Ion and electron transport in stable, electroactive tetrathiafulvalene polymer coated electrodes

Kaufman, F. B.; Schroeder, Albert H.; Engler, E. M.; Krämer, Stephan; Chambers, James Q.

doi:10.1021/ja00522a007

Cited by 246 publications

(98 citation statements)

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“…Polymer lattice motions and changes in polymer conformation may also occur to accommodate the doping/ de-doping and charge transfer processes through the conjugated Osystem during any redox switching. [19][20][21] Although the peak current decreases slightly upon repetitive cycling, the peak shapes remain virtually unchanged. For all films, the i pa /i pc ratio varied between 1.23-1.92.…”

Section: Electrochemistry 83(12) 1061-1066 (2015)mentioning

confidence: 99%

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

et al. 2015

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A new compound with the core luminescent dye unit diketopyrrolopyrrole (DPP), namely 3,6-dithiophen-2-yl-2,5-dihydropyrrole [3,4-c]pyrrole-1,4-dione (DTDPP), attached to 3,4-ethylenedioxythiophene (EDOT) was synthesized. From this monomer, polymer films were prepared on glassy carbon and indium tin oxide surfaces using cyclic voltammetry. The films were characterized using cyclic voltammetry, chronocoulometry, and atomic force microscopy. The electropolymerization of the monomer exhibits reversible electrochemistry that transitions to quasireversible electrochemistry. During electropolymerization, the overpotential for the reduction process exceeds the overpotential for the oxidation process and cyclic voltammetric characterization of the films demonstrates that oxidation is more favored than reduction. Spectroelectrochemical measurements confirm that the polymer films demonstrate electrochromic behavior that correlates to the electrochemical observations during characterization of the films.

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Section: Electrochemistry 83(12) 1061-1066 (2015)mentioning

confidence: 99%

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

et al. 2015

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“…Depending on the distance separating the active sites, the motion of polymer chain segments may be required to bridge the interstice separation for charge transport. 16,19 The permeation of ClO4 -possibly decreases the polymer chain motion, resulting in a change in the peak currents.…”

Section: With Increasing Clo4mentioning

confidence: 99%

“…The charge transport rate through the film depends on these factors. 16 Because highredox site concentration results in a fast-electron self-exchange rate, the charge transport within the redox polymer modified electrodes is rapid. 17,18 On the other hand, the charge transport is related to the motion of counterions in polymer film for the requirement of electroneutrality.…”

mentioning

confidence: 99%

Electrolyte Effects on Electrochemical Properties of Osmium Complex Polymer Modified Electrodes

Gong

Zhu

2001

ANAL. SCI.

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Chemical and biosensors based on chemically modified electrodes, particularly polymer modified electrodes, have become an important field of study. [1][2][3] A modification of the electrode surface greatly improves the chemical, optical and electrical characteristics, leading to many applications as chemical sensors, electrochromic devices, electronic devices and energy storage as well as corrosion protection. 4 [Os(bpy)2(PVI)10Cl]Cl and [Os(bpy)2(PVP)10Cl]Cl, where bpy is 2,2′-bipyridyl, PVI is poly(N-vinylimidazole), and PVP is poly(4-vinylpyridine), are two typical electron transfer mediators with a near-ideal electrochemical behavior, 5 which have been extensively used for the preparation of electrochemical enzyme sensors. [6][7][8][9][10][11] Modified electrodes based on these polymers show high electrochemical activity and can catalyze those reactions that are difficult for direct electron transfer, such as the electrochemical oxidations of epinephrine and dopamine, 6 ascorbic acid 7 and glucose. 8 After further crosslinking with enzymes, these modified electrodes have been designed for the determination of enzyme activity or their substrates 9,10 and as immunosensors. 11 However, the electrochemical behaviors of these metallopolymers are dependent on many factors, including the pH of the supporting electrolyte, electrolyte species, and solvent. Some of their influences, such as electrolyte species and solvents have been extensively reported by Vos, Forster and Hillman. [1][2][3][12][13][14][15] Vos and Forster studied the effects of the Cl -and ClO4 -concentrations and the time scale of electrochemical methods on the homogeneous and heterogeneous charge transfer dynamics of Os-PVPn (n = 1 -25) 12 and the difference of SO4 2-and ClO4 -at Os-PVP10. 13 In order to better understand and exert greater control over the transport properties of the electroactive polymers, the present work further compared the electrochemical behaviors of Os-PVP10 and Os-PVI10 modified electrodes under the same solution environments, and exhaustively studied the effects of the pH, electrolyte cations and anions on these properties by using cyclic voltammetry.The film structure has a profound effect on the properties of polymer modified electrodes, because it influences both the transport rate of mobile species through a film and the local environment within which it undergoes a mediated charge transfer reaction with polymer-bond redox sites. 15 As generally accepted, the charge transport in such redox polymers undergoes an electron hopping or self-exchange process, accompanying the motion of charge-compensating counterions, solvent and polymer chain segments. The charge transport rate through the film depends on these factors. 16 Because highredox site concentration results in a fast-electron self-exchange rate, the charge transport within the redox polymer modified electrodes is rapid. 17,18 On the other hand, the charge transport is related to the motion of counterions in polymer film for the requirement of electroneutrality. In...

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“…Kaufman et al 9 have proposed a model for charge transportation through polymeric films in the sense that propagation of charge takes place by auto exchange electronic reactions among oxidized and reduced species positioned at neighboring sites in the film. This model has been also suggested for PANI films in a recent paper 10 dealing with the optical behavior of poly(2-ethyl aniline) films.…”

Section: Introductionmentioning

confidence: 99%

Structural, morphological and spectroelectrochemical characterization of poly (2-ethyl aniline)

Schemid

Torresi

Bassetto

et al. 2000

J. Braz. Chem. Soc.

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Neste trabalho foi feito um estudo comparativo da estrutura, morfologia e resposta espectroeletroquímica da poli (2-etilanilina) e da polianilina em função do contra-íon. Os ácidos minerais conferem uma estrutura mais esponjosa a filmes de poli (2-etilanilina) enquanto que ácidos orgânicos tornam a estrutura homogênea e compacta. Para a poli (2-etilanilina) a resposta eletroquímica depende muito da relação carga/tamanho do eletrólito utilizado, devido a efeitos estéricos e eletrônicos. As relações entre as bandas de absorção e os pares redox mostram que mudanças na absorbância são proporcionais a corrente faradaica que é observada nos voltamogramas.In this paper a comparative study of the structure, morphology, and the spectroelectrochemical response of poly (2-ethyl aniline) and polyaniline for different counterions is presented. Spongeous structure of poly (2-ethyl aniline) is obtained when mineral acids are used, while homogeneous and compact films are formed using organic acids. The electrochemical response of poly (2-ethyl aniline) depends on the charge/size ratio of the counterion due to both steric and electronic effects. The correlation between the absorption bands and the redox couple show that the changes in absorbance are proportional to the faradaic current observed in the voltammograms.

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Ion and electron transport in stable, electroactive tetrathiafulvalene polymer coated electrodes

Cited by 246 publications

References 2 publications

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

Electrolyte Effects on Electrochemical Properties of Osmium Complex Polymer Modified Electrodes

Structural, morphological and spectroelectrochemical characterization of poly (2-ethyl aniline)

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