Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation

Modification of transition metals with p-block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi-hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi-hydrogenati...

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Autores: Albani, Davide, Karajovic, Konstantin, Tata, Bharath, Li, Qiang, Mitchell, Sharon, López, Núria, Pérez-Ramírez, Javier
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
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:2072/359791
Acceso en línea:http://hdl.handle.net/2072/359791
https://doi.org/10.1002/cctc.201801430
Access Level:acceso abierto
Palabra clave:54
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spelling Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-HydrogenationAlbani, DavideKarajovic, KonstantinTata, BharathLi, QiangMitchell, SharonLópez, NúriaPérez-Ramírez, Javier54Modification of transition metals with p-block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi-hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi-hydrogenation of 1-hexyne and 2-methyl-3-butyn-2-ol shows that the phosphides present higher rate and selectivity than unmodified nickel catalysts. While no activity and selectivity differences are displayed in the semi-hydrogenation of 1-hexyne over Ni2P and Ni5P4, in the case of 2-methyl-3-butyn-2-ol a higher rate and lower selectivity to 2-methyl-3-buten-2-ol are observed over Ni2P. Density functional theory reveals that the hydroxyl group facilitates the reaction, but also increases the barrier for product desorption. Detailed analyses of the ensemble show the potential of phosphorus to create spatially-isolated nickel trimers that surpass the performance of unmodified nickel, but also its limited ability to modulate the electronic properties and related binding energies of organic intermediates, which is key to preventing undesired side reactions.2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion457 p.application/pdfhttp://hdl.handle.net/2072/359791https://doi.org/10.1002/cctc.201801430RECERCAT (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:2072/3597912026-05-29T05:05:01Z
dc.title.none.fl_str_mv Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
title Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
spellingShingle Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
Albani, Davide
54
title_short Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
title_full Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
title_fullStr Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
title_full_unstemmed Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
title_sort Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation
dc.creator.none.fl_str_mv Albani, Davide
Karajovic, Konstantin
Tata, Bharath
Li, Qiang
Mitchell, Sharon
López, Núria
Pérez-Ramírez, Javier
author Albani, Davide
author_facet Albani, Davide
Karajovic, Konstantin
Tata, Bharath
Li, Qiang
Mitchell, Sharon
López, Núria
Pérez-Ramírez, Javier
author_role author
author2 Karajovic, Konstantin
Tata, Bharath
Li, Qiang
Mitchell, Sharon
López, Núria
Pérez-Ramírez, Javier
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv 54
topic 54
description Modification of transition metals with p-block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi-hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi-hydrogenation of 1-hexyne and 2-methyl-3-butyn-2-ol shows that the phosphides present higher rate and selectivity than unmodified nickel catalysts. While no activity and selectivity differences are displayed in the semi-hydrogenation of 1-hexyne over Ni2P and Ni5P4, in the case of 2-methyl-3-butyn-2-ol a higher rate and lower selectivity to 2-methyl-3-buten-2-ol are observed over Ni2P. Density functional theory reveals that the hydroxyl group facilitates the reaction, but also increases the barrier for product desorption. Detailed analyses of the ensemble show the potential of phosphorus to create spatially-isolated nickel trimers that surpass the performance of unmodified nickel, but also its limited ability to modulate the electronic properties and related binding energies of organic intermediates, which is key to preventing undesired side reactions.
publishDate 2018
dc.date.none.fl_str_mv 2018
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/2072/359791
https://doi.org/10.1002/cctc.201801430
url http://hdl.handle.net/2072/359791
https://doi.org/10.1002/cctc.201801430
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 457 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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