Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane

Autores
Wang, Qi; Fu, Fangyu; Yang, Sha; Martinez Moro, Marta; Ramirez, Maria de Los Angeles; Moya, Sergio Enrique; Salmon, Lionel; Ruiz, Jaime; Astruc, Didier
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hydrolysis of ammonia borane (AB) is a very convenient source of H 2 , but this reaction needs catalytic activation to become practical under ambient conditions. Here this reaction is catalyzed by bimetallic late transition-metal nanoparticles (NPs) that are stabilized and activated by "click" dendrimers. Dendrimers 1 and 2 contain 27 or 81 triethylene glycol terminal groups and 9 or 27 1,2,3-triazole ligands, respectively, located on the dendritic tethers. A remarkable synergy between Pt and Co in the Pt-Co/"click" dendrimer nanocatalysts is revealed. These Pt-Co/"click" dendrimer catalysts are much more efficient for hydrolysis of AB than either "click" dendrimer-stabilized Co or Pt analogues alone. The best catalyst, Pt 1 Co 1 1, stabilized by the nonatriazole "click" dendrimer 1 achieves a turnover frequency number (TOF) of 303 mol H 2 mol cat -1 min -1 (606 mol H 2 mol Pt -1 min -1 ) at 20 ± 1 °C. The AB hydrolysis reaction catalyzed by Pt 1 Co 1 1 is boosted by NaOH, the TOF value reaching 476.2 mol H 2 mol cat -1 min -1 (952.4 mol H2 mol Pt -1 min -1 ), one of the very best results ever obtained for this reaction. The presence of ≥25% Pt in the CoPt nanoalloy provides a reaction rate higher than that obtained with the pure PtNP catalyst alone. The kinetics involves in particular a kinetic isotope effect k D k H of 2.46 obtained for the hydrolysis reaction with D 2 O, suggesting that an O-H bond of water is cleaved in the rate-determining step. Tandem reactions were carried out for the hydrogenation of styrene with hydrogen generated from the hydrolysis of AB. Performing this tandem reaction with D 2 O shows deuteration of the ethylbenzene products, confirming O-D bond cleavage and H/D scrambling on the bimetallic NP surface. Finally, a full reaction mechanism is proposed. This dramatic synergy type should also prove to be useful in a number of other catalytic systems.
Fil: Wang, Qi. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Fu, Fangyu. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Yang, Sha. Anhui University; China
Fil: Martinez Moro, Marta. Centro de Investigacion Cooperativa En Biomateriales.; España
Fil: Ramirez, Maria de Los Angeles. Centro de Investigacion Cooperativa En Biomateriales.; España. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Moya, Sergio Enrique. Centro de Investigacion Cooperativa En Biomateriales.; España
Fil: Salmon, Lionel. Centre National de la Recherche Scientifique; Francia
Fil: Ruiz, Jaime. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Astruc, Didier. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Materia
AMMONIA BORANE
COBALT
DENDRIMER
HYDROLYSIS
NANOCATALYST
SYNERGY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/125351
Acceder
id CONICETDig_9edea438b62edae0da95d737c60490d6
oai_identifier_str oai:ri.conicet.gov.ar:11336/125351
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia boraneWang, QiFu, FangyuYang, ShaMartinez Moro, MartaRamirez, Maria de Los AngelesMoya, Sergio EnriqueSalmon, LionelRuiz, JaimeAstruc, DidierAMMONIA BORANECOBALTDENDRIMERHYDROLYSISNANOCATALYSTSYNERGYhttps://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2Hydrolysis of ammonia borane (AB) is a very convenient source of H 2 , but this reaction needs catalytic activation to become practical under ambient conditions. Here this reaction is catalyzed by bimetallic late transition-metal nanoparticles (NPs) that are stabilized and activated by "click" dendrimers. Dendrimers 1 and 2 contain 27 or 81 triethylene glycol terminal groups and 9 or 27 1,2,3-triazole ligands, respectively, located on the dendritic tethers. A remarkable synergy between Pt and Co in the Pt-Co/"click" dendrimer nanocatalysts is revealed. These Pt-Co/"click" dendrimer catalysts are much more efficient for hydrolysis of AB than either "click" dendrimer-stabilized Co or Pt analogues alone. The best catalyst, Pt 1 Co 1 1, stabilized by the nonatriazole "click" dendrimer 1 achieves a turnover frequency number (TOF) of 303 mol H 2 mol cat -1 min -1 (606 mol H 2 mol Pt -1 min -1 ) at 20 ± 1 °C. The AB hydrolysis reaction catalyzed by Pt 1 Co 1 1 is boosted by NaOH, the TOF value reaching 476.2 mol H 2 mol cat -1 min -1 (952.4 mol H2 mol Pt -1 min -1 ), one of the very best results ever obtained for this reaction. The presence of ≥25% Pt in the CoPt nanoalloy provides a reaction rate higher than that obtained with the pure PtNP catalyst alone. The kinetics involves in particular a kinetic isotope effect k D k H of 2.46 obtained for the hydrolysis reaction with D 2 O, suggesting that an O-H bond of water is cleaved in the rate-determining step. Tandem reactions were carried out for the hydrogenation of styrene with hydrogen generated from the hydrolysis of AB. Performing this tandem reaction with D 2 O shows deuteration of the ethylbenzene products, confirming O-D bond cleavage and H/D scrambling on the bimetallic NP surface. Finally, a full reaction mechanism is proposed. This dramatic synergy type should also prove to be useful in a number of other catalytic systems.Fil: Wang, Qi. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; FranciaFil: Fu, Fangyu. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; FranciaFil: Yang, Sha. Anhui University; ChinaFil: Martinez Moro, Marta. Centro de Investigacion Cooperativa En Biomateriales.; EspañaFil: Ramirez, Maria de Los Angeles. Centro de Investigacion Cooperativa En Biomateriales.; España. