Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions

Autores
Soria, Federico Ariel; Di Valentin, Cristiana
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In many potential applications, nanoparticles are typically in an aqueous medium. This has strong influence on the stability, optical properties and reactivity, in particular for their functionalization. Therefore, the understanding of the chemistry at the interface between the solvent and the nanoparticle is of utmost importance. In this work, we present a comparative ReaxFF reactive molecular dynamics investigation on spherical TiO2 nanoparticles (NSs) of realistic size, with diameters from 2.2 to 4.4 nm, immersed in a large drop of bulk water. After force field validation for its use for a curved anatase TiO2 surface/water interface, we performed several simulations of the TiO2 nanoparticles of increasing size in a water drop. We found that water can be adsorbed jointly in a molecular and dissociative way on the surface. A Langmuir isotherm indicating an adsorption/desorption mechanism of water on the NS is observed. Regarding the dissociative adsorption, atomistic details reveal two different mechanisms, depending on the water concentration around the NS. At low coverage, the first mechanism involves direct dissociation of a single water molecule, whereas, at higher water coverage, the second mechanism is a proton transfer reaction involving two water molecules, also known as Grotthuss-like mechanism. Thermal annealing simulations show that several water molecules remain on the surface in agreement with the experimental reports. The capacity of adsorption is higher for the 2.2 and 3.0 nm NSs than for the 4.4 nm NS. Finally, a comparative investigation with flat surfaces indicates that NSs present a higher water adsorption capacity (undissociated and dissociated) than flat surfaces, which can be rationalized considering that NSs present many more low-coordinated Ti atoms available for water adsorption. This journal is.
Fil: Soria, Federico Ariel. Universita Di Milano Bicocca; Italia. 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: Di Valentin, Cristiana. Università Di Milano Bicocca; Italia
Materia
TiO2
WATER
REAXFF
REACTIVITY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/172912
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactionsSoria, Federico ArielDi Valentin, CristianaTiO2WATERREAXFFREACTIVITYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In many potential applications, nanoparticles are typically in an aqueous medium. This has strong influence on the stability, optical properties and reactivity, in particular for their functionalization. Therefore, the understanding of the chemistry at the interface between the solvent and the nanoparticle is of utmost importance. In this work, we present a comparative ReaxFF reactive molecular dynamics investigation on spherical TiO2 nanoparticles (NSs) of realistic size, with diameters from 2.2 to 4.4 nm, immersed in a large drop of bulk water. After force field validation for its use for a curved anatase TiO2 surface/water interface, we performed several simulations of the TiO2 nanoparticles of increasing size in a water drop. We found that water can be adsorbed jointly in a molecular and dissociative way on the surface. A Langmuir isotherm indicating an adsorption/desorption mechanism of water on the NS is observed. Regarding the dissociative adsorption, atomistic details reveal two different mechanisms, depending on the water concentration around the NS. At low coverage, the first mechanism involves direct dissociation of a single water molecule, whereas, at higher water coverage, the second mechanism is a proton transfer reaction involving two water molecules, also known as Grotthuss-like mechanism. Thermal annealing simulations show that several water molecules remain on the surface in agreement with the experimental reports. The capacity of adsorption is higher for the 2.2 and 3.0 nm NSs than for the 4.4 nm NS. Finally, a comparative investigation with flat surfaces indicates that NSs present a higher water adsorption capacity (undissociated and dissociated) than flat surfaces, which can be rationalized considering that NSs present many more low-coordinated Ti atoms available for water adsorption. This journal is.Fil: Soria, Federico Ariel. Universita Di Milano Bicocca; Italia. 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: Di Valentin, Cristiana. Università Di Milano Bicocca; ItaliaRoyal Society of Chemistry2021-02info: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/11336/172912Soria, Federico Ariel; Di Valentin, Cristiana; Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions; Royal Society of Chemistry; Nanoscale; 13; 7; 2-2021; 4151-41662040-33642040-3372CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2021/NR/D0NR07503Einfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0NR07503Einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:50:49Zoai:ri.conicet.gov.ar:11336/172912instacron: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 09:50:49.902CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
title Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
spellingShingle Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
Soria, Federico Ariel
TiO2
WATER
REAXFF
REACTIVITY
title_short Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
