Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations

Autores
Chevallier Boutell, Ignacio José; Monti, Gustavo Alberto; Corti, Horacio Roberto; Olmos Asar, Jimena Anahí; Franzoni, Maria Belen; Acosta, Rodolfo Héctor
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Alkanes, due to their hydrophobicity, are extensively used in NMR experiments as probe molecules for geometric tortuosity measurement of polar mesopores. In this work, ab-initio calculations results show that the interactions between linear and cyclic alkanes with the walls of silica mesopores are non-negligible. The dependence of the adsorption energy with the molecular length and shape is determined. Furthermore, a geometrical model is used to calculate a weighted adsorption energy that takes into account the fraction of molecules that reside close to the pore's wall compared to those in the pore's bulk. A dependence of the weighted energy with the pore diameter is found to correlate with restricted diffusion coefficients determined previously by nuclear magnetic resonance experiments. We conclude that the determination of the system's geometric tortuosity by this methodology is not accurate for pore diameters smaller than ca. 6 nm.
Fil: Chevallier Boutell, Ignacio José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Monti, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Corti, Horacio Roberto. 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: Olmos Asar, Jimena Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Franzoni, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Materia
ALKANES
DFT
NMR
SELF-DIFFUSIVITY
SILICA
TORTUOSITY
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:11336/217178
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/217178
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculationsChevallier Boutell, Ignacio JoséMonti, Gustavo AlbertoCorti, Horacio RobertoOlmos Asar, Jimena AnahíFranzoni, Maria BelenAcosta, Rodolfo HéctorALKANESDFTNMRSELF-DIFFUSIVITYSILICATORTUOSITYhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Alkanes, due to their hydrophobicity, are extensively used in NMR experiments as probe molecules for geometric tortuosity measurement of polar mesopores. In this work, ab-initio calculations results show that the interactions between linear and cyclic alkanes with the walls of silica mesopores are non-negligible. The dependence of the adsorption energy with the molecular length and shape is determined. Furthermore, a geometrical model is used to calculate a weighted adsorption energy that takes into account the fraction of molecules that reside close to the pore's wall compared to those in the pore's bulk. A dependence of the weighted energy with the pore diameter is found to correlate with restricted diffusion coefficients determined previously by nuclear magnetic resonance experiments. We conclude that the determination of the system's geometric tortuosity by this methodology is not accurate for pore diameters smaller than ca. 6 nm.Fil: Chevallier Boutell, Ignacio José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Monti, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Corti, Horacio Roberto. 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: Olmos Asar, Jimena Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Franzoni, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaElsevier Science2021-10info: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/pdfhttp://hdl.handle.net/11336/217178Chevallier Boutell, Ignacio José; Monti, Gustavo Alberto; Corti, Horacio Roberto; Olmos Asar, Jimena Anahí; Franzoni, Maria Belen; et al.; Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations; Elsevier Science; Microporous and Mesoporous Materials; 326; 10-2021; 1-161387-1811CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://doi.org/10.1016/j.micromeso.2021.111315info:eu-repo/semantics/altIdentifier/doi/10.1016/j.micromeso.2021.111315info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:19:47Zoai:ri.conicet.gov.ar:11336/217178instacron: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:34982025-10-22 12:19:47.953CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
title Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
spellingShingle Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
Chevallier Boutell, Ignacio José
ALKANES
DFT
NMR
SELF-DIFFUSIVITY
SILICA
TORTUOSITY
title_short Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
title_full Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
title_fullStr Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
title_full_unstemmed Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
title_sort Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations
dc.creator.none.fl_str_mv Chevallier Boutell, Ignacio José
Monti, Gustavo Alberto
Corti, Horacio Roberto
Olmos Asar, Jimena Anahí
Franzoni, Maria Belen
Acosta, Rodolfo Héctor
author Chevallier Boutell, Ignacio José
author_facet Chevallier Boutell, Ignacio José
Monti, Gustavo Alberto
Corti, Horacio Roberto
Olmos Asar, Jimena Anahí
Franzoni, Maria Belen
Acosta, Rodolfo Héctor
author_role author
author2 Monti, Gustavo Alberto
Corti, Horacio Roberto
Olmos Asar, Jimena Anahí
Franzoni, Maria Belen
Acosta, Rodolfo Héctor
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv ALKANES
DFT
NMR
SELF-DIFFUSIVITY
SILICA
TORTUOSITY
topic ALKANES
DFT
NMR
SELF-DIFFUSIVITY
SILICA
TORTUOSITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Alkanes, due to their hydrophobicity, are extensively used in NMR experiments as probe molecules for geometric tortuosity measurement of polar mesopores. In this work, ab-initio calculations results show that the interactions between linear and cyclic alkanes with the walls of silica mesopores are non-negligible. The dependence of the adsorption energy with the molecular length and shape is determined. Furthermore, a geometrical model is used to calculate a weighted adsorption energy that takes into account the fraction of molecules that reside close to the pore's wall compared to those in the pore's bulk. A dependence of the weighted energy with the pore diameter is found to correlate with restricted diffusion coefficients determined previously by nuclear magnetic resonance experiments. We conclude that the determination of the system's geometric tortuosity by this methodology is not accurate for pore diameters smaller than ca. 6 nm.
Fil: Chevallier Boutell, Ignacio José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Monti, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Corti, Horacio Roberto. 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: Olmos Asar, Jimena Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Franzoni, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
description Alkanes, due to their hydrophobicity, are extensively used in NMR experiments as probe molecules for geometric tortuosity measurement of polar mesopores. In this work, ab-initio calculations results show that the interactions between linear and cyclic alkanes with the walls of silica mesopores are non-negligible. The dependence of the adsorption energy with the molecular length and shape is determined. Furthermore, a geometrical model is used to calculate a weighted adsorption energy that takes into account the fraction of molecules that reside close to the pore's wall compared to those in the pore's bulk. A dependence of the weighted energy with the pore diameter is found to correlate with restricted diffusion coefficients determined previously by nuclear magnetic resonance experiments. We conclude that the determination of the system's geometric tortuosity by this methodology is not accurate for pore diameters smaller than ca. 6 nm.
publishDate 2021
dc.date.none.fl_str_mv 2021-10
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/11336/217178
Chevallier Boutell, Ignacio José; Monti, Gustavo Alberto; Corti, Horacio Roberto; Olmos Asar, Jimena Anahí; Franzoni, Maria Belen; et al.; Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations; Elsevier Science; Microporous and Mesoporous Materials; 326; 10-2021; 1-16
1387-1811
CONICET Digital
CONICET
url http://hdl.handle.net/11336/217178
identifier_str_mv Chevallier Boutell, Ignacio José; Monti, Gustavo Alberto; Corti, Horacio Roberto; Olmos Asar, Jimena Anahí; Franzoni, Maria Belen; et al.; Non-negligible interactions of alkanes with silica mesopores affect self-diffusivity: Insights from first-principles calculations; Elsevier Science; Microporous and Mesoporous Materials; 326; 10-2021; 1-16
1387-1811
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://doi.org/10.1016/j.micromeso.2021.111315
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.micromeso.2021.111315
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
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 12.982451

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