TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane

The potential of TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in the dry reforming of methane (DRM) is highlighted. The comparison of a nickel catalyst supported on natural bentonite and one prepared on TiO2-modified bentonite revealed a significantly different beha...

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Autores: Boudiaf, Meriem, Holgado, Juan P., Halliche, Djamila, Caballero Martínez, Alfonso
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/182448
Acceso en línea:https://hdl.handle.net/11441/182448
https://doi.org/10.1007/s11164-025-05674-6
Access Level:acceso abierto
Palabra clave:Dry reforming
Nickel
TiO2-modified clay
SMSI
Coke resistance
In situ XPS
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repository_id_str
spelling TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methaneBoudiaf, MeriemHolgado, Juan P.Halliche, DjamilaCaballero Martínez, AlfonsoDry reformingNickelTiO2-modified claySMSICoke resistanceIn situ XPSThe potential of TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in the dry reforming of methane (DRM) is highlighted. The comparison of a nickel catalyst supported on natural bentonite and one prepared on TiO2-modified bentonite revealed a significantly different behavior between the two catalysts under diluted and concentrated DRM reaction conditions. The unmodified bentonite catalyst, 15Ni/Na-Bent, exhibits high activity under diluted conditions (20CH4:20CO2:60He) but deactivates quickly under concentrated DRM conditions (40CH4:40CO2:20He). On the other hand, 15Ni/TiO2-Bent is less active at diluted conditions but demonstrates superior stability and activity in concentrated conditions. In situ XPS analysis of the O 1s, Al 2p, Si 2p, and Ti 2p regions of the calcined, reduced, and post-DRM samples revealed that TiO2 stabilizes the clay structure and prevents nickel reoxidation. The formation of TiO2-x species after reduction creates oxygen vacancies that trap oxidizing species in the reaction medium, thus limiting nickel reoxidation and reducing carbon deposition on the surface. Moreover, these TiO2-x species migrate to the nickel surface, forming a thin protective layer that partially encapsulates the nickel, improving metal–support interactions and providing resistance against sintering and reoxidation. In addition to XPS spectroscopy, which provided insights into the nature of the metal–support interactions in the 15Ni/Na-Bent and 15Ni/TiO2-Bent catalysts, the materials were also characterized using XRF, XRD, SEM, BET, TPR-H2, and Raman spectroscopy. These techniques offered complementary structural, textural, and morphological information, leading to a more comprehensive understanding of the catalysts’ physicoch emical properties.SpringerQuímica InorgánicaJunta de AndalucíaMinisterio de Ciencia e Innovación (MICIN). España2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/182448https://doi.org/10.1007/s11164-025-05674-6reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésResearch on Chemical Intermediates, 51 (9), 4781-4810.PID2020-119946RB-I00ENE2017-88818-C2-1-Rhttps://doi.org/10.1007/s11164-025-05674-6info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1824482026-06-17T12:51:07Z
dc.title.none.fl_str_mv TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
title TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
spellingShingle TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
Boudiaf, Meriem
Dry reforming
Nickel
TiO2-modified clay
SMSI
Coke resistance
In situ XPS
title_short TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
title_full TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
title_fullStr TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
title_full_unstemmed TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
title_sort TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in dry reforming of methane
dc.creator.none.fl_str_mv Boudiaf, Meriem
Holgado, Juan P.
Halliche, Djamila
Caballero Martínez, Alfonso
author Boudiaf, Meriem
author_facet Boudiaf, Meriem
Holgado, Juan P.
Halliche, Djamila
Caballero Martínez, Alfonso
author_role author
author2 Holgado, Juan P.
Halliche, Djamila
Caballero Martínez, Alfonso
author2_role author
author
author
dc.contributor.none.fl_str_mv Química Inorgánica
Junta de Andalucía
Ministerio de Ciencia e Innovación (MICIN). España
dc.subject.none.fl_str_mv Dry reforming
Nickel
TiO2-modified clay
SMSI
Coke resistance
In situ XPS
topic Dry reforming
Nickel
TiO2-modified clay
SMSI
Coke resistance
In situ XPS
description The potential of TiO2-modified bentonite as a cost-effective support for nickel-based catalysts in the dry reforming of methane (DRM) is highlighted. The comparison of a nickel catalyst supported on natural bentonite and one prepared on TiO2-modified bentonite revealed a significantly different behavior between the two catalysts under diluted and concentrated DRM reaction conditions. The unmodified bentonite catalyst, 15Ni/Na-Bent, exhibits high activity under diluted conditions (20CH4:20CO2:60He) but deactivates quickly under concentrated DRM conditions (40CH4:40CO2:20He). On the other hand, 15Ni/TiO2-Bent is less active at diluted conditions but demonstrates superior stability and activity in concentrated conditions. In situ XPS analysis of the O 1s, Al 2p, Si 2p, and Ti 2p regions of the calcined, reduced, and post-DRM samples revealed that TiO2 stabilizes the clay structure and prevents nickel reoxidation. The formation of TiO2-x species after reduction creates oxygen vacancies that trap oxidizing species in the reaction medium, thus limiting nickel reoxidation and reducing carbon deposition on the surface. Moreover, these TiO2-x species migrate to the nickel surface, forming a thin protective layer that partially encapsulates the nickel, improving metal–support interactions and providing resistance against sintering and reoxidation. In addition to XPS spectroscopy, which provided insights into the nature of the metal–support interactions in the 15Ni/Na-Bent and 15Ni/TiO2-Bent catalysts, the materials were also characterized using XRF, XRD, SEM, BET, TPR-H2, and Raman spectroscopy. These techniques offered complementary structural, textural, and morphological information, leading to a more comprehensive understanding of the catalysts’ physicoch emical properties.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/182448
https://doi.org/10.1007/s11164-025-05674-6
url https://hdl.handle.net/11441/182448
https://doi.org/10.1007/s11164-025-05674-6
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Research on Chemical Intermediates, 51 (9), 4781-4810.
PID2020-119946RB-I00
ENE2017-88818-C2-1-R
https://doi.org/10.1007/s11164-025-05674-6
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Springer
publisher.none.fl_str_mv Springer
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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