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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/29193
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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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13.22299 |