Role of Ion Pairing in Double-Layer Effects at Self-Assembled Monolayers Containing a Simple Redox Couple

Andreu, Rafael; Calvente, Juan José; Fawcett, W. Ronald; Molero, M.

doi:10.1021/jp963701k

Cited by 46 publications

(52 citation statements)

References 21 publications

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“…Discreteness-of-charge effects were also discussed for a self-assembled monolayer containing a simple redox couple [64]. In a later paper, the role of ion pairing on double layer effects in these systems was detailed [65].…”

Section: The 1990smentioning

confidence: 99%

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Fawcett

2011

J Solid State Electrochem

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Developments in the treatment of double layer effects in electrode kinetics are outlined. These include discreteness-of-charge effects in the presence of specific adsorption, solvent effects in electron transfer reactions, and effects related to the distribution of charge in polyatomic reactants. The importance of studies at single crystal electrodes is emphasized, and the development of a single crystal ultramicroelectrode described. Finally, a method of improving the estimate of the diffuse layer potential drop on the basis of Monte Carlo simulations is presented.

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Section: The 1990smentioning

confidence: 99%

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Fawcett

2011

J Solid State Electrochem

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“…In the latter case, the change in charge density of the SAM surface causes a variation in the local electrostatic potential. 139,155 The distortion of the CV is reduced when the coverage of redox centers is low and/or ion-pairing reduces the change in charge density with oxidation state. Sharp CVs with small E fwhm values are obtained if the redox centers tend to form a solid-like phase; this occurs only in the most densely packed electroactive SAMs.…”

Section: Attached Redox Centersmentioning

confidence: 99%

Self‐Assembled Monolayers on Electrodes

Finklea

2000

Encyclopedia of Analytical Chemistry

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Alkanethiols and related molecules spontaneously adsorb from solution or vapor phase onto oxide‐free metals, especially gold, to form close‐packed oriented monolayers. The ease and flexibility of the self‐assembly process provides a convenient method for altering the properties of the metal as an electrode. The close‐packed hydrocarbon layer blocks access of most solution species to the electrode surface. Consequently, interfacial capacitances are markedly reduced and most electron‐transfer reactions are strongly inhibited. The monolayers also provide a foundation for attachment of additional molecules or molecular layers to electrodes. Self‐assembled monolayers (SAMs) on electrodes have been used in voltammetric methods to improve the analytical sensitivity and to impart greater selectivity towards specific analytes. Redox molecules have been anchored at fixed and controllable distances from the electrode surface, thereby permitting the study of electron‐transfer kinetics over long distances and at large driving forces. The ability of SAMs to inhibit metal corrosion and to promote better adhesion of electroactive polymers has been demonstrated.

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“…Recent theoretical work has focused on the effects of ionizeable acid-bases groups located at the monolayer solution interface [2][3][4] , ion pairing [5][6][7] and discreteness of charge effects 6,8 on the voltammetric response and the effect of the IPD on potential step chronoamperometry (PSCA) of reversible reactions 9 . Application of these models is not limited to SAMs.…”

Section: Introductionmentioning

confidence: 99%

Effect of the Interfacial Potential Distribution on the Measurement of the Rate Constant for Electron Transfer between Electrodes and Redox Adsorbates

Honeychurch

1998

Langmuir

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The effects of the interfacial potential distribution on cyclic voltammetry (CV) of adsorbed redox molecules exhibiting slow (quasi-reversible and irreversible) electron transfer is considered in a theoretical model. Results of numerical simulations based on this model are presented and compared to CVs and measurements in the absence of double layer effects. The slopes of plots of peak potential versus Log sweep rate are the same, i.e.RT nF and RT 1 ( )nF for the cathodic and anodic reactions respectively, as predicted in the absence of double layer effects. The calculation of the rate constant can be greatly influenced by the double layer effects.2

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Role of Ion Pairing in Double-Layer Effects at Self-Assembled Monolayers Containing a Simple Redox Couple

Cited by 46 publications

References 21 publications

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Self‐Assembled Monolayers on Electrodes

Effect of the Interfacial Potential Distribution on the Measurement of the Rate Constant for Electron Transfer between Electrodes and Redox Adsorbates

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