Revisiting the Redox Transitions of Polyaniline. Semiquantitative Interpretation of Electrochemically Induced IR Bands
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Title: | Revisiting the Redox Transitions of Polyaniline. Semiquantitative Interpretation of Electrochemically Induced IR Bands |
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Authors: | Huerta Arráez, Francisco | Quijada Tomás, César | Montilla, Francisco | Morallon, Emilia |
Research Group/s: | Electrocatálisis y Electroquímica de Polímeros |
Center, Department or Service: | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Materiales |
Keywords: | Redox transitions | Polyaniline | Electrochemically | IR bands |
Knowledge Area: | Química Física |
Issue Date: | 12-Aug-2021 |
Publisher: | Elsevier |
Citation: | Journal of Electroanalytical Chemistry. 2021, 897: 115593. https://doi.org/10.1016/j.jelechem.2021.115593 |
Abstract: | The redox transitions of PANI in acidic medium have been monitored by a combination of cyclic voltammetry, in situ conductance and in situ FTIR spectroscopy. The results of the semiquantitative analysis strongly suggest that the classical tetrameric model of PANI does not satisfactorily describe the actual structures of the polymer at different redox states. An octameric model is revisited, with the inclusion of essential resonant structures, to provide an appropriate prediction of the relative IR intensity changes of the aromatic C-C stretching (at around 1520 cm-1) and the quinoid C=C stretching (at around 1590 cm-1) vibrations observed by FTIR, which are difficult to interpret by considering only 4 aniline rings. Particularly, it is found that the emeraldine state is better described as a resonance hybrid of the classical bipolaronic and semiquinoid (polaron lattice) structures, while most of the charge transferred at the onset of the second voltammetric peak comes from the additional oxidation of this hybrid, which becomes unstable in the electrochemical environment producing mineralization to CO2 and release of soluble quinones. |
Sponsor: | This work was financed by the Spanish Ministerio de Ciencia e Innovación (project PID2019-105923RB-I00) and by Generalitat Valenciana (Conselleria de Educación, Investigación, Cultura y Deporte through project PROMETEO/2018/087). |
URI: | http://hdl.handle.net/10045/117231 |
ISSN: | 1572-6657 (Print) | 1873-2569 (Online) |
DOI: | 10.1016/j.jelechem.2021.115593 |
Language: | eng |
Type: | info:eu-repo/semantics/article |
Rights: | © 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). |
Peer Review: | si |
Publisher version: | https://doi.org/10.1016/j.jelechem.2021.115593 |
Appears in Collections: | INV - GEPE - Artículos de Revistas |
Files in This Item:
File | Description | Size | Format | |
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Huerta_etal_2021_JElectroanalChem.pdf | 2,17 MB | Adobe PDF | Open Preview | |
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