Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation

Supported palladium nanoparticles, prepared by reducing the active metal in the presence of the hexadecylIJ2-hydroxyethyl)dimethylammonium dihydrogen-phosphate (HHDMA) ligand and depositing the resulting colloids on titanium silicate (TiSi2O6), represent a proven alternative to the archetypal poison...

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Autores: Albani, Davide, Vilé, Gianvito, Mitchell, Sharon, Witte, Peter T., Almora-Barrios, Neyvis, Verel, René, López, Núria, Pérez-Ramírez, Javier
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/358882
Acceso en línea:http://hdl.handle.net/2072/358882
https://doi.org/10.1039/C5CY01921D
Access Level:acceso abierto
Palabra clave:54
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spelling Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenationAlbani, DavideVilé, GianvitoMitchell, SharonWitte, Peter T.Almora-Barrios, NeyvisVerel, RenéLópez, NúriaPérez-Ramírez, Javier54Supported palladium nanoparticles, prepared by reducing the active metal in the presence of the hexadecylIJ2-hydroxyethyl)dimethylammonium dihydrogen-phosphate (HHDMA) ligand and depositing the resulting colloids on titanium silicate (TiSi2O6), represent a proven alternative to the archetypal poisoned catalysts in industrially-relevant selective hydrogenations. To date, a key aspect in the design of these hybrid nanocatalysts remains unaddressed, namely the impact of the ligand content on the catalytic behaviour. In order to assess the structural and associated catalytic implications of this variable, we have prepared a series of Pd-HHDMA/TiSi2O6 catalysts with different HHDMA content (0.3–16.8 wt%), keeping the average particle size (5 nm) and Pd content (0.3 wt%) constant. The materials are characterised with a toolbox of methods, including advanced microscopy and solid-state nuclear magnetic resonance, in order to assess the structure metal–ligand interface and the mobility of the alkyl chain. Continuous-flow three- phase hydrogenations of short-chain acetylenic compounds, nitriles, and carbonyls reveal an increase in the catalytic activity with the ligand content. Density Functional Theory indicates that the ligand behaves as a self-assembled monolayer, changing its adsorption configuration as a function of the HHDMA concentra- tion. At low coverage, the organic layer lies almost flat on the surface of the metal nanoparticle blocking a large number of metal sites and resembling a two-dimensional catalyst; high HHDMA coverages favour an extended three-dimensional configuration of the alkyl chain, and consequently a lower fraction of Pd sites are poisoned. These results provide new fundamental insights into the role of the ligand on the catalytic activity and can enable the design of hybrid nanocatalysts with optimised performance.2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion1621 p.application/pdfhttp://hdl.handle.net/2072/358882https://doi.org/10.1039/C5CY01921DRECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésL'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/3588822026-05-29T05:05:01Z
dc.title.none.fl_str_mv Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
title Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
spellingShingle Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
Albani, Davide
54
title_short Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
title_full Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
title_fullStr Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
title_full_unstemmed Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
title_sort Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation
dc.creator.none.fl_str_mv Albani, Davide
Vilé, Gianvito
Mitchell, Sharon
Witte, Peter T.
Almora-Barrios, Neyvis
Verel, René
López, Núria
Pérez-Ramírez, Javier
author Albani, Davide
author_facet Albani, Davide
Vilé, Gianvito
Mitchell, Sharon
Witte, Peter T.
Almora-Barrios, Neyvis
Verel, René
López, Núria
Pérez-Ramírez, Javier
author_role author
author2 Vilé, Gianvito
Mitchell, Sharon
Witte, Peter T.
Almora-Barrios, Neyvis
Verel, René
López, Núria
Pérez-Ramírez, Javier
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv 54
topic 54
description Supported palladium nanoparticles, prepared by reducing the active metal in the presence of the hexadecylIJ2-hydroxyethyl)dimethylammonium dihydrogen-phosphate (HHDMA) ligand and depositing the resulting colloids on titanium silicate (TiSi2O6), represent a proven alternative to the archetypal poisoned catalysts in industrially-relevant selective hydrogenations. To date, a key aspect in the design of these hybrid nanocatalysts remains unaddressed, namely the impact of the ligand content on the catalytic behaviour. In order to assess the structural and associated catalytic implications of this variable, we have prepared a series of Pd-HHDMA/TiSi2O6 catalysts with different HHDMA content (0.3–16.8 wt%), keeping the average particle size (5 nm) and Pd content (0.3 wt%) constant. The materials are characterised with a toolbox of methods, including advanced microscopy and solid-state nuclear magnetic resonance, in order to assess the structure metal–ligand interface and the mobility of the alkyl chain. Continuous-flow three- phase hydrogenations of short-chain acetylenic compounds, nitriles, and carbonyls reveal an increase in the catalytic activity with the ligand content. Density Functional Theory indicates that the ligand behaves as a self-assembled monolayer, changing its adsorption configuration as a function of the HHDMA concentra- tion. At low coverage, the organic layer lies almost flat on the surface of the metal nanoparticle blocking a large number of metal sites and resembling a two-dimensional catalyst; high HHDMA coverages favour an extended three-dimensional configuration of the alkyl chain, and consequently a lower fraction of Pd sites are poisoned. These results provide new fundamental insights into the role of the ligand on the catalytic activity and can enable the design of hybrid nanocatalysts with optimised performance.
publishDate 2015
dc.date.none.fl_str_mv 2015
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 http://hdl.handle.net/2072/358882
https://doi.org/10.1039/C5CY01921D
url http://hdl.handle.net/2072/358882
https://doi.org/10.1039/C5CY01921D
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 1621 p.
application/pdf
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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