Oscillatory instabilities during the electrochemical oxidation of sulfide on a Pt electrode

Miller, B.; Chen, Aicheng

doi:10.1016/j.jelechem.2006.01.006

Cited by 27 publications

(27 citation statements)

References 48 publications

(57 reference statements)

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“…For example, Chen and Miller reported the potential oscillations on a microstructured Ti/Ta 2 O 5 -IrO 2 electrode [22] , and two oscillatory regions were found in this system. However, oscillatory phenomena seems cannot be obtained under potentiostatic condition, which was quite different from the cases on pyrite and platinum electrode [23][24][25][26] . Most recently, we reported various nonlinear phenomena in the oxidation of sulfide on a polycrystalline platinum electrode [25] , and multi-oscillatory windows were found under galvanostatic condition.…”

mentioning

confidence: 77%

“…Both of the two oscillations have been reported in our previous work. According to previous work [26] , it can be classified as N-NDR and HN-NDR oscillators, respectively. It means that in both of these two oscillatory regimes, double layer potential is an autocatalytic variable, and the external circuit plays an important role in the oscillatory mechanism.…”

Section: Methodsmentioning

confidence: 99%

“…Oxidations of sulfur-containing species, including sulfide, have garnered increasing attention in the past two decades [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] . The oxidation could take place by reacting with various oxidants or via an electrochemical method, and various nonlinear phenomena have been observed in the oxidation of sulfur-containing species.…”

mentioning

confidence: 99%

“…Recently, dynamical instabilities have been observed in the electrochemical oxidation of sulfide on various electrodes [22][23][24][25][26] . For example, Chen and Miller reported the potential oscillations on a microstructured Ti/Ta 2 O 5 -IrO 2 electrode [22] , and two oscillatory regions were found in this system.…”

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confidence: 99%

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Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Feng

Gao

et al. 2008

Sci. China Ser. B-Chem.

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The electrochemical oxidation of sulfide on a polycrystalline platinum electrode was studied under potentiostatic condition when an external resistor is in series with the working electrode. Only two oscillatory regions can be obtained in the absence of the external resistance, but four oscillatory regions, including two new current oscillations, were found in this system by controlling the external resistance. It is demonstrated that three oscillatory regimes, which arise on the positive branch of current-potential curve, can be classified as HN-NDR (Hidden N-shaped Negative Differential Resistance) oscillators. For the first oscillatory region, various transient complex phenomena, which result from the change of the electrode/electrolyte interface by accumulation of adsorbed element sulfur on the electrode, have been observed. The dynamic behavior of NDR (Negative Differential Resistance) oscillations, appearing along with negative branch of polarization curve, can transform from oscillations into bistability with a sufficient large external resistance in series. Two oscillatory regions in high-potential region classified as HN-NDR type oscillations are separated by a saddle-loop bifurcation. They displayed a sequence of bursting oscillations and irregular oscillations, respectively. The electrochemical oxidation of sulfide provides a model system for studying complex dynamics and possible application in sulfur removal.sulfide, electrochemical oxidation, series resistance, bistability and oscillations, mixed-mode and bursting oscillations One of the important achievements in the last century has revealed that systems kept far from thermodynamic equilibrium can result in the occurrence of self-organization, and complex oscillations and chaos can arise in deterministic systems (those with only a few active degrees of freedom) [1,2] . Spontaneous oscillatory reactions are widespread in electrochemistry [3,4] , and understanding the onset of non-equilibrium phenomena in electrochemical reactions has far reaching impacts [5,6] . The observation of Turing-type patterns on electrode surfaces [6] , for example, points to a prospective exploitation of pattern-forming mechanism to manufacture structured electrodes similar of those being developed for the (bio)sensors, where wavelength of the pattern could be conveniently manipulated by changing reaction conditions, such as temperature, concentrations of electrolytes, and values of the applied potential/current. In the past few decades, a great deal of work has been done to reveal the origin of electrochemical spatiotemporal instabilities [7][8][9][10][11] , and new methods and concepts are developed in nonlinear dynamics of electrochemistry. Even general models for temporal [8] and spatial [11] instabilities were given about 15 and 10 years ago, respectively, However, there are still many observations that cannot be explained, for example, complex temporal behavior under galvanostatic conditions and various spatiotemporal behavior during metal electrodissolution. As show...

