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Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces

Electrochemistry is an old but still flourishing field of research due to the importance of the efficiency and kinetics of electrochemical reactions in industrial processes and (bio-)electrochemical devices. The heterogeneous electron transfer from an electrode to a reactant in the solution has been...

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Autores principales: Wijeratne, Kosala, Ail, Ujwala, Brooke, Robert, Vagin, Mikhail, Liu, Xianjie, Fahlman, Mats, Crispin, Xavier
Formato: Online Artículo Texto
Lenguaje:English
Publicado: National Academy of Sciences 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6255154/
https://www.ncbi.nlm.nih.gov/pubmed/30397110
http://dx.doi.org/10.1073/pnas.1806087115
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author Wijeratne, Kosala
Ail, Ujwala
Brooke, Robert
Vagin, Mikhail
Liu, Xianjie
Fahlman, Mats
Crispin, Xavier
author_facet Wijeratne, Kosala
Ail, Ujwala
Brooke, Robert
Vagin, Mikhail
Liu, Xianjie
Fahlman, Mats
Crispin, Xavier
author_sort Wijeratne, Kosala
collection PubMed
description Electrochemistry is an old but still flourishing field of research due to the importance of the efficiency and kinetics of electrochemical reactions in industrial processes and (bio-)electrochemical devices. The heterogeneous electron transfer from an electrode to a reactant in the solution has been well studied for metal, semiconductor, metal oxide, and carbon electrodes. For those electrode materials, there is little correlation between the electronic transport within the electrode material and the electron transfer occurring at the interface between the electrode and the solution. Here, we investigate the heterogeneous electron transfer between a conducting polymer electrode and a redox couple in an electrolyte. As a benchmark system, we use poly(3,4-ethylenedioxythiophene) (PEDOT) and the Ferro/ferricyanide redox couple in an aqueous electrolyte. We discovered a strong correlation between the electronic transport within the PEDOT electrode and the rate of electron transfer to the organometallic molecules in solution. We attribute this to a percolation-based charge transport within the polymer electrode directly involved in the electron transfer. We show the impact of this finding by optimizing an electrochemical thermogalvanic cell that transforms a heat flux into electrical power. The power generated by the cell increased by four orders of magnitude on changing the morphology and conductivity of the polymer electrode. As all conducting polymers are recognized to have percolation transport, we believe that this is a general phenomenon for this family of conductors.
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spelling pubmed-62551542018-11-30 Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces Wijeratne, Kosala Ail, Ujwala Brooke, Robert Vagin, Mikhail Liu, Xianjie Fahlman, Mats Crispin, Xavier Proc Natl Acad Sci U S A Physical Sciences Electrochemistry is an old but still flourishing field of research due to the importance of the efficiency and kinetics of electrochemical reactions in industrial processes and (bio-)electrochemical devices. The heterogeneous electron transfer from an electrode to a reactant in the solution has been well studied for metal, semiconductor, metal oxide, and carbon electrodes. For those electrode materials, there is little correlation between the electronic transport within the electrode material and the electron transfer occurring at the interface between the electrode and the solution. Here, we investigate the heterogeneous electron transfer between a conducting polymer electrode and a redox couple in an electrolyte. As a benchmark system, we use poly(3,4-ethylenedioxythiophene) (PEDOT) and the Ferro/ferricyanide redox couple in an aqueous electrolyte. We discovered a strong correlation between the electronic transport within the PEDOT electrode and the rate of electron transfer to the organometallic molecules in solution. We attribute this to a percolation-based charge transport within the polymer electrode directly involved in the electron transfer. We show the impact of this finding by optimizing an electrochemical thermogalvanic cell that transforms a heat flux into electrical power. The power generated by the cell increased by four orders of magnitude on changing the morphology and conductivity of the polymer electrode. As all conducting polymers are recognized to have percolation transport, we believe that this is a general phenomenon for this family of conductors. National Academy of Sciences 2018-11-20 2018-11-05 /pmc/articles/PMC6255154/ /pubmed/30397110 http://dx.doi.org/10.1073/pnas.1806087115 Text en Copyright © 2018 the Author(s). Published by PNAS. https://creativecommons.org/licenses/by-nc-nd/4.0/ This open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND) (https://creativecommons.org/licenses/by-nc-nd/4.0/) .
spellingShingle Physical Sciences
Wijeratne, Kosala
Ail, Ujwala
Brooke, Robert
Vagin, Mikhail
Liu, Xianjie
Fahlman, Mats
Crispin, Xavier
Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title_full Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title_fullStr Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title_full_unstemmed Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title_short Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
title_sort bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces
topic Physical Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6255154/
https://www.ncbi.nlm.nih.gov/pubmed/30397110
http://dx.doi.org/10.1073/pnas.1806087115
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