Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers

Autores
Floridia Addato, María Alejandra; Rubert, Aldo Alberto; Benitez, Guillermo Alfredo; Fonticelli, Mariano Hernan; Carrasco, Javier; Carro, Pilar; Salvarezza, Roberto Carlos
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The adsorption of butanethiol (BT), hexanethiol (HT), and dodecanethiol (DT) on Pt from ethanolic solutions has been studied by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. XPS data show two main S 2p components at 162.3 and 163.4 eV. The barrier properties estimated by double-layer capacitance and the blockage of the electron transfer from a redox couple in solution are markedly improved for self-assembled monolayers (SAMs) of the longer DT molecule. While the behavior of DT monolayers on Pt is comparable to that found for those grown on Au, HT and BT SAMs on Pt are more defective, are less blocking, and have a slightly lower thiolate coverage than their Au counterparts. The chain length dependent quality of these SAMs is explained based on DFT and thermodynamics calculations. It is demonstrated that a lying down (LD) surface structure dominates the stability diagram for the shorter chain thiols, while the standing up (SU) phase is more important for DT. We propose that the poor quality observed for SAMs of short chain thiolates results from an easier C?S bond scission of the thioalkyl radical in a LD configuration.
Fil: Floridia Addato, María Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Rubert, Aldo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Benitez, Guillermo Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Carrasco, Javier. Consejo Superior de Investigaciones Científicas; España
Fil: Carro, Pilar. Universidad de La Laguna; España
Fil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
ALKANETHIOLS
PLATINUM
ELECTROCHEMISTRY
DFT
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:11336/278645
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/278645
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled MonolayersFloridia Addato, María AlejandraRubert, Aldo AlbertoBenitez, Guillermo AlfredoFonticelli, Mariano HernanCarrasco, JavierCarro, PilarSalvarezza, Roberto CarlosALKANETHIOLSPLATINUMELECTROCHEMISTRYDFThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The adsorption of butanethiol (BT), hexanethiol (HT), and dodecanethiol (DT) on Pt from ethanolic solutions has been studied by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. XPS data show two main S 2p components at 162.3 and 163.4 eV. The barrier properties estimated by double-layer capacitance and the blockage of the electron transfer from a redox couple in solution are markedly improved for self-assembled monolayers (SAMs) of the longer DT molecule. While the behavior of DT monolayers on Pt is comparable to that found for those grown on Au, HT and BT SAMs on Pt are more defective, are less blocking, and have a slightly lower thiolate coverage than their Au counterparts. The chain length dependent quality of these SAMs is explained based on DFT and thermodynamics calculations. It is demonstrated that a lying down (LD) surface structure dominates the stability diagram for the shorter chain thiols, while the standing up (SU) phase is more important for DT. We propose that the poor quality observed for SAMs of short chain thiolates results from an easier C?S bond scission of the thioalkyl radical in a LD configuration.Fil: Floridia Addato, María Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Rubert, Aldo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Benitez, Guillermo Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Carrasco, Javier. Consejo Superior de Investigaciones Científicas; EspañaFil: Carro, Pilar. Universidad de La Laguna; EspañaFil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaAmerican Chemical Society2011-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/278645Floridia Addato, María Alejandra; Rubert, Aldo Alberto; Benitez, Guillermo Alfredo; Fonticelli, Mariano Hernan; Carrasco, Javier; et al.; Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers; American Chemical Society; Journal of Physical Chemistry C; 115; 36; 8-2011; 17788-177981932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp201390minfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp201390minfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-01-14T11:45:07Zoai:ri.conicet.gov.ar:11336/278645instacron: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:34982026-01-14 11:45:07.908CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
title Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
spellingShingle Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
Floridia Addato, María Alejandra
ALKANETHIOLS
PLATINUM
ELECTROCHEMISTRY
DFT
title_short Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