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confidence: 77%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Feng

Gao

et al. 2008

Sci. China Ser. B-Chem.

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“…Also Miller and Chen, in more recent studies [152] have described the anodic oxidation of sulfide ions at the Pt electrode. Besides the type A and B (or / and b) galvanostatic oscillations (analogously to Ti/Ta 2 O 5 -IrO 2 electrode), current oscillations, as well as bistability were reported.…”

Section: Oscillatory Oxidation Of Sulfur Compoundsmentioning

confidence: 99%

Temporal Instabilities in Anodic Oxidation of Small Molecules/Ions at Solid Electrodes

Orlik

2012

Monographs in Electrochemistry

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Oscillations and multistability in oxidation processes at solid electrodes are important for several reasons. First, they were reported for species that are (or can appear) important in chemical engineering of fuels, including the fuel cells: hydrogen, carbon monoxide, formaldehyde, formic acid/formate ions, 2-propanol, 1-butanol, hydrazine, or ethylene glycol. It can be useful to know how to avoid instabilities involving these species or, on the contrary, to profit from them. Second, electrooxidation of these molecules exhibits rich variety of nonlinear dynamic behaviors which can be treated in a model way for the sake of generalization. Third, some of these processes, under appropriate conditions, can become a source of spatial or spatiotemporal patterns on electrodes which phenomena only recently gained satisfactory explanation and description. In this chapter, we shall summarize the temporal phenomena associated with the oxidation of the above-mentioned molecules, while pattern formation will be discussed in separate Chap. 2 of volume II.Current research data indicate that such processes should be qualified as electrocatalytic, i.e., the electrode surface is actively engaged in the kinetics of the electron transfer reaction, usually involving the process taking place via the adsorbed intermediate. As in the case of other types of electrochemical oscillators, one can observe the evolution of the understanding of the source of chemical instabilitiesfrom early, sometimes oversimplified explanations oriented exclusively on the properties of the electrode/electrolyte interface toward more recent concepts, involving the analysis of the system's stability in terms of nonlinear dynamics. In particular, oscillations under galvanostatic conditions could be understood only recently in terms of the concept of the HN-NDR oscillator [1] (cf. Chap. 3).The anodic oxidation of H 2 on Pt electrode is an electrocatalytic process, in which the electron transfer is preceded by the adsorption of H 2 molecule on the active surface site. Hence, the oscillatory course of this process can be associated M. Orlik, Self-Organization in Electrochemical Systems I, Monographs in Electrochemistry,

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A novel H₂S/H₂O₂fuel cell operating at the temperature of 298 K

Sanlı¹,

Yılmaz

Aytaç

2012

Int. J. Energy Res.

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SUMMARY In this study, the oxidation mechanism of hydrogen sulfide (H2S) is investigated, and a fuel cell operating with acidic peroxide as oxidant and basic hydrogen sulfide as fuel is constructed. A stable solid state H2S/H2O2 fuel cell has been developed at the temperature of 298 K. A nickel anode catalyst has been examined using Nafion‐117 as a proton‐conducting membrane. In an operating with the acidic hydrogen peroxide (H2O2) as oxidant, the cell potential was increased to a value of 0.85 V at 298 K. The main conclusion of this study is the management to increase the cell potential to 850 mV at 25 °C, whereas this value can only be achieved in the H2S/O2 fuel cell at 850–1000 °C. Moreover, there exists no prior work on the H2S/H2O2 fuel cell research. Copyright © 2012 John Wiley & Sons, Ltd.

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Oscillatory instabilities during the electrochemical oxidation of sulfide on a Pt electrode

Cited by 27 publications

References 48 publications

Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Temporal Instabilities in Anodic Oxidation of Small Molecules/Ions at Solid Electrodes

A novel H₂S/H₂O₂fuel cell operating at the temperature of 298 K

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Oscillatory instabilities during the electrochemical oxidation of sulfide on a Pt electrode

Cited by 27 publications

References 48 publications

Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Temporal Instabilities in Anodic Oxidation of Small Molecules/Ions at Solid Electrodes

A novel H2S/H2O2fuel cell operating at the temperature of 298 K

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A novel H₂S/H₂O₂fuel cell operating at the temperature of 298 K