Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms

Autores
Mendive, Cecilia Beatriz; Bredow, Thomas; Schneider, Jenny; Blesa, Miguel Angel; Bahnemann, Detlef
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
It is through the comparison of experimental results and theoretical calculations that the mechanistic details of several surface photoreactions initiated upon UV(A) illumination of adsorbed oxalic acid on rutile and anatase can be proposed. The absorption of light is found to be rather localized at surface Ti atoms and at the adsorbed species on both TiO2 polymorphs, respectively. Different surface complexes exhibit different photoreactivities, and consequently, each of them may follow a different reaction mechanism. Experimental data can be explained involving reactions such as the interconversion of monodentate into bidentate species which may further be oxidized to CO2 or may even produce OH radicals, while the reduction of monodentate species to the respective aldehyde results in combination with the oxidation of a neighbouring adsorbed OH group into the formation of an adsorbed OOH radical. On the basis of the results presented herein, it is concluded that the direct action of the photocatalytically produced electron-hole pairs on the adsorbed species is the primary step of the photocatalytic reaction, while the intermediate formation of free radical species followed by their reaction with an oxalate molecule can be regarded as a secondary process. Within the system described in this work, OH radicals only appear to be produced following the direct interaction of a hole with the adsorbed organic compound, but not with chemisorbed water molecules.
Fil: Mendive, Cecilia Beatriz. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Leibniz Universitaet Hannover; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Bredow, Thomas. Universitaet Bonn; Alemania
Fil: Schneider, Jenny. Leibniz Universitaet Hannover; Alemania
Fil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de General Sarmiento; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Bahnemann, Detlef. Leibniz Universitaet Hannover; Alemania
Materia
Oxalic Acid
Photocatalysis
Surface Complexes
Surface Reactions
Titanium Dioxide
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:11336/37578
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/37578
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanismsMendive, Cecilia BeatrizBredow, ThomasSchneider, JennyBlesa, Miguel AngelBahnemann, DetlefOxalic AcidPhotocatalysisSurface ComplexesSurface ReactionsTitanium Dioxidehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1It is through the comparison of experimental results and theoretical calculations that the mechanistic details of several surface photoreactions initiated upon UV(A) illumination of adsorbed oxalic acid on rutile and anatase can be proposed. The absorption of light is found to be rather localized at surface Ti atoms and at the adsorbed species on both TiO2 polymorphs, respectively. Different surface complexes exhibit different photoreactivities, and consequently, each of them may follow a different reaction mechanism. Experimental data can be explained involving reactions such as the interconversion of monodentate into bidentate species which may further be oxidized to CO2 or may even produce OH radicals, while the reduction of monodentate species to the respective aldehyde results in combination with the oxidation of a neighbouring adsorbed OH group into the formation of an adsorbed OOH radical. On the basis of the results presented herein, it is concluded that the direct action of the photocatalytically produced electron-hole pairs on the adsorbed species is the primary step of the photocatalytic reaction, while the intermediate formation of free radical species followed by their reaction with an oxalate molecule can be regarded as a secondary process. Within the system described in this work, OH radicals only appear to be produced following the direct interaction of a hole with the adsorbed organic compound, but not with chemisorbed water molecules.Fil: Mendive, Cecilia Beatriz. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Leibniz Universitaet Hannover; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bredow, Thomas. Universitaet Bonn; AlemaniaFil: Schneider, Jenny. Leibniz Universitaet Hannover; AlemaniaFil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de General Sarmiento; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bahnemann, Detlef. Leibniz Universitaet Hannover; AlemaniaAcademic Press Inc Elsevier Science2015-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/37578Mendive, Cecilia Beatriz; Bredow, Thomas; Schneider, Jenny; Blesa, Miguel Angel; Bahnemann, Detlef; Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms; Academic Press Inc Elsevier Science; Journal of Catalysis; 322; 2-2015; 60-720021-9517CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2014.11.008info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0021951714003200info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:29:52Zoai:ri.conicet.gov.ar:11336/37578instacron: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:34982025-10-15 14:29:52.515CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
title Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
spellingShingle Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
Mendive, Cecilia Beatriz
Oxalic Acid
Photocatalysis
Surface Complexes
Surface Reactions
Titanium Dioxide
