Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study

Periodic DFT calculations are performed to unravel the effect of the incorporation of Fe and Mn into the tung-stated zirconia catalyst, (WO3)x/ZrO2 (x = 1,3), in their electronic, geometric, and catalytic properties. Our results suggest that both Mn and Fe have a proclivity to occupy the same positi...

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Autores: Madrigal Carrillo, Karina G., Rodríguez, Juan I., Hernández Pichardo, Martha L., Jiménez Izal, Elisa
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/58514
Acceso en línea:http://hdl.handle.net/10810/58514
Access Level:acceso abierto
Palabra clave:DFT
tungstated zirconia
catalysis
alkane isomerization
WOx clusters
deprotonation
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spelling Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT studyMadrigal Carrillo, Karina G.Rodríguez, Juan I.Hernández Pichardo, Martha L.Jiménez Izal, ElisaDFTtungstated zirconiacatalysisalkane isomerizationWOx clustersdeprotonationPeriodic DFT calculations are performed to unravel the effect of the incorporation of Fe and Mn into the tung-stated zirconia catalyst, (WO3)x/ZrO2 (x = 1,3), in their electronic, geometric, and catalytic properties. Our results suggest that both Mn and Fe have a proclivity to occupy the same positions and thus both metals will compete for the same adsorption sites. The addition of Fe or Mn slightly destabilizes the WO3 monomer while stabilizes the (WO3)3 trimer. Hence, medium size clusters, which are the most catalytically active species, will be more sinter resistant in the presence of the promoters, leading to catalysts with longer lifetimes. The computed deprotonation energies evidence that the overall Bronstead acidity is increased upon the addition of the dopant atoms. It is proposed that the metals lead to a reduction of WZ and induce a local spin density imbalance.The function as redox initiators of these metals is confirmed.This work is supported by grant PID2020-114754GA-I00 funded by MCIN/ AEI/10.13039/501100011033 and funding provided by Gobierno Vasco-Eusko Jaurlaritza (IT1254-19). We also thank DIPC and SGI-IZO-SGIker (UPV/EHU) for the generous allocation of computa-tional resources. The authors thankfully acknowledge also the computer resources at MareNostrum and the technical support provided by Bar-celona Supercomputing Center (QHS-2021-3-0004). The authors acknowledge the Instituto Politecnico Nacional for the financial support received through project SIP-20221590. J.I.R. thanks SIP-IPN for financial support (projects SIP20210100 and SIP20221613). K.G.M.C. thanks CONACYT-Mexico for the doctorate fellowship (CVU: 745592).Elsevier202220222022info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/58514reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MICINN/PID2020-114754GA-I00/https://www.sciencedirect.com/science/article/pii/S0169433222015902?via%3Dihubinfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/3.0/es/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by- nc-nd/4.0/Atribución-NoComercial-SinDerivadas 3.0 Españaoai:addi.ehu.eus:10810/585142026-06-18T09:23:17Z
dc.title.none.fl_str_mv Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
title Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
spellingShingle Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
Madrigal Carrillo, Karina G.
DFT
tungstated zirconia
catalysis
alkane isomerization
WOx clusters
deprotonation
title_short Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
title_full Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
title_fullStr Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
title_full_unstemmed Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
title_sort Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst: A DFT study
dc.creator.none.fl_str_mv Madrigal Carrillo, Karina G.
Rodríguez, Juan I.
Hernández Pichardo, Martha L.
Jiménez Izal, Elisa
author Madrigal Carrillo, Karina G.
author_facet Madrigal Carrillo, Karina G.
Rodríguez, Juan I.
Hernández Pichardo, Martha L.
Jiménez Izal, Elisa
author_role author
author2 Rodríguez, Juan I.
Hernández Pichardo, Martha L.
Jiménez Izal, Elisa
author2_role author
author
author
dc.subject.none.fl_str_mv DFT
tungstated zirconia
catalysis
alkane isomerization
WOx clusters
deprotonation
topic DFT
tungstated zirconia
catalysis
alkane isomerization
WOx clusters
deprotonation
description Periodic DFT calculations are performed to unravel the effect of the incorporation of Fe and Mn into the tung-stated zirconia catalyst, (WO3)x/ZrO2 (x = 1,3), in their electronic, geometric, and catalytic properties. Our results suggest that both Mn and Fe have a proclivity to occupy the same positions and thus both metals will compete for the same adsorption sites. The addition of Fe or Mn slightly destabilizes the WO3 monomer while stabilizes the (WO3)3 trimer. Hence, medium size clusters, which are the most catalytically active species, will be more sinter resistant in the presence of the promoters, leading to catalysts with longer lifetimes. The computed deprotonation energies evidence that the overall Bronstead acidity is increased upon the addition of the dopant atoms. It is proposed that the metals lead to a reduction of WZ and induce a local spin density imbalance.The function as redox initiators of these metals is confirmed.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/58514
url http://hdl.handle.net/10810/58514
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MICINN/PID2020-114754GA-I00/
https://www.sciencedirect.com/science/article/pii/S0169433222015902?via%3Dihub
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Atribución-NoComercial-SinDerivadas 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Atribución-NoComercial-SinDerivadas 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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