was shown, in terms of the model approach, that the diffusive coupling of the transmembrane voltage, in the presence of a strong deformation of the phase flow in the vicinity of the limit cycle, can cause the dephasing of oscillators and bursting oscillations [3]. The model of electrochemical M. Orlik, Self-Organization in Electrochemical Systems II, Monographs in Electrochemistry,

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Synchronized current oscillations of formic acid electro-oxidation in a microchip-based dual-electrode flow cell

Cited by 20 publications

References 51 publications

Electrochemical oscillations of nickel electrodissolution in an epoxy-based microchip flow cell

Electrochemical oscillations of nickel electrodissolution in an epoxy-based microchip flow cell

Dynamics of electrochemical oscillators with electrode size disparity: asymmetrical coupling and anomalous phase synchronization

Cooperative Dynamics of Coupled and Forced Oscillators

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