Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation

Autores
Planes, Gabriel Angel; Rodríguez, J. L.; Miras, Maria Cristina; García, G.; Pastor, E.; Barbero, César Alfredo
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO2 are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO2 during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO2 by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed. © the Owner Societies.
Fil: Planes, Gabriel Angel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Rodríguez, J. L.. Universidad de La Laguna; España
Fil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto; Argentina
Fil: García, G.. Universidad de La Laguna; España
Fil: Pastor, E.. Universidad de La Laguna; España
Fil: Barbero, César Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Materia
FTIR
POLYANILINE
DEGRADATION
ELECTROPOLYMERIZATION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/209460
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/209460
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradationPlanes, Gabriel AngelRodríguez, J. L.Miras, Maria CristinaGarcía, G.Pastor, E.Barbero, César AlfredoFTIRPOLYANILINEDEGRADATIONELECTROPOLYMERIZATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO2 are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO2 during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO2 by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed. © the Owner Societies.Fil: Planes, Gabriel Angel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Rodríguez, J. L.. Universidad de La Laguna; EspañaFil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto; ArgentinaFil: García, G.. Universidad de La Laguna; EspañaFil: Pastor, E.. Universidad de La Laguna; EspañaFil: Barbero, César Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaRoyal Society of Chemistry2010-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/mswordapplication/pdfhttp://hdl.handle.net/11336/209460Planes, Gabriel Angel; Rodríguez, J. L.; Miras, Maria Cristina; García, G.; Pastor, E.; et al.; Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 35; 2-2010; 10584-105931463-90760005-9021CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C002920Cinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2010/CP/c002920cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:45:50Zoai:ri.conicet.gov.ar:11336/209460instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:45:51.12CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
title Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
spellingShingle Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
Planes, Gabriel Angel
FTIR
POLYANILINE
DEGRADATION
ELECTROPOLYMERIZATION
title_short Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
title_full Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
title_fullStr Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
title_full_unstemmed Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
title_sort Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation
dc.creator.none.fl_str_mv Planes, Gabriel Angel
Rodríguez, J. L.
Miras, Maria Cristina
García, G.
Pastor, E.
Barbero, César Alfredo
author Planes, Gabriel Angel
author_facet Planes, Gabriel Angel
Rodríguez, J. L.
Miras, Maria Cristina
García, G.
Pastor, E.
Barbero, César Alfredo
author_role author
author2 Rodríguez, J. L.
Miras, Maria Cristina
García, G.
Pastor, E.
Barbero, César Alfredo
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv FTIR
POLYANILINE
DEGRADATION
ELECTROPOLYMERIZATION
topic FTIR
POLYANILINE
DEGRADATION
ELECTROPOLYMERIZATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO2 are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO2 during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO2 by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed. © the Owner Societies.
Fil: Planes, Gabriel Angel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Rodríguez, J. L.. Universidad de La Laguna; España
Fil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto; Argentina
Fil: García, G.. Universidad de La Laguna; España
Fil: Pastor, E.. Universidad de La Laguna; España
Fil: Barbero, César Alfredo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
description Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO2 are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO2 during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO2 by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed. © the Owner Societies.
publishDate 2010
dc.date.none.fl_str_mv 2010-02
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/209460
Planes, Gabriel Angel; Rodríguez, J. L.; Miras, Maria Cristina; García, G.; Pastor, E.; et al.; Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 35; 2-2010; 10584-10593
1463-9076
0005-9021
CONICET Digital
CONICET
url http://hdl.handle.net/11336/209460
identifier_str_mv Planes, Gabriel Angel; Rodríguez, J. L.; Miras, Maria Cristina; García, G.; Pastor, E.; et al.; Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 12; 35; 2-2010; 10584-10593
1463-9076
0005-9021
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C002920C
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2010/CP/c002920c
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/msword
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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