Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis...

Autores
Roncaroli, Federico; Martínez, Eduardo David; Soler Illia, Galo Juan de Avila Arturo; Blesa, Miguel Angel
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Highly organized titanium dioxide (TiO2) mesoporous thin films were deposited directly on silicon attenuated total reflection (ATR) crystals by dip-coating, submitted to two different thermal treatments, and characterized by ellipsometric porosimetry analysis (EPA), X-ray diffraction, and electron microscopy. The kinetics and equilibrium of the adsorption of oxalic acid as well as their photocatalytic efficiency were studied in situ by Fourier transformed infrared spectroscopy (FTIR-ATR). The spectral properties and the Langmuir constants of the detected surface complexes resemble those previously found in TiO2 Degussa P25 and anatase particulate films. The photocatalytic activity for the oxidation of oxalic acid was found to be similar to the corresponding one for Degussa P25. The kinetics of adsorption of oxalic acid follows a pseudo-first-order behavior. The pseudo-first-order rate constants show a linear relationship with the oxalic acid concentration. Adsorption (ka) and desorption rate constants (kd) were obtained. The ka values were analyzed in relation to the pore and neck sizes, accessible volume, thickness, and film area. The film area affects strongly the kinetic parameters, while no clear dependence on the thickness value was observed. When the film area is taken into account, adsorption rates on mesoporous films are appreciably larger than on particulate films. Thus, enhanced adsorption rates make mesoporous films better candidates as photocatalysts. The difference is interpreted in terms of a reduced tortousity in the ordered mesoporous films, probably due to their regular spatial order. It is also concluded that sensors and catalysts based on mesoporous films should respond faster than those based on conventional films.
Fil: Roncaroli, Federico. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; Argentina
Materia
Titanium Dioxide
Infrared Spectroscopy
Mesoporous Materials
Adsorption Kinetics
Ellipsometry
Photocatalysis
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:11336/29193

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spelling Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic AcidsRoncaroli, FedericoMartínez, Eduardo DavidSoler Illia, Galo Juan de Avila ArturoBlesa, Miguel AngelTitanium DioxideInfrared SpectroscopyMesoporous MaterialsAdsorption KineticsEllipsometryPhotocatalysishttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Highly organized titanium dioxide (TiO2) mesoporous thin films were deposited directly on silicon attenuated total reflection (ATR) crystals by dip-coating, submitted to two different thermal treatments, and characterized by ellipsometric porosimetry analysis (EPA), X-ray diffraction, and electron microscopy. The kinetics and equilibrium of the adsorption of oxalic acid as well as their photocatalytic efficiency were studied in situ by Fourier transformed infrared spectroscopy (FTIR-ATR). The spectral properties and the Langmuir constants of the detected surface complexes resemble those previously found in TiO2 Degussa P25 and anatase particulate films. The photocatalytic activity for the oxidation of oxalic acid was found to be similar to the corresponding one for Degussa P25. The kinetics of adsorption of oxalic acid follows a pseudo-first-order behavior. The pseudo-first-order rate constants show a linear relationship with the oxalic acid concentration. Adsorption (ka) and desorption rate constants (kd) were obtained. The ka values were analyzed in relation to the pore and neck sizes, accessible volume, thickness, and film area. The film area affects strongly the kinetic parameters, while no clear dependence on the thickness value was observed. When the film area is taken into account, adsorption rates on mesoporous films are appreciably larger than on particulate films. Thus, enhanced adsorption rates make mesoporous films better candidates as photocatalysts. The difference is interpreted in terms of a reduced tortousity in the ordered mesoporous films, probably due to their regular spatial order. It is also concluded that sensors and catalysts based on mesoporous films should respond faster than those based on conventional films.Fil: Roncaroli, Federico. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; ArgentinaAmerican Chemical Society2013-06info: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/11336/29193Roncaroli, Federico; Martínez, Eduardo David; Soler Illia, Galo Juan de Avila Arturo; Blesa, Miguel Angel; Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids; American Chemical Society; Journal of Physical Chemistry C; 117; 29; 6-2013; 15026-150341932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp312334yinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp312334yinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:08:44Zoai:ri.conicet.gov.ar:11336/29193instacron: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 15:08:45.105CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
title Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
spellingShingle Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
Roncaroli, Federico
Titanium Dioxide
Infrared Spectroscopy
Mesoporous Materials
Adsorption Kinetics
Ellipsometry
Photocatalysis
title_short Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
title_full Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
title_fullStr Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
