High-order periodic voltammograms, period doubling and chaotic cyclic voltammetric behaviour

Schell, Mark; Xiao-rong, Cai

doi:10.1039/ft9918702255

Cited by 15 publications

(10 citation statements)

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“…Additionally, the bistability region observed in Figure A occurs in the same region as Au surface oxidation. It was already stated that metallic surface oxides can also act as poisonous species. ,,, …”

Section: Resultsmentioning

confidence: 99%

“…It was already stated that metallic surface oxides can also act as poisonous species. 49,54,57,58 The occurrence of oscillatory behavior that is exclusive to chaotropic and "neutral" media suggests that the SO 2 adsorbed by the S atom, observed just in these electrolytes, is the main reason for the bifurcation, the phase changing from linear to nonlinear dynamics. This leads to the conclusion that pyrosulfite is the main poison and a cyclic autocatalytic mechanism, as presented in Scheme 3, is proposed.…”

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confidence: 99%

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Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation

et al. 2019

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The current electrochemical method for H2 production is water electrolysis, a process with a high energy demand, which is limited by the oxygen evolution reaction (OER). One way to handle the problems related to the OER is to use other oxidative reactions by so-called coupled water electrolysis. One option is the SO2 oxidation reaction (SO2OR), a process that generates H2SO4, which has industrial use, by the consumption of an abundant pollutant that demands, under standard conditions, 0.70 V less than the OER according to theoretical predictions. On the basis of theoretical calculations the mechanism is expected to be the same for a range of metallic catalysts, with the best ones being Pt and Au, in order. Here, the SO2 electro-oxidation on Pt and Au electrodes was investigated by in situ infrared reflection–absorption (IRRA) spectroelectrochemistry, aiming to elucidate the mechanism. On Pt, species such as dithionate, S2O6 2–, not commonly cited in the literature, were found as intermediates, and PtOH and PtO were suggested as oxidative species. On Au electrodes, the situation observed was completely different. The electrolyte chaotropicity strongly influenced the adsorption of SO2 on Au, changing from Au–O for highly kosmotropic media to Au–S for more chaotropic systems. When the Au–S bond is formed, dithionate and S2O5 2– species were simultaneously present along with the Au(SO3) complex in solution. The observation of these two species was accompanied by potential oscillations, and an HN-NDR (hidden N-shaped negative differential resistor) oscillator was observed. Different mechanisms for different electrolytes are proposed for Au electrodes.

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Section: Resultsmentioning

confidence: 99%

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Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation

et al. 2019

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“…6,7 A detailed study of the mechanistic cause of the instabilities has not been completed. However, the responses are similar to the responses obtained in application of cyclic voltammetry to methanol oxidation for which such a study has been completed.…”

Section: Experiments and Backgroundmentioning

confidence: 99%

Superstable nonequilibrium states

Amini

Schell

1995

The Journal of Chemical Physics

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Relaxation times were measured from the decay to period-one attractors, a period-two attractor, and a period-three attractor in two reaction processes: the voltammetric oxidations of ethanol and 1-propanol. The results provide strong evidence that a periodic state that can undergo a subharmonic bifurcation is most stable near the point where the relaxation changes from a monotone to an alternating approach. The relation between the experimental results and theory is discussed and it is concluded that the reaction processes are in what is called the strongly contracting limit.

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“…They have employed a variety of measurements other than the electrochemical ones [2][3][4][5][6][7][8], such as using an electrochemical quartz crystal microbalance (EQCM) [9][10][11], differential electrochemical mass spectroscopy (DEMS) [12], probe beam deflection [13], surface stresses [11,14], ultrasound [15], and surface-enhanced infrared absorption spectroscopy (SEIRAS) [16,17]. Based on these studies, it has been established that adsorbed CO [18][19][20], a reaction intermediate in the indirect path of the dual path mechanism [21,22], plays a crucial role in the appearance of oscillation.…”

Section: Introductionmentioning

confidence: 99%

Chloride ion influencing potential oscillation generated by formaldehyde oxidation

Kikuchi

Mukouyama

Okamoto

2008

Electrochimica Acta

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High-order periodic voltammograms, period doubling and chaotic cyclic voltammetric behaviour

Abstract: Cyclic voltammograms with periods longer than the period of the potential, a period-doubling bifurcation, and chaotic voltammetric responses are presented from a study of the oxidation of ethanol at a rotating platinum disk in alkaline solution.

Cited by 15 publications

References 4 publications

Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation

Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation

Superstable nonequilibrium states

Chloride ion influencing potential oscillation generated by formaldehyde oxidation

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High-order periodic voltammograms, period doubling and chaotic cyclic voltammetric behaviour

Abstract: Cyclic voltammograms with periods longer than the period of the potential, a period-doubling bifurcation, and chaotic voltammetric responses are presented from a study of the oxidation of ethanol at a rotating platinum disk in alkaline solution.

Cited by 15 publications

References 4 publications

Opportunities and Knowledge Gaps of SO2 Electrocatalytic Oxidation for H2 Electrochemical Generation

Opportunities and Knowledge Gaps of SO2 Electrocatalytic Oxidation for H2 Electrochemical Generation

Superstable nonequilibrium states

Chloride ion influencing potential oscillation generated by formaldehyde oxidation

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Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation

Opportunities and Knowledge Gaps of SO₂ Electrocatalytic Oxidation for H₂ Electrochemical Generation