Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers

Autores
Tagliazucchi, Mario Eugenio; Calvo, Ernesto Julio
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of surface charge on the electron transfer and charge propagation in layer by layer (LbL) electrostatically self-assembled redox poly-electrolyte multilayers (PEMs) has been studied. Thin films comprised of sequential layers of cationic poly(allylamine) covalently modified by osmium bipyridyl pyridine complexes (PAH-Os) and anionic poly(vinylsulfonate) (PVS) have been studied using electro-chemical impedance spectroscopy (EIS) and ellipsometry. For positively charged topmost layers a transition from low frequency redox pseudocapacitance to diffusion due to electron hopping between adjacent redox sites has been observed. This behavior could be modelled by a bound-diffusion modified Randles electrical equivalent circuit. Negatively charged surfaces terminated in PVS, on the other hand, presented a kinetic hindrance for the osmium redox switching process. This may be ascribed to a limitation in the flux of mobile anions compensating charge due to a skin Donnan potential at the film/electrolyte interface or effects on the local electrostatic environment of the osmium sites. Further adsorption of polycations or charge screening by increasing the electrolyte ionic strength restores the redox charge seen when the polycation was the topmost layer. 
Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Calvo, Ernesto Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
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:11336/103855
Acceder
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spelling Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayersTagliazucchi, Mario EugenioCalvo, Ernesto Juliohttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The effect of surface charge on the electron transfer and charge propagation in layer by layer (LbL) electrostatically self-assembled redox poly-electrolyte multilayers (PEMs) has been studied. Thin films comprised of sequential layers of cationic poly(allylamine) covalently modified by osmium bipyridyl pyridine complexes (PAH-Os) and anionic poly(vinylsulfonate) (PVS) have been studied using electro-chemical impedance spectroscopy (EIS) and ellipsometry. For positively charged topmost layers a transition from low frequency redox pseudocapacitance to diffusion due to electron hopping between adjacent redox sites has been observed. This behavior could be modelled by a bound-diffusion modified Randles electrical equivalent circuit. Negatively charged surfaces terminated in PVS, on the other hand, presented a kinetic hindrance for the osmium redox switching process. This may be ascribed to a limitation in the flux of mobile anions compensating charge due to a skin Donnan potential at the film/electrolyte interface or effects on the local electrostatic environment of the osmium sites. Further adsorption of polycations or charge screening by increasing the electrolyte ionic strength restores the redox charge seen when the polycation was the topmost layer. Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Calvo, Ernesto Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaElsevier Science Sa2007-01-15info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/103855Tagliazucchi, Mario Eugenio; Calvo, Ernesto Julio; Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 599; 2; 15-1-2007; 249-2591572-6657CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022072806001434info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2006.03.014info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:06:53Zoai:ri.conicet.gov.ar:11336/103855instacron: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:34982025-09-03 10:06:53.7CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
title Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
spellingShingle Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
Tagliazucchi, Mario Eugenio
title_short Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
title_full Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
title_fullStr Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
title_full_unstemmed Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
title_sort Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers
dc.creator.none.fl_str_mv Tagliazucchi, Mario Eugenio
Calvo, Ernesto Julio
author Tagliazucchi, Mario Eugenio
author_facet Tagliazucchi, Mario Eugenio
Calvo, Ernesto Julio
author_role author
author2 Calvo, Ernesto Julio
author2_role author
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The effect of surface charge on the electron transfer and charge propagation in layer by layer (LbL) electrostatically self-assembled redox poly-electrolyte multilayers (PEMs) has been studied. Thin films comprised of sequential layers of cationic poly(allylamine) covalently modified by osmium bipyridyl pyridine complexes (PAH-Os) and anionic poly(vinylsulfonate) (PVS) have been studied using electro-chemical impedance spectroscopy (EIS) and ellipsometry. For positively charged topmost layers a transition from low frequency redox pseudocapacitance to diffusion due to electron hopping between adjacent redox sites has been observed. This behavior could be modelled by a bound-diffusion modified Randles electrical equivalent circuit. Negatively charged surfaces terminated in PVS, on the other hand, presented a kinetic hindrance for the osmium redox switching process. This may be ascribed to a limitation in the flux of mobile anions compensating charge due to a skin Donnan potential at the film/electrolyte interface or effects on the local electrostatic environment of the osmium sites. Further adsorption of polycations or charge screening by increasing the electrolyte ionic strength restores the redox charge seen when the polycation was the topmost layer. 
Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Calvo, Ernesto Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description The effect of surface charge on the electron transfer and charge propagation in layer by layer (LbL) electrostatically self-assembled redox poly-electrolyte multilayers (PEMs) has been studied. Thin films comprised of sequential layers of cationic poly(allylamine) covalently modified by osmium bipyridyl pyridine complexes (PAH-Os) and anionic poly(vinylsulfonate) (PVS) have been studied using electro-chemical impedance spectroscopy (EIS) and ellipsometry. For positively charged topmost layers a transition from low frequency redox pseudocapacitance to diffusion due to electron hopping between adjacent redox sites has been observed. This behavior could be modelled by a bound-diffusion modified Randles electrical equivalent circuit. Negatively charged surfaces terminated in PVS, on the other hand, presented a kinetic hindrance for the osmium redox switching process. This may be ascribed to a limitation in the flux of mobile anions compensating charge due to a skin Donnan potential at the film/electrolyte interface or effects on the local electrostatic environment of the osmium sites. Further adsorption of polycations or charge screening by increasing the electrolyte ionic strength restores the redox charge seen when the polycation was the topmost layer. 
publishDate 2007
dc.date.none.fl_str_mv 2007-01-15
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/11336/103855
Tagliazucchi, Mario Eugenio; Calvo, Ernesto Julio; Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 599; 2; 15-1-2007; 249-259
1572-6657
CONICET Digital
CONICET
url http://hdl.handle.net/11336/103855
identifier_str_mv Tagliazucchi, Mario Eugenio; Calvo, Ernesto Julio; Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 599; 2; 15-1-2007; 249-259
1572-6657
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022072806001434
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2006.03.014
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/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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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score 13.13397

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