Quantum chemical study on surface complex structures of phosphate on gibbsite

Autores
Luengo, Carina Vanesa; Castellani, Norberto Jorge; Ferullo, Ricardo
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Quantum mechanics calculations based on the density functional theory (DFT) were used to identify phosphate surface complexes on gibbsite at low and high pH. The different phosphate species were represented using the Al6(OH)18(H2O)6 cluster model considering four different geometries: monodentate mononuclear (Pmm), monodentate binuclear (Pmb), bidentate mononuclear (Pbm) and bidentate binuclear (Pbb). The corresponding adsorption reactions were modelled via ligand exchange between phosphate species and surface functional groups (hydroxyls and protonated hydroxyls at high and low pH, respectively). The theoretical results indicate that phosphate surface complexes are thermodynamically more favored at acid pH, in agreement with experimental evidences. The first step in these reactions, i.e., the generation of required aluminum vacant sites, was predicted to be particularly favorable when singly coordinated aquo groups are released. Stretching and bending vibrational frequencies associated with the different surface structures were calculated at both pH conditions. The corresponding values at low pH were found to be shifted to higher frequencies with respect to those ones at high pH. ATR-FTIR studies were also carried out. The resulting spectra are dominated by a strong band within the 800?840 cm-1 interval due to P?OH stretching modes. The corresponding peak appearing around 820 cm_1 at high pH is shifted to lower frequencies with respect to the position at low pH, a tendency well predicted by DFT calculations.
Fil: Luengo, Carina Vanesa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina. Universidad Nacional del Sur; Argentina
Materia
Gibbsite
Phosphate
Dft
Adsorption
Atr-Ftir
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/4658
Acceder
id CONICETDig_893ef09e02ae17d311314db25a1acef9
oai_identifier_str oai:ri.conicet.gov.ar:11336/4658
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Quantum chemical study on surface complex structures of phosphate on gibbsiteLuengo, Carina VanesaCastellani, Norberto JorgeFerullo, RicardoGibbsitePhosphateDftAdsorptionAtr-Ftirhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Quantum mechanics calculations based on the density functional theory (DFT) were used to identify phosphate surface complexes on gibbsite at low and high pH. The different phosphate species were represented using the Al6(OH)18(H2O)6 cluster model considering four different geometries: monodentate mononuclear (Pmm), monodentate binuclear (Pmb), bidentate mononuclear (Pbm) and bidentate binuclear (Pbb). The corresponding adsorption reactions were modelled via ligand exchange between phosphate species and surface functional groups (hydroxyls and protonated hydroxyls at high and low pH, respectively). The theoretical results indicate that phosphate surface complexes are thermodynamically more favored at acid pH, in agreement with experimental evidences. The first step in these reactions, i.e., the generation of required aluminum vacant sites, was predicted to be particularly favorable when singly coordinated aquo groups are released. Stretching and bending vibrational frequencies associated with the different surface structures were calculated at both pH conditions. The corresponding values at low pH were found to be shifted to higher frequencies with respect to those ones at high pH. ATR-FTIR studies were also carried out. The resulting spectra are dominated by a strong band within the 800?840 cm-1 interval due to P?OH stretching modes. The corresponding peak appearing around 820 cm_1 at high pH is shifted to lower frequencies with respect to the position at low pH, a tendency well predicted by DFT calculations.Fil: Luengo, Carina Vanesa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina. Universidad Nacional del Sur; ArgentinaElsevier2015-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/4658Luengo, Carina Vanesa; Castellani, Norberto Jorge; Ferullo, Ricardo; Quantum chemical study on surface complex structures of phosphate on gibbsite; Elsevier; Spectrochimica Acta Part A: Molecular And Biomolecular Spectroscopy; 147; 3-2015; 193-1991386-1425enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1386142515003091info:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1016/j.saa.2015.03.013info:eu-repo/semantics/altIdentifier/issn/1386-1425info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:40:27Zoai:ri.conicet.gov.ar:11336/4658instacron: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:34982025-09-29 10:40:27.973CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Quantum chemical study on surface complex structures of phosphate on gibbsite
title Quantum chemical study on surface complex structures of phosphate on gibbsite
spellingShingle Quantum chemical study on surface complex structures of phosphate on gibbsite
Luengo, Carina Vanesa
Gibbsite
Phosphate
Dft
Adsorption
Atr-Ftir
