Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying

Autores
Carrera, Alvaro Daniel; Cristina, Lucila Josefina; Bengió, Silvina; Cossaro, A.; Verdini, A.; Floreano, L.; Fuhr, Javier Daniel; Gayone, Julio Esteban; Ascolani, Hugo del Lujan
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We find that for adsorbed terephthalic acid (TPA) molecules surface Sn alloying deactivates the Cu(001) surface by decoupling the adsorbed molecules from the substrate. This effect is investigated for the case of the 0.5 ML phase of the Sn/Cu(001) surface alloy by applying fast X-ray photoemission spectroscopy, scanning tunneling microscopy, near-edge Xray absorption fine structure spectroscopy, and density functional theory calculations. The experimental results conclusively show that the deprotonation reaction of the carboxyl groups occurring in the clean Cu(001) is fully inhibited on this Sn/Cu(001) surface alloy, which allows the molecules to form two-dimensional arrays stabilized by [OH···O] hydrogen bonds. The formed arrays exhibit a crystal structure that is practically indistinguishable from that theoretically obtained for unsupported TPA sheets, suggesting an extremely weak molecule/substrate interaction. This is supported by DFT calculations of the adsorption energy landscape of the TPA sheets formed on the Sn/Cu(001) template: the lateral variation of the adsorption energy (corrugation) is estimated to be less than 0.2 eV, with an adsorption energy per molecule in the range 1.6−1.8 eV and a contribution of each double [OH···O] bond of 1 eV. Finally, the performed thermal desorption experiments show that the TPA sheets remain stable on the surface alloy until their desorption. From these experiments, a value of 1.5 eV was determined for the desorption energy barrier, which is consistent with the important contribution of the [OH···O] bonds to the stability of the sheets as theoretically predicted. The results reported in this study suggest that a gradual activation of the interaction between the TPA molecules and the Cu(001) surface will also be obtained for decreasing Sn coverage.
Fil: Carrera, Alvaro Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Bengió, Silvina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Cossaro, A. . Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Verdini, A. . Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Floreano, L.. Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Materia
Surfaces
Alloys
Autoassemblies
Hydrogen bonds
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:11336/11328
Acceder
id CONICETDig_8977b02ce5ddf9027b2cd3101d09a9a7
oai_identifier_str oai:ri.conicet.gov.ar:11336/11328
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn AlloyingCarrera, Alvaro DanielCristina, Lucila JosefinaBengió, SilvinaCossaro, A. Verdini, A. Floreano, L.Fuhr, Javier DanielGayone, Julio EstebanAscolani, Hugo del LujanSurfacesAlloysAutoassembliesHydrogen bondshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We find that for adsorbed terephthalic acid (TPA) molecules surface Sn alloying deactivates the Cu(001) surface by decoupling the adsorbed molecules from the substrate. This effect is investigated for the case of the 0.5 ML phase of the Sn/Cu(001) surface alloy by applying fast X-ray photoemission spectroscopy, scanning tunneling microscopy, near-edge Xray absorption fine structure spectroscopy, and density functional theory calculations. The experimental results conclusively show that the deprotonation reaction of the carboxyl groups occurring in the clean Cu(001) is fully inhibited on this Sn/Cu(001) surface alloy, which allows the molecules to form two-dimensional arrays stabilized by [OH···O] hydrogen bonds. The formed arrays exhibit a crystal structure that is practically indistinguishable from that theoretically obtained for unsupported TPA sheets, suggesting an extremely weak molecule/substrate interaction. This is supported by DFT calculations of the adsorption energy landscape of the TPA sheets formed on the Sn/Cu(001) template: the lateral variation of the adsorption energy (corrugation) is estimated to be less than 0.2 eV, with an adsorption energy per molecule in the range 1.6−1.8 eV and a contribution of each double [OH···O] bond of 1 eV. Finally, the performed thermal desorption experiments show that the TPA sheets remain stable on the surface alloy until their desorption. From these experiments, a value of 1.5 eV was determined for the desorption energy barrier, which is consistent with the important contribution of the [OH···O] bonds to the stability of the sheets as theoretically predicted. The results reported in this study suggest that a gradual activation of the interaction between the TPA molecules and the Cu(001) surface will also be obtained for decreasing Sn coverage.Fil: Carrera, Alvaro Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaFil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaFil: Bengió, Silvina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaFil: Cossaro, A. . Italian National Research Council. Istituto Officina dei Materiali; ItaliaFil: Verdini, A. . Italian National Research Council. Istituto Officina dei Materiali; ItaliaFil: Floreano, L.. Italian National Research Council. Istituto Officina dei Materiali; ItaliaFil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaFil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaFil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); ArgentinaAmerican Chemical Society2013-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/11328Carrera, Alvaro Daniel; Cristina, Lucila Josefina; Bengió, Silvina; Cossaro, A. ; Verdini, A. ; et al.; Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying; American Chemical Society; Journal Of Physical Chemistry C; 117; 8-2013; 1-11932-7447enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp404983ninfo:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1021/jp404983ninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:43:17Zoai:ri.conicet.gov.ar:11336/11328instacron: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 09:43:17.931CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
title Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
spellingShingle Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
Carrera, Alvaro Daniel
Surfaces
Alloys
Autoassemblies
Hydrogen bonds
title_short Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
title_full Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
title_fullStr Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
title_full_unstemmed Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
title_sort Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying
dc.creator.none.fl_str_mv Carrera, Alvaro Daniel
Cristina, Lucila Josefina
Bengió, Silvina
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author Carrera, Alvaro Daniel
author_facet Carrera, Alvaro Daniel
Cristina, Lucila Josefina
Bengió, Silvina
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author_role author
author2 Cristina, Lucila Josefina
Bengió, Silvina
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Surfaces
Alloys
Autoassemblies
Hydrogen bonds
topic Surfaces
Alloys
Autoassemblies
Hydrogen bonds
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We find that for adsorbed terephthalic acid (TPA) molecules surface Sn alloying deactivates the Cu(001) surface by decoupling the adsorbed molecules from the substrate. This effect is investigated for the case of the 0.5 ML phase of the Sn/Cu(001) surface alloy by applying fast X-ray photoemission spectroscopy, scanning tunneling microscopy, near-edge Xray absorption fine structure spectroscopy, and density functional theory calculations. The experimental results conclusively show that the deprotonation reaction of the carboxyl groups occurring in the clean Cu(001) is fully inhibited on this Sn/Cu(001) surface alloy, which allows the molecules to form two-dimensional arrays stabilized by [OH···O] hydrogen bonds. The formed arrays exhibit a crystal structure that is practically indistinguishable from that theoretically obtained for unsupported TPA sheets, suggesting an extremely weak molecule/substrate interaction. This is supported by DFT calculations of the adsorption energy landscape of the TPA sheets formed on the Sn/Cu(001) template: the lateral variation of the adsorption energy (corrugation) is estimated to be less than 0.2 eV, with an adsorption energy per molecule in the range 1.6−1.8 eV and a contribution of each double [OH···O] bond of 1 eV. Finally, the performed thermal desorption experiments show that the TPA sheets remain stable on the surface alloy until their desorption. From these experiments, a value of 1.5 eV was determined for the desorption energy barrier, which is consistent with the important contribution of the [OH···O] bonds to the stability of the sheets as theoretically predicted. The results reported in this study suggest that a gradual activation of the interaction between the TPA molecules and the Cu(001) surface will also be obtained for decreasing Sn coverage.
Fil: Carrera, Alvaro Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Bengió, Silvina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Cossaro, A. . Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Verdini, A. . Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Floreano, L.. Italian National Research Council. Istituto Officina dei Materiali; Italia
Fil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina
description We find that for adsorbed terephthalic acid (TPA) molecules surface Sn alloying deactivates the Cu(001) surface by decoupling the adsorbed molecules from the substrate. This effect is investigated for the case of the 0.5 ML phase of the Sn/Cu(001) surface alloy by applying fast X-ray photoemission spectroscopy, scanning tunneling microscopy, near-edge Xray absorption fine structure spectroscopy, and density functional theory calculations. The experimental results conclusively show that the deprotonation reaction of the carboxyl groups occurring in the clean Cu(001) is fully inhibited on this Sn/Cu(001) surface alloy, which allows the molecules to form two-dimensional arrays stabilized by [OH···O] hydrogen bonds. The formed arrays exhibit a crystal structure that is practically indistinguishable from that theoretically obtained for unsupported TPA sheets, suggesting an extremely weak molecule/substrate interaction. This is supported by DFT calculations of the adsorption energy landscape of the TPA sheets formed on the Sn/Cu(001) template: the lateral variation of the adsorption energy (corrugation) is estimated to be less than 0.2 eV, with an adsorption energy per molecule in the range 1.6−1.8 eV and a contribution of each double [OH···O] bond of 1 eV. Finally, the performed thermal desorption experiments show that the TPA sheets remain stable on the surface alloy until their desorption. From these experiments, a value of 1.5 eV was determined for the desorption energy barrier, which is consistent with the important contribution of the [OH···O] bonds to the stability of the sheets as theoretically predicted. The results reported in this study suggest that a gradual activation of the interaction between the TPA molecules and the Cu(001) surface will also be obtained for decreasing Sn coverage.
publishDate 2013
dc.date.none.fl_str_mv 2013-08
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/11336/11328
Carrera, Alvaro Daniel; Cristina, Lucila Josefina; Bengió, Silvina; Cossaro, A. ; Verdini, A. ; et al.; Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying; American Chemical Society; Journal Of Physical Chemistry C; 117; 8-2013; 1-1
1932-7447
url http://hdl.handle.net/11336/11328
identifier_str_mv Carrera, Alvaro Daniel; Cristina, Lucila Josefina; Bengió, Silvina; Cossaro, A. ; Verdini, A. ; et al.; Controlling Carboxyl Deprotonation on Cu(001) by Surface Sn Alloying; American Chemical Society; Journal Of Physical Chemistry C; 117; 8-2013; 1-1
1932-7447
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/jp404983n
info:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1021/jp404983n
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
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
_version_ 1842268591289794560
score 13.13397

Publicaciones similares