title_full Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
title_fullStr Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
title_full_unstemmed Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
title_sort Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers
dc.creator.none.fl_str_mv Floridia Addato, María Alejandra
Rubert, Aldo Alberto
Benitez, Guillermo Alfredo
Fonticelli, Mariano Hernan
Carrasco, Javier
Carro, Pilar
Salvarezza, Roberto Carlos
author Floridia Addato, María Alejandra
author_facet Floridia Addato, María Alejandra
Rubert, Aldo Alberto
Benitez, Guillermo Alfredo
Fonticelli, Mariano Hernan
Carrasco, Javier
Carro, Pilar
Salvarezza, Roberto Carlos
author_role author
author2 Rubert, Aldo Alberto
Benitez, Guillermo Alfredo
Fonticelli, Mariano Hernan
Carrasco, Javier
Carro, Pilar
Salvarezza, Roberto Carlos
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv ALKANETHIOLS
PLATINUM
ELECTROCHEMISTRY
DFT
topic ALKANETHIOLS
PLATINUM
ELECTROCHEMISTRY
DFT
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 adsorption of butanethiol (BT), hexanethiol (HT), and dodecanethiol (DT) on Pt from ethanolic solutions has been studied by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. XPS data show two main S 2p components at 162.3 and 163.4 eV. The barrier properties estimated by double-layer capacitance and the blockage of the electron transfer from a redox couple in solution are markedly improved for self-assembled monolayers (SAMs) of the longer DT molecule. While the behavior of DT monolayers on Pt is comparable to that found for those grown on Au, HT and BT SAMs on Pt are more defective, are less blocking, and have a slightly lower thiolate coverage than their Au counterparts. The chain length dependent quality of these SAMs is explained based on DFT and thermodynamics calculations. It is demonstrated that a lying down (LD) surface structure dominates the stability diagram for the shorter chain thiols, while the standing up (SU) phase is more important for DT. We propose that the poor quality observed for SAMs of short chain thiolates results from an easier C?S bond scission of the thioalkyl radical in a LD configuration.
Fil: Floridia Addato, María Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Rubert, Aldo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Benitez, Guillermo Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Carrasco, Javier. Consejo Superior de Investigaciones Científicas; España
Fil: Carro, Pilar. Universidad de La Laguna; España
Fil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description The adsorption of butanethiol (BT), hexanethiol (HT), and dodecanethiol (DT) on Pt from ethanolic solutions has been studied by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. XPS data show two main S 2p components at 162.3 and 163.4 eV. The barrier properties estimated by double-layer capacitance and the blockage of the electron transfer from a redox couple in solution are markedly improved for self-assembled monolayers (SAMs) of the longer DT molecule. While the behavior of DT monolayers on Pt is comparable to that found for those grown on Au, HT and BT SAMs on Pt are more defective, are less blocking, and have a slightly lower thiolate coverage than their Au counterparts. The chain length dependent quality of these SAMs is explained based on DFT and thermodynamics calculations. It is demonstrated that a lying down (LD) surface structure dominates the stability diagram for the shorter chain thiols, while the standing up (SU) phase is more important for DT. We propose that the poor quality observed for SAMs of short chain thiolates results from an easier C?S bond scission of the thioalkyl radical in a LD configuration.
publishDate 2011
dc.date.none.fl_str_mv 2011-08
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/11336/278645
Floridia Addato, María Alejandra; Rubert, Aldo Alberto; Benitez, Guillermo Alfredo; Fonticelli, Mariano Hernan; Carrasco, Javier; et al.; Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers; American Chemical Society; Journal of Physical Chemistry C; 115; 36; 8-2011; 17788-17798
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/278645
identifier_str_mv Floridia Addato, María Alejandra; Rubert, Aldo Alberto; Benitez, Guillermo Alfredo; Fonticelli, Mariano Hernan; Carrasco, Javier; et al.; Alkanethiol Adsorption on Platinum: Chain Length Effects on the Quality of Self-Assembled Monolayers; American Chemical Society; Journal of Physical Chemistry C; 115; 36; 8-2011; 17788-17798
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp201390m
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp201390m
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
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.113929

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