title_short Quantum chemical study on surface complex structures of phosphate on gibbsite
title_full Quantum chemical study on surface complex structures of phosphate on gibbsite
title_fullStr Quantum chemical study on surface complex structures of phosphate on gibbsite
title_full_unstemmed Quantum chemical study on surface complex structures of phosphate on gibbsite
title_sort Quantum chemical study on surface complex structures of phosphate on gibbsite
dc.creator.none.fl_str_mv Luengo, Carina Vanesa
Castellani, Norberto Jorge
Ferullo, Ricardo
author Luengo, Carina Vanesa
author_facet Luengo, Carina Vanesa
Castellani, Norberto Jorge
Ferullo, Ricardo
author_role author
author2 Castellani, Norberto Jorge
Ferullo, Ricardo
author2_role author
author
dc.subject.none.fl_str_mv Gibbsite
Phosphate
Dft
Adsorption
Atr-Ftir
topic Gibbsite
Phosphate
Dft
Adsorption
Atr-Ftir
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Quantum mechanics calculations based on the density functional theory (DFT) were used to identify phosphate surface complexes on gibbsite at low and high pH. The different phosphate species were represented using the Al6(OH)18(H2O)6 cluster model considering four different geometries: monodentate mononuclear (Pmm), monodentate binuclear (Pmb), bidentate mononuclear (Pbm) and bidentate binuclear (Pbb). The corresponding adsorption reactions were modelled via ligand exchange between phosphate species and surface functional groups (hydroxyls and protonated hydroxyls at high and low pH, respectively). The theoretical results indicate that phosphate surface complexes are thermodynamically more favored at acid pH, in agreement with experimental evidences. The first step in these reactions, i.e., the generation of required aluminum vacant sites, was predicted to be particularly favorable when singly coordinated aquo groups are released. Stretching and bending vibrational frequencies associated with the different surface structures were calculated at both pH conditions. The corresponding values at low pH were found to be shifted to higher frequencies with respect to those ones at high pH. ATR-FTIR studies were also carried out. The resulting spectra are dominated by a strong band within the 800?840 cm-1 interval due to P?OH stretching modes. The corresponding peak appearing around 820 cm_1 at high pH is shifted to lower frequencies with respect to the position at low pH, a tendency well predicted by DFT calculations.
Fil: Luengo, Carina Vanesa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina. Universidad Nacional del Sur; Argentina
description Quantum mechanics calculations based on the density functional theory (DFT) were used to identify phosphate surface complexes on gibbsite at low and high pH. The different phosphate species were represented using the Al6(OH)18(H2O)6 cluster model considering four different geometries: monodentate mononuclear (Pmm), monodentate binuclear (Pmb), bidentate mononuclear (Pbm) and bidentate binuclear (Pbb). The corresponding adsorption reactions were modelled via ligand exchange between phosphate species and surface functional groups (hydroxyls and protonated hydroxyls at high and low pH, respectively). The theoretical results indicate that phosphate surface complexes are thermodynamically more favored at acid pH, in agreement with experimental evidences. The first step in these reactions, i.e., the generation of required aluminum vacant sites, was predicted to be particularly favorable when singly coordinated aquo groups are released. Stretching and bending vibrational frequencies associated with the different surface structures were calculated at both pH conditions. The corresponding values at low pH were found to be shifted to higher frequencies with respect to those ones at high pH. ATR-FTIR studies were also carried out. The resulting spectra are dominated by a strong band within the 800?840 cm-1 interval due to P?OH stretching modes. The corresponding peak appearing around 820 cm_1 at high pH is shifted to lower frequencies with respect to the position at low pH, a tendency well predicted by DFT calculations.
publishDate 2015
dc.date.none.fl_str_mv 2015-03
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/11336/4658
Luengo, Carina Vanesa; Castellani, Norberto Jorge; Ferullo, Ricardo; Quantum chemical study on surface complex structures of phosphate on gibbsite; Elsevier; Spectrochimica Acta Part A: Molecular And Biomolecular Spectroscopy; 147; 3-2015; 193-199
1386-1425
url http://hdl.handle.net/11336/4658
identifier_str_mv Luengo, Carina Vanesa; Castellani, Norberto Jorge; Ferullo, Ricardo; Quantum chemical study on surface complex structures of phosphate on gibbsite; Elsevier; Spectrochimica Acta Part A: Molecular And Biomolecular Spectroscopy; 147; 3-2015; 193-199
1386-1425
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1386142515003091
info:eu-repo/semantics/altIdentifier/url/http://dx.doi.org/10.1016/j.saa.2015.03.013
info:eu-repo/semantics/altIdentifier/issn/1386-1425
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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 13.070432

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