Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance

Time dependence of the electrochemical impedance of an overoxidized glassy carbon|poly(3,4-ethylenedioxytiophene) (PEDOT)|0.1 mol·dm-3 sulfuric acid (aq.) elec­trode has been investigated. To follow the changes occurring at the film/substrate interface after the overoxidation procedure, successive i...

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Main Authors: Dora Zalka, Soma Vesztergom, Mária Ujvári, Gyözö G. Láng
Format: Article
Language:English
Published: International Association of Physical Chemists (IAPC) 2018-05-01
Series:Journal of Electrochemical Science and Engineering
Subjects:
Online Access:http://pub.iapchem.org/ojs/index.php/JESE/article/view/508
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author Dora Zalka
Soma Vesztergom
Mária Ujvári
Gyözö G. Láng
author_facet Dora Zalka
Soma Vesztergom
Mária Ujvári
Gyözö G. Láng
author_sort Dora Zalka
collection DOAJ
description Time dependence of the electrochemical impedance of an overoxidized glassy carbon|poly(3,4-ethylenedioxytiophene) (PEDOT)|0.1 mol·dm-3 sulfuric acid (aq.) elec­trode has been investigated. To follow the changes occurring at the film/substrate interface after the overoxidation procedure, successive impedance measurements were carried out. Although the system is intrinsically nonstationary, the charge transfer resis­tance (Rct) cor­res­ponding to different time instants could be determined by using the so-called 4-dimensional analysis method. The same post-experimental mathematic­cal/ana­lytical procedure could be used also for the estimation of the charge transfer resistance corresponding to the time instant just after overoxidation of the PEDOT film. The increase of the charge transfer resistance of the overoxidized system with respect to that of the pristine electrode suggests that during overoxidation the electrochemical activity of the film decreases and the charge transfer process at the metal/film interface beco­mes more hindered. After the overoxidation procedure, when the electrode potential was held in the “stability region” (at E = 0.4 V vs. SSCE in the present case) the Rct decre­ased continuously with experiment time to a value somewhat higher than that of the pristine electrode. By comparing the properties of the GC|PEDOT|0.1 M H2SO4 and the Au|PEDOT|0.1 M H2SO4 electrodes a possible mechanistic explanation for the observed behavior has been proposed. This is based on the assumption that in the case of the GC|PEDOT|0.1 M H2SO4 electrode two processes may occur simultaneously during the impedance measurements: (a) reduction of the oxidized surface of the GC substrate, including the reduction of the oxygen-containing surface functionalities and (b) read­sorption of the polymer chains (polymer chain ends) on the surface.
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spelling doaj.art-dcc73b3cebc54b079ade13108d56249d2022-12-22T00:37:26ZengInternational Association of Physical Chemists (IAPC)Journal of Electrochemical Science and Engineering1847-92862018-05-018210.5599/jese.508306Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistanceDora Zalka0Soma Vesztergom1Mária Ujvári2Gyözö G. Láng3Institute of Chemistry, Laboratory of Electrochemistry and Electroanalytical Chemistry, Eötvös Loránd University, Pázmány P. s. 1/A, H-1117 BudapestInstitute of Chemistry, Laboratory of Electrochemistry and Electroanalytical Chemistry, Eötvös Loránd University, Pázmány P. s. 1/A, H-1117 BudapestInstitute of Chemistry, Laboratory of Electrochemistry and Electroanalytical Chemistry, Eötvös Loránd University, Pázmány P. s. 1/A, H-1117 BudapestInstitute of Chemistry, Laboratory of Electrochemistry and Electroanalytical Chemistry, Eötvös Loránd University, Pázmány P. s. 1/A, H-1117 BudapestTime dependence of the electrochemical impedance of an overoxidized glassy carbon|poly(3,4-ethylenedioxytiophene) (PEDOT)|0.1 mol·dm-3 sulfuric acid (aq.) elec­trode has been investigated. To follow the changes occurring at the film/substrate interface after the overoxidation procedure, successive impedance measurements were carried out. Although the system is intrinsically nonstationary, the charge transfer resis­tance (Rct) cor­res­ponding to different time instants could be determined by using the so-called 4-dimensional analysis method. The same post-experimental mathematic­cal/ana­lytical procedure could be used also for the estimation of the charge transfer resistance corresponding to the time instant just after overoxidation of the PEDOT film. The increase of the charge transfer resistance of the overoxidized system with respect to that of the pristine electrode suggests that during overoxidation the electrochemical activity of the film decreases and the charge transfer process at the metal/film interface beco­mes more hindered. After the overoxidation procedure, when the electrode potential was held in the “stability region” (at E = 0.4 V vs. SSCE in the present case) the Rct decre­ased continuously with experiment time to a value somewhat higher than that of the pristine electrode. By comparing the properties of the GC|PEDOT|0.1 M H2SO4 and the Au|PEDOT|0.1 M H2SO4 electrodes a possible mechanistic explanation for the observed behavior has been proposed. This is based on the assumption that in the case of the GC|PEDOT|0.1 M H2SO4 electrode two processes may occur simultaneously during the impedance measurements: (a) reduction of the oxidized surface of the GC substrate, including the reduction of the oxygen-containing surface functionalities and (b) read­sorption of the polymer chains (polymer chain ends) on the surface.http://pub.iapchem.org/ojs/index.php/JESE/article/view/508Non-stationary system4-dimensional analysis methodsubstrate-polymer interactionoxidation of glassy carbon
spellingShingle Dora Zalka
Soma Vesztergom
Mária Ujvári
Gyözö G. Láng
Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
Journal of Electrochemical Science and Engineering
Non-stationary system
4-dimensional analysis method
substrate-polymer interaction
oxidation of glassy carbon
title Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
title_full Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
title_fullStr Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
title_full_unstemmed Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
title_short Electrochemical behaviour of poly(3,4-ethylenedioxytiophene) modified glassy carbon electrodes after overoxidation − the influence of the substrate on the charge transfer resistance
title_sort electrochemical behaviour of poly 3 4 ethylenedioxytiophene modified glassy carbon electrodes after overoxidation the influence of the substrate on the charge transfer resistance
topic Non-stationary system
4-dimensional analysis method
substrate-polymer interaction
oxidation of glassy carbon
url http://pub.iapchem.org/ojs/index.php/JESE/article/view/508
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