Confined Polar Mixtures within Cylindrical Nanocavities

Autores
Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel Hector
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Using molecular dynamics experiments, we have extended our previous analysis of equimolar mixtures of water and acetonitrile confined between silica walls [J. Phys. Chem. B 2009, 113, 12744] to examine similar solutions trapped within carbon nanotubes and cylindrical silica pores. Two different carbon tube sizes were investigated, (8,8) tubes, with radius Rcnt ) 0.55 nm, and (16,16) ones, with Rcnt ) 1.1 nm. In the narrowest tubes, we found that the cylindrical cavity is filled exclusively by acetonitrile; as the radius of the tube reaches 1 nm, water begins to get incorporated within the inner cavities. In (16,16) tubes, the analysis of global andlocal concentration fluctuations shows a net increment of the global acetonitrile concentration; in addition, the aprotic solvent is also the prevailing species at the vicinity of the tube walls. Mixtures confined within silica nanopores of radius ∼1.5 nm were also investigated. Three pores, differing in the effective wall/solvent interactions, were analyzed, (i) a first class, in which dispersive forces prevail (hydrophobic cavities), (ii) a second type, where oxygen sites at the pore walls are transformed into polar silanol groups (hydrophilic cavities), and (iii) finally, an intermediate scenario, in which 60% of the OH groups are replaced by mobile trimethylsilyl groups. Within the different pores, we found clear distinctions between the solvent layers that lie in close contact with the silica substrate and those with more central locations. Dynamical modes of the confined liquid phases were investigated in terms of diffusive and rotational time correlation functions.Compared to bulk results, the characteristic time scales describing different solvent motions exhibit significant increments. In carbon nanotubes, the most prominent modifications operate in the narrower tubes, where translations and rotations become severely hindered. In silica nanopores, the manifestations of the overall retardations are more dramatic for solvent species lying at the vicinity of trimethylsilyl groups.
Fil: Rodriguez, Javier. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Dolores Elola, M.. Comisión Nacional de Energía Atómica; Argentina
Fil: Laria, Daniel Hector. 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
Materia
Dinamica Molecular
Confinamiento
Nanocavidades
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:11336/236651

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spelling Confined Polar Mixtures within Cylindrical NanocavitiesRodriguez, JavierDolores Elola, M.Laria, Daniel HectorDinamica MolecularConfinamientoNanocavidadeshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Using molecular dynamics experiments, we have extended our previous analysis of equimolar mixtures of water and acetonitrile confined between silica walls [J. Phys. Chem. B 2009, 113, 12744] to examine similar solutions trapped within carbon nanotubes and cylindrical silica pores. Two different carbon tube sizes were investigated, (8,8) tubes, with radius Rcnt ) 0.55 nm, and (16,16) ones, with Rcnt ) 1.1 nm. In the narrowest tubes, we found that the cylindrical cavity is filled exclusively by acetonitrile; as the radius of the tube reaches 1 nm, water begins to get incorporated within the inner cavities. In (16,16) tubes, the analysis of global andlocal concentration fluctuations shows a net increment of the global acetonitrile concentration; in addition, the aprotic solvent is also the prevailing species at the vicinity of the tube walls. Mixtures confined within silica nanopores of radius ∼1.5 nm were also investigated. Three pores, differing in the effective wall/solvent interactions, were analyzed, (i) a first class, in which dispersive forces prevail (hydrophobic cavities), (ii) a second type, where oxygen sites at the pore walls are transformed into polar silanol groups (hydrophilic cavities), and (iii) finally, an intermediate scenario, in which 60% of the OH groups are replaced by mobile trimethylsilyl groups. Within the different pores, we found clear distinctions between the solvent layers that lie in close contact with the silica substrate and those with more central locations. Dynamical modes of the confined liquid phases were investigated in terms of diffusive and rotational time correlation functions.Compared to bulk results, the characteristic time scales describing different solvent motions exhibit significant increments. In carbon nanotubes, the most prominent modifications operate in the narrower tubes, where translations and rotations become severely hindered. In silica nanopores, the manifestations of the overall retardations are more dramatic for solvent species lying at the vicinity of trimethylsilyl groups.Fil: Rodriguez, Javier. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Dolores Elola, M.. Comisión Nacional de Energía Atómica; ArgentinaFil: Laria, Daniel Hector. 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; ArgentinaAmerican Chemical Society2010-06info: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/11336/236651Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel Hector; Confined Polar Mixtures within Cylindrical Nanocavities; American Chemical Society; Journal of Physical Chemistry B; 114; 23; 6-2010; 7900-79081520-6106CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp101836binfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp101836binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:48Zoai:ri.conicet.gov.ar:11336/236651instacron: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 09:47:48.731CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Confined Polar Mixtures within Cylindrical Nanocavities
title Confined Polar Mixtures within Cylindrical Nanocavities
spellingShingle Confined Polar Mixtures within Cylindrical Nanocavities
Rodriguez, Javier
Dinamica Molecular
Confinamiento
Nanocavidades
title_short Confined Polar Mixtures within Cylindrical Nanocavities
title_full Confined Polar Mixtures within Cylindrical Nanocavities
title_fullStr Confined Polar Mixtures within Cylindrical Nanocavities
title_full_unstemmed Confined Polar Mixtures within Cylindrical Nanocavities
title_sort Confined Polar Mixtures within Cylindrical Nanocavities
dc.creator.none.fl_str_mv Rodriguez, Javier
Dolores Elola, M.