title_full_unstemmed Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
title_sort Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids
dc.creator.none.fl_str_mv Roncaroli, Federico
Martínez, Eduardo David
Soler Illia, Galo Juan de Avila Arturo
Blesa, Miguel Angel
author Roncaroli, Federico
author_facet Roncaroli, Federico
Martínez, Eduardo David
Soler Illia, Galo Juan de Avila Arturo
Blesa, Miguel Angel
author_role author
author2 Martínez, Eduardo David
Soler Illia, Galo Juan de Avila Arturo
Blesa, Miguel Angel
author2_role author
author
author
dc.subject.none.fl_str_mv Titanium Dioxide
Infrared Spectroscopy
Mesoporous Materials
Adsorption Kinetics
Ellipsometry
Photocatalysis
topic Titanium Dioxide
Infrared Spectroscopy
Mesoporous Materials
Adsorption Kinetics
Ellipsometry
Photocatalysis
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Highly organized titanium dioxide (TiO2) mesoporous thin films were deposited directly on silicon attenuated total reflection (ATR) crystals by dip-coating, submitted to two different thermal treatments, and characterized by ellipsometric porosimetry analysis (EPA), X-ray diffraction, and electron microscopy. The kinetics and equilibrium of the adsorption of oxalic acid as well as their photocatalytic efficiency were studied in situ by Fourier transformed infrared spectroscopy (FTIR-ATR). The spectral properties and the Langmuir constants of the detected surface complexes resemble those previously found in TiO2 Degussa P25 and anatase particulate films. The photocatalytic activity for the oxidation of oxalic acid was found to be similar to the corresponding one for Degussa P25. The kinetics of adsorption of oxalic acid follows a pseudo-first-order behavior. The pseudo-first-order rate constants show a linear relationship with the oxalic acid concentration. Adsorption (ka) and desorption rate constants (kd) were obtained. The ka values were analyzed in relation to the pore and neck sizes, accessible volume, thickness, and film area. The film area affects strongly the kinetic parameters, while no clear dependence on the thickness value was observed. When the film area is taken into account, adsorption rates on mesoporous films are appreciably larger than on particulate films. Thus, enhanced adsorption rates make mesoporous films better candidates as photocatalysts. The difference is interpreted in terms of a reduced tortousity in the ordered mesoporous films, probably due to their regular spatial order. It is also concluded that sensors and catalysts based on mesoporous films should respond faster than those based on conventional films.
Fil: Roncaroli, Federico. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Blesa, Miguel Angel. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; Argentina
description Highly organized titanium dioxide (TiO2) mesoporous thin films were deposited directly on silicon attenuated total reflection (ATR) crystals by dip-coating, submitted to two different thermal treatments, and characterized by ellipsometric porosimetry analysis (EPA), X-ray diffraction, and electron microscopy. The kinetics and equilibrium of the adsorption of oxalic acid as well as their photocatalytic efficiency were studied in situ by Fourier transformed infrared spectroscopy (FTIR-ATR). The spectral properties and the Langmuir constants of the detected surface complexes resemble those previously found in TiO2 Degussa P25 and anatase particulate films. The photocatalytic activity for the oxidation of oxalic acid was found to be similar to the corresponding one for Degussa P25. The kinetics of adsorption of oxalic acid follows a pseudo-first-order behavior. The pseudo-first-order rate constants show a linear relationship with the oxalic acid concentration. Adsorption (ka) and desorption rate constants (kd) were obtained. The ka values were analyzed in relation to the pore and neck sizes, accessible volume, thickness, and film area. The film area affects strongly the kinetic parameters, while no clear dependence on the thickness value was observed. When the film area is taken into account, adsorption rates on mesoporous films are appreciably larger than on particulate films. Thus, enhanced adsorption rates make mesoporous films better candidates as photocatalysts. The difference is interpreted in terms of a reduced tortousity in the ordered mesoporous films, probably due to their regular spatial order. It is also concluded that sensors and catalysts based on mesoporous films should respond faster than those based on conventional films.
publishDate 2013
dc.date.none.fl_str_mv 2013-06
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/11336/29193
Roncaroli, Federico; Martínez, Eduardo David; Soler Illia, Galo Juan de Avila Arturo; Blesa, Miguel Angel; Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids; American Chemical Society; Journal of Physical Chemistry C; 117; 29; 6-2013; 15026-15034
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/29193
identifier_str_mv Roncaroli, Federico; Martínez, Eduardo David; Soler Illia, Galo Juan de Avila Arturo; Blesa, Miguel Angel; Mesoporous Thin Films of TiO2 on Attenuated Total Reflection Crystals. An In Situ Fourier-Transform Infrared Study of the Kinetics and Equilibrium of Adsorption and Photocatalysis of Carboxylic Acids; American Chemical Society; Journal of Physical Chemistry C; 117; 29; 6-2013; 15026-15034
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp312334y
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp312334y
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)
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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