Analytical I–E response for several multistep potential techniques applied to an electrocatalytic process at mediator modified electrodes

González, Joaquı́n; Soto, Carmen M.; Molina, Á.

doi:10.1016/j.electacta.2009.05.068

Cited by 13 publications

(33 citation statements)

References 14 publications

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“…(3) it can be seen that in both mechanisms the decrease of the sweep rate v leads to a decrease of the current. Nevertheless, for the catalytic mechanism the peak heights are higher than those of an E mechanism and also the current reaches the value k c Q MAX at cathodic potentials, independently of the sweep rate [19,29].…”

Section: ( )mentioning

confidence: 99%

“…By taking into account the charge transfer constant obtained in the same conditions ( k 0 = 480 s 1 ), the theoretical curves have been calculated using the following parameters: n = 2 , = 0. [19].…”

Section: ( )mentioning

confidence: 99%

“…Hydrazobenzene, formed by electrochemical reduction of azobenzene, is reoxidized by hydrogen peroxide, and the whole electrode reaction turns into a surface catalytic mechanism in according to the next scheme [19,27]:…”

Section: ( )mentioning

confidence: 99%

“…A + ne The expression of the current-potential curves in staircase voltammetry, for any reversibility degree of the charge transfer of the electrocatalytic process, is given by [19]:…”

Section: Catalytic Mechanism At a Modified Electrodementioning

confidence: 99%

“…Analytical and easy manageable expressions for the current of a simple charge transfer process and of an electrocatalytic process at mediator modified electrodes for any multipotential pulse technique were deduced in previous papers [13,14,18,19].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Study of the Electrocatalytic Reaction of Hydrogen Peroxide Mediated by Azobenzene Monolayer with Several Multipotential Pulse Techniques

González¹,

Soto²,

Molina³

2009

TOELECJ

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Abstract:The comparison between the response corresponding to a simple charge transfer taking place at an electroactive monolayer with that of an electrocatalytic process at a modified electrode are presented by using the multipulse potential techniques cyclic staircase voltammetry (CSCV) and cyclic square wave voltammetry (CSWV). General analytical and explicit equations for the I E responses have been tested by means of the study of the reduction of azobenzene monolayer at mercury electrode. The value of the chemical rate constant ( k c ' = 40 M 1 s 1 ) has been easily obtained from the cathodic plateau of the CSCV curves and from the best fitting between theoretical and experimental CSWV curves.

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Section: ( )mentioning

confidence: 99%

Section: ( )mentioning

confidence: 99%

Section: ( )mentioning

confidence: 99%

“…A + ne The expression of the current-potential curves in staircase voltammetry, for any reversibility degree of the charge transfer of the electrocatalytic process, is given by [19]:…”

Section: Catalytic Mechanism At a Modified Electrodementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Study of the Electrocatalytic Reaction of Hydrogen Peroxide Mediated by Azobenzene Monolayer with Several Multipotential Pulse Techniques

González¹,

Soto²,

Molina³

2009

TOELECJ

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Analysis of the Electrochemical Response of Surface‐confined Bidirectional Molecular Electrocatalysts in the Presence of Intermolecular Interactions

González

Sequí

2020

ChemCatChem

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A theoretical model for the response of bidirectional surface confined molecular electrocatalysts in the presence of intermolecular interactions is presented. Particular cases corresponding to Nernstian and fully irreversible redox behaviour are discussed, with the main features of the stationary current‐potential response being analysed in detail. This analysis has revealed important nuances in the understanding of the overall process relative to the limits of validity of some frequent assumptions, as for example, a Nernstian behaviour of the charge transfer step and therefore of the complete catalytic mechanism. The presence of interactions leads to a distortion of the current‐potential responses for which, in the case of repulsive interactions, higher overpotential values are required for a given conversion rate. In the case of non‐Nernstian charge transfer processes, high catalytic rates give rise to an increase of the overall irreversibility of the catalytic currents. The experimental verification of the model corresponding to the response of binary 11‐(ferrocenyl)undecanethiol/decanethiol in presence of ferro/ferricyanide is presented and discussed. The impact of the experimental conditions on the apparent values of the formal potential and redox rate constants of the molecular electrocatalyst is also analysed.

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Comparison Between a Charge Transfer Process and an Electrocatalytic Process in Cyclic Voltammetry and Cyclic Voltcoulommetry. Application to the Oxidation of Ferrocyanide at a Ferrocene‐Monolayer Modified Gold Electrode

2009

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Ferrocyanide oxidation catalyzed by a ferrocene-alkylthiolate monolayer at gold electrodes has been investigated by using cyclic voltammetry (CV) and cyclic voltcoulommetry (CVC). The voltammetric current-potential curves obtained present a stationary sigmoidal feature which points out to a very high rate constant for the chemical step, whereas the charge-potential curves do not reach an stationary behavior in any case. Simple expressions are presented for the characterization of the CV and CVC curves under Nernstian conditions for the charge transfer step. From these expressions, a value for the chemical rate constant 2.5 Â 10 4 M À1 s À1 has been easily obtained from an anodic plateau of the CV curves or from the linear anodic region of the CVC curves.

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Analytical I–E response for several multistep potential techniques applied to an electrocatalytic process at mediator modified electrodes

Cited by 13 publications

References 14 publications

Study of the Electrocatalytic Reaction of Hydrogen Peroxide Mediated by Azobenzene Monolayer with Several Multipotential Pulse Techniques

Study of the Electrocatalytic Reaction of Hydrogen Peroxide Mediated by Azobenzene Monolayer with Several Multipotential Pulse Techniques

Analysis of the Electrochemical Response of Surface‐confined Bidirectional Molecular Electrocatalysts in the Presence of Intermolecular Interactions

Comparison Between a Charge Transfer Process and an Electrocatalytic Process in Cyclic Voltammetry and Cyclic Voltcoulommetry. Application to the Oxidation of Ferrocyanide at a Ferrocene‐Monolayer Modified Gold Electrode

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