Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions

The interaction of molecular hydrogen with a series of 28 two-dimensional (2D) carbides and nitrides, known as MXenes, has been studied by means of periodic density functional calculations. This study shows that trends in atomic and molecular adsorption energies can be rationalized in terms of the e...

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Autores: López, Martí, Morales García, Ángel, Viñes Solana, Francesc, Illas i Riera, Francesc
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2021
País:España
Recursos:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/195453
Acesso em linha:https://hdl.handle.net/2445/195453
Access Level:acceso abierto
Palavra-chave:Termodinàmica
Adsorció
Hidrogen
Thermodynamics
Adsorption
Hydrogen
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spelling Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation ReactionsLópez, MartíMorales García, ÁngelViñes Solana, FrancescIllas i Riera, FrancescTermodinàmicaAdsorcióHidrogenThermodynamicsAdsorptionHydrogenThe interaction of molecular hydrogen with a series of 28 two-dimensional (2D) carbides and nitrides, known as MXenes, has been studied by means of periodic density functional calculations. This study shows that trends in atomic and molecular adsorption energies can be rationalized in terms of the electrostatic potential above the surface site and the Bader charge on the surface metal atoms. For all systems, molecular hydrogen is found to dissociate with almost negligible barriers, meaning that at low temperature the MXene surface will be passivated by adsorbed atomic hydrogen. The conditions at which the MXene surface is partly covered and, hence, able to participate in hydrogenation reactions are investigated by means of ab initio thermodynamics and phase diagrams derived from microkinetic simulations. The first provide the equilibrium conditions for a given H coverage on the MXene of interest, whereas the second provides the conditions at which a given configuration is reachable at the working conditions. For fast enough processes, both approaches necessarily lead to the same result, but this may differ when high energy barriers are involved, as it the case here for the H adatoms recombination step. With this suite, we show that Fe2C, W2N, and Mo2C are promising hydrogenation catalysts. This work serves as a first step toward the rational design and implementation of MXene-based hydrogenation catalysts.American Chemical Society2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/195453Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1021/acscatal.1c03150ACS Catalysis, 2021, vol. 11, num. 21, p. 12850-12857https://doi.org/10.1021/acscatal.1c03150cc-by (c) López, Martí et al., 2021http://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1954532026-05-27T06:46:51Z
dc.title.none.fl_str_mv Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
title Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
spellingShingle Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
López, Martí
Termodinàmica
Adsorció
Hidrogen
Thermodynamics
Adsorption
Hydrogen
title_short Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
title_full Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
title_fullStr Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
title_full_unstemmed Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
title_sort Thermodynamics and Kinetics of Molecular Hydrogen Adsorption and Dissociation on MXenes: Relevance to Heterogeneously Catalyzed Hydrogenation Reactions
dc.creator.none.fl_str_mv López, Martí
Morales García, Ángel
Viñes Solana, Francesc
Illas i Riera, Francesc
author López, Martí
author_facet López, Martí
Morales García, Ángel
Viñes Solana, Francesc
Illas i Riera, Francesc
author_role author
author2 Morales García, Ángel
Viñes Solana, Francesc
Illas i Riera, Francesc
author2_role author
author
author
dc.subject.none.fl_str_mv Termodinàmica
Adsorció
Hidrogen
Thermodynamics
Adsorption
Hydrogen
topic Termodinàmica
Adsorció
Hidrogen
Thermodynamics
Adsorption
Hydrogen
description The interaction of molecular hydrogen with a series of 28 two-dimensional (2D) carbides and nitrides, known as MXenes, has been studied by means of periodic density functional calculations. This study shows that trends in atomic and molecular adsorption energies can be rationalized in terms of the electrostatic potential above the surface site and the Bader charge on the surface metal atoms. For all systems, molecular hydrogen is found to dissociate with almost negligible barriers, meaning that at low temperature the MXene surface will be passivated by adsorbed atomic hydrogen. The conditions at which the MXene surface is partly covered and, hence, able to participate in hydrogenation reactions are investigated by means of ab initio thermodynamics and phase diagrams derived from microkinetic simulations. The first provide the equilibrium conditions for a given H coverage on the MXene of interest, whereas the second provides the conditions at which a given configuration is reachable at the working conditions. For fast enough processes, both approaches necessarily lead to the same result, but this may differ when high energy barriers are involved, as it the case here for the H adatoms recombination step. With this suite, we show that Fe2C, W2N, and Mo2C are promising hydrogenation catalysts. This work serves as a first step toward the rational design and implementation of MXene-based hydrogenation catalysts.
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/195453
url https://hdl.handle.net/2445/195453
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1021/acscatal.1c03150
ACS Catalysis, 2021, vol. 11, num. 21, p. 12850-12857
https://doi.org/10.1021/acscatal.1c03150
dc.rights.none.fl_str_mv cc-by (c) López, Martí et al., 2021
http://creativecommons.org/licenses/by/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) López, Martí et al., 2021
http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 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 Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301603

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