title_short Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
title_full Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
title_fullStr Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
title_full_unstemmed Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
title_sort Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms
dc.creator.none.fl_str_mv Mendive, Cecilia Beatriz
Bredow, Thomas
Schneider, Jenny
Blesa, Miguel Angel
Bahnemann, Detlef
author Mendive, Cecilia Beatriz
author_facet Mendive, Cecilia Beatriz
Bredow, Thomas
Schneider, Jenny
Blesa, Miguel Angel
Bahnemann, Detlef
author_role author
author2 Bredow, Thomas
Schneider, Jenny
Blesa, Miguel Angel
Bahnemann, Detlef
author2_role author
author
author
author
dc.subject.none.fl_str_mv Oxalic Acid
Photocatalysis
Surface Complexes
Surface Reactions
Titanium Dioxide
topic Oxalic Acid
Photocatalysis
Surface Complexes
Surface Reactions
Titanium Dioxide
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv It is through the comparison of experimental results and theoretical calculations that the mechanistic details of several surface photoreactions initiated upon UV(A) illumination of adsorbed oxalic acid on rutile and anatase can be proposed. The absorption of light is found to be rather localized at surface Ti atoms and at the adsorbed species on both TiO2 polymorphs, respectively. Different surface complexes exhibit different photoreactivities, and consequently, each of them may follow a different reaction mechanism. Experimental data can be explained involving reactions such as the interconversion of monodentate into bidentate species which may further be oxidized to CO2 or may even produce OH radicals, while the reduction of monodentate species to the respective aldehyde results in combination with the oxidation of a neighbouring adsorbed OH group into the formation of an adsorbed OOH radical. On the basis of the results presented herein, it is concluded that the direct action of the photocatalytically produced electron-hole pairs on the adsorbed species is the primary step of the photocatalytic reaction, while the intermediate formation of free radical species followed by their reaction with an oxalate molecule can be regarded as a secondary process. Within the system described in this work, OH radicals only appear to be produced following the direct interaction of a hole with the adsorbed organic compound, but not with chemisorbed water molecules.
Fil: Mendive, Cecilia Beatriz. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Leibniz Universitaet Hannover; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Bredow, Thomas. Universitaet Bonn; Alemania
Fil: Schneider, Jenny. Leibniz Universitaet Hannover; Alemania
Fil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de General Sarmiento; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Bahnemann, Detlef. Leibniz Universitaet Hannover; Alemania
description It is through the comparison of experimental results and theoretical calculations that the mechanistic details of several surface photoreactions initiated upon UV(A) illumination of adsorbed oxalic acid on rutile and anatase can be proposed. The absorption of light is found to be rather localized at surface Ti atoms and at the adsorbed species on both TiO2 polymorphs, respectively. Different surface complexes exhibit different photoreactivities, and consequently, each of them may follow a different reaction mechanism. Experimental data can be explained involving reactions such as the interconversion of monodentate into bidentate species which may further be oxidized to CO2 or may even produce OH radicals, while the reduction of monodentate species to the respective aldehyde results in combination with the oxidation of a neighbouring adsorbed OH group into the formation of an adsorbed OOH radical. On the basis of the results presented herein, it is concluded that the direct action of the photocatalytically produced electron-hole pairs on the adsorbed species is the primary step of the photocatalytic reaction, while the intermediate formation of free radical species followed by their reaction with an oxalate molecule can be regarded as a secondary process. Within the system described in this work, OH radicals only appear to be produced following the direct interaction of a hole with the adsorbed organic compound, but not with chemisorbed water molecules.
publishDate 2015
dc.date.none.fl_str_mv 2015-02
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/11336/37578
Mendive, Cecilia Beatriz; Bredow, Thomas; Schneider, Jenny; Blesa, Miguel Angel; Bahnemann, Detlef; Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms; Academic Press Inc Elsevier Science; Journal of Catalysis; 322; 2-2015; 60-72
0021-9517
CONICET Digital
CONICET
url http://hdl.handle.net/11336/37578
identifier_str_mv Mendive, Cecilia Beatriz; Bredow, Thomas; Schneider, Jenny; Blesa, Miguel Angel; Bahnemann, Detlef; Oxalic acid at the TiO2/water interface under UV(A) illumination: Surface reaction mechanisms; Academic Press Inc Elsevier Science; Journal of Catalysis; 322; 2-2015; 60-72
0021-9517
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2014.11.008
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0021951714003200
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
dc.publisher.none.fl_str_mv Academic Press Inc Elsevier Science
publisher.none.fl_str_mv Academic Press Inc 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 13.22299

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