Laria, Daniel Hector
author Rodriguez, Javier
author_facet Rodriguez, Javier
Dolores Elola, M.
Laria, Daniel Hector
author_role author
author2 Dolores Elola, M.
Laria, Daniel Hector
author2_role author
author
dc.subject.none.fl_str_mv Dinamica Molecular
Confinamiento
Nanocavidades
topic Dinamica Molecular
Confinamiento
Nanocavidades
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Using molecular dynamics experiments, we have extended our previous analysis of equimolar mixtures of water and acetonitrile confined between silica walls [J. Phys. Chem. B 2009, 113, 12744] to examine similar solutions trapped within carbon nanotubes and cylindrical silica pores. Two different carbon tube sizes were investigated, (8,8) tubes, with radius Rcnt ) 0.55 nm, and (16,16) ones, with Rcnt ) 1.1 nm. In the narrowest tubes, we found that the cylindrical cavity is filled exclusively by acetonitrile; as the radius of the tube reaches 1 nm, water begins to get incorporated within the inner cavities. In (16,16) tubes, the analysis of global andlocal concentration fluctuations shows a net increment of the global acetonitrile concentration; in addition, the aprotic solvent is also the prevailing species at the vicinity of the tube walls. Mixtures confined within silica nanopores of radius ∼1.5 nm were also investigated. Three pores, differing in the effective wall/solvent interactions, were analyzed, (i) a first class, in which dispersive forces prevail (hydrophobic cavities), (ii) a second type, where oxygen sites at the pore walls are transformed into polar silanol groups (hydrophilic cavities), and (iii) finally, an intermediate scenario, in which 60% of the OH groups are replaced by mobile trimethylsilyl groups. Within the different pores, we found clear distinctions between the solvent layers that lie in close contact with the silica substrate and those with more central locations. Dynamical modes of the confined liquid phases were investigated in terms of diffusive and rotational time correlation functions.Compared to bulk results, the characteristic time scales describing different solvent motions exhibit significant increments. In carbon nanotubes, the most prominent modifications operate in the narrower tubes, where translations and rotations become severely hindered. In silica nanopores, the manifestations of the overall retardations are more dramatic for solvent species lying at the vicinity of trimethylsilyl groups.
Fil: Rodriguez, Javier. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Dolores Elola, M.. Comisión Nacional de Energía Atómica; Argentina
Fil: Laria, Daniel Hector. 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 Using molecular dynamics experiments, we have extended our previous analysis of equimolar mixtures of water and acetonitrile confined between silica walls [J. Phys. Chem. B 2009, 113, 12744] to examine similar solutions trapped within carbon nanotubes and cylindrical silica pores. Two different carbon tube sizes were investigated, (8,8) tubes, with radius Rcnt ) 0.55 nm, and (16,16) ones, with Rcnt ) 1.1 nm. In the narrowest tubes, we found that the cylindrical cavity is filled exclusively by acetonitrile; as the radius of the tube reaches 1 nm, water begins to get incorporated within the inner cavities. In (16,16) tubes, the analysis of global andlocal concentration fluctuations shows a net increment of the global acetonitrile concentration; in addition, the aprotic solvent is also the prevailing species at the vicinity of the tube walls. Mixtures confined within silica nanopores of radius ∼1.5 nm were also investigated. Three pores, differing in the effective wall/solvent interactions, were analyzed, (i) a first class, in which dispersive forces prevail (hydrophobic cavities), (ii) a second type, where oxygen sites at the pore walls are transformed into polar silanol groups (hydrophilic cavities), and (iii) finally, an intermediate scenario, in which 60% of the OH groups are replaced by mobile trimethylsilyl groups. Within the different pores, we found clear distinctions between the solvent layers that lie in close contact with the silica substrate and those with more central locations. Dynamical modes of the confined liquid phases were investigated in terms of diffusive and rotational time correlation functions.Compared to bulk results, the characteristic time scales describing different solvent motions exhibit significant increments. In carbon nanotubes, the most prominent modifications operate in the narrower tubes, where translations and rotations become severely hindered. In silica nanopores, the manifestations of the overall retardations are more dramatic for solvent species lying at the vicinity of trimethylsilyl groups.
publishDate 2010
dc.date.none.fl_str_mv 2010-06
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/11336/236651
Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel Hector; Confined Polar Mixtures within Cylindrical Nanocavities; American Chemical Society; Journal of Physical Chemistry B; 114; 23; 6-2010; 7900-7908
1520-6106
CONICET Digital
CONICET
url http://hdl.handle.net/11336/236651
identifier_str_mv Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel Hector; Confined Polar Mixtures within Cylindrical Nanocavities; American Chemical Society; Journal of Physical Chemistry B; 114; 23; 6-2010; 7900-7908
1520-6106
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://pubs.acs.org/doi/10.1021/jp101836b
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp101836b
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 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)
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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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