title_full Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
title_fullStr Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
title_full_unstemmed Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
title_sort Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
dc.creator.none.fl_str_mv Soria, Federico Ariel
Di Valentin, Cristiana
author Soria, Federico Ariel
author_facet Soria, Federico Ariel
Di Valentin, Cristiana
author_role author
author2 Di Valentin, Cristiana
author2_role author
dc.subject.none.fl_str_mv TiO2
WATER
REAXFF
REACTIVITY
topic TiO2
WATER
REAXFF
REACTIVITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In many potential applications, nanoparticles are typically in an aqueous medium. This has strong influence on the stability, optical properties and reactivity, in particular for their functionalization. Therefore, the understanding of the chemistry at the interface between the solvent and the nanoparticle is of utmost importance. In this work, we present a comparative ReaxFF reactive molecular dynamics investigation on spherical TiO2 nanoparticles (NSs) of realistic size, with diameters from 2.2 to 4.4 nm, immersed in a large drop of bulk water. After force field validation for its use for a curved anatase TiO2 surface/water interface, we performed several simulations of the TiO2 nanoparticles of increasing size in a water drop. We found that water can be adsorbed jointly in a molecular and dissociative way on the surface. A Langmuir isotherm indicating an adsorption/desorption mechanism of water on the NS is observed. Regarding the dissociative adsorption, atomistic details reveal two different mechanisms, depending on the water concentration around the NS. At low coverage, the first mechanism involves direct dissociation of a single water molecule, whereas, at higher water coverage, the second mechanism is a proton transfer reaction involving two water molecules, also known as Grotthuss-like mechanism. Thermal annealing simulations show that several water molecules remain on the surface in agreement with the experimental reports. The capacity of adsorption is higher for the 2.2 and 3.0 nm NSs than for the 4.4 nm NS. Finally, a comparative investigation with flat surfaces indicates that NSs present a higher water adsorption capacity (undissociated and dissociated) than flat surfaces, which can be rationalized considering that NSs present many more low-coordinated Ti atoms available for water adsorption. This journal is.
Fil: Soria, Federico Ariel. Universita Di Milano Bicocca; Italia. 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: Di Valentin, Cristiana. Università Di Milano Bicocca; Italia
description In many potential applications, nanoparticles are typically in an aqueous medium. This has strong influence on the stability, optical properties and reactivity, in particular for their functionalization. Therefore, the understanding of the chemistry at the interface between the solvent and the nanoparticle is of utmost importance. In this work, we present a comparative ReaxFF reactive molecular dynamics investigation on spherical TiO2 nanoparticles (NSs) of realistic size, with diameters from 2.2 to 4.4 nm, immersed in a large drop of bulk water. After force field validation for its use for a curved anatase TiO2 surface/water interface, we performed several simulations of the TiO2 nanoparticles of increasing size in a water drop. We found that water can be adsorbed jointly in a molecular and dissociative way on the surface. A Langmuir isotherm indicating an adsorption/desorption mechanism of water on the NS is observed. Regarding the dissociative adsorption, atomistic details reveal two different mechanisms, depending on the water concentration around the NS. At low coverage, the first mechanism involves direct dissociation of a single water molecule, whereas, at higher water coverage, the second mechanism is a proton transfer reaction involving two water molecules, also known as Grotthuss-like mechanism. Thermal annealing simulations show that several water molecules remain on the surface in agreement with the experimental reports. The capacity of adsorption is higher for the 2.2 and 3.0 nm NSs than for the 4.4 nm NS. Finally, a comparative investigation with flat surfaces indicates that NSs present a higher water adsorption capacity (undissociated and dissociated) than flat surfaces, which can be rationalized considering that NSs present many more low-coordinated Ti atoms available for water adsorption. This journal is.
publishDate 2021
dc.date.none.fl_str_mv 2021-02
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/11336/172912
Soria, Federico Ariel; Di Valentin, Cristiana; Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions; Royal Society of Chemistry; Nanoscale; 13; 7; 2-2021; 4151-4166
2040-3364
2040-3372
CONICET Digital
CONICET
url http://hdl.handle.net/11336/172912
identifier_str_mv Soria, Federico Ariel; Di Valentin, Cristiana; Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions; Royal Society of Chemistry; Nanoscale; 13; 7; 2-2021; 4151-4166
2040-3364
2040-3372
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.rsc.org/en/content/articlelanding/2021/NR/D0NR07503E
info:eu-repo/semantics/altIdentifier/doi/10.1039/D0NR07503E
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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