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Moya, Sergio Enrique. Centro de Investigacion Cooperativa En Biomateriales.; EspañaFil: Salmon, Lionel. Centre National de la Recherche Scientifique; FranciaFil: Ruiz, Jaime. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; FranciaFil: Astruc, Didier. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; FranciaAmerican Chemical Society2019-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/125351Wang, Qi; Fu, Fangyu; Yang, Sha; Martinez Moro, Marta; Ramirez, Maria de Los Angeles; et al.; Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane; American Chemical Society; ACS Catalysis; 9; 2; 2-2019; 1110-11192155-5435CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.8b04498info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acscatal.8b04498info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:07:23Zoai:ri.conicet.gov.ar:11336/125351instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 15:07:23.861CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
title Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
spellingShingle Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
Wang, Qi
AMMONIA BORANE
COBALT
DENDRIMER
HYDROLYSIS
NANOCATALYST
SYNERGY
title_short Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
title_full Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
title_fullStr Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
title_full_unstemmed Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
title_sort Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane
dc.creator.none.fl_str_mv Wang, Qi
Fu, Fangyu
Yang, Sha
Martinez Moro, Marta
Ramirez, Maria de Los Angeles
Moya, Sergio Enrique
Salmon, Lionel
Ruiz, Jaime
Astruc, Didier
author Wang, Qi
author_facet Wang, Qi
Fu, Fangyu
Yang, Sha
Martinez Moro, Marta
Ramirez, Maria de Los Angeles
Moya, Sergio Enrique
Salmon, Lionel
Ruiz, Jaime
Astruc, Didier
author_role author
author2 Fu, Fangyu
Yang, Sha
Martinez Moro, Marta
Ramirez, Maria de Los Angeles
Moya, Sergio Enrique
Salmon, Lionel
Ruiz, Jaime
Astruc, Didier
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv AMMONIA BORANE
COBALT
DENDRIMER
HYDROLYSIS
NANOCATALYST
SYNERGY
topic AMMONIA BORANE
COBALT
DENDRIMER
HYDROLYSIS
NANOCATALYST
SYNERGY
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Hydrolysis of ammonia borane (AB) is a very convenient source of H 2 , but this reaction needs catalytic activation to become practical under ambient conditions. Here this reaction is catalyzed by bimetallic late transition-metal nanoparticles (NPs) that are stabilized and activated by "click" dendrimers. Dendrimers 1 and 2 contain 27 or 81 triethylene glycol terminal groups and 9 or 27 1,2,3-triazole ligands, respectively, located on the dendritic tethers. A remarkable synergy between Pt and Co in the Pt-Co/"click" dendrimer nanocatalysts is revealed. These Pt-Co/"click" dendrimer catalysts are much more efficient for hydrolysis of AB than either "click" dendrimer-stabilized Co or Pt analogues alone. The best catalyst, Pt 1 Co 1 1, stabilized by the nonatriazole "click" dendrimer 1 achieves a turnover frequency number (TOF) of 303 mol H 2 mol cat -1 min -1 (606 mol H 2 mol Pt -1 min -1 ) at 20 ± 1 °C. The AB hydrolysis reaction catalyzed by Pt 1 Co 1 1 is boosted by NaOH, the TOF value reaching 476.2 mol H 2 mol cat -1 min -1 (952.4 mol H2 mol Pt -1 min -1 ), one of the very best results ever obtained for this reaction. The presence of ≥25% Pt in the CoPt nanoalloy provides a reaction rate higher than that obtained with the pure PtNP catalyst alone. The kinetics involves in particular a kinetic isotope effect k D k H of 2.46 obtained for the hydrolysis reaction with D 2 O, suggesting that an O-H bond of water is cleaved in the rate-determining step. Tandem reactions were carried out for the hydrogenation of styrene with hydrogen generated from the hydrolysis of AB. Performing this tandem reaction with D 2 O shows deuteration of the ethylbenzene products, confirming O-D bond cleavage and H/D scrambling on the bimetallic NP surface. Finally, a full reaction mechanism is proposed. This dramatic synergy type should also prove to be useful in a number of other catalytic systems.
Fil: Wang, Qi. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Fu, Fangyu. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Yang, Sha. Anhui University; China
Fil: Martinez Moro, Marta. Centro de Investigacion Cooperativa En Biomateriales.; España
Fil: Ramirez, Maria de Los Angeles. Centro de Investigacion Cooperativa En Biomateriales.; España. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Moya, Sergio Enrique. Centro de Investigacion Cooperativa En Biomateriales.; España
Fil: Salmon, Lionel. Centre National de la Recherche Scientifique; Francia
Fil: Ruiz, Jaime. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Astruc, Didier. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia
description Hydrolysis of ammonia borane (AB) is a very convenient source of H 2 , but this reaction needs catalytic activation to become practical under ambient conditions. Here this reaction is catalyzed by bimetallic late transition-metal nanoparticles (NPs) that are stabilized and activated by "click" dendrimers. Dendrimers 1 and 2 contain 27 or 81 triethylene glycol terminal groups and 9 or 27 1,2,3-triazole ligands, respectively, located on the dendritic tethers. A remarkable synergy between Pt and Co in the Pt-Co/"click" dendrimer nanocatalysts is revealed. These Pt-Co/"click" dendrimer catalysts are much more efficient for hydrolysis of AB than either "click" dendrimer-stabilized Co or Pt analogues alone. The best catalyst, Pt 1 Co 1 1, stabilized by the nonatriazole "click" dendrimer 1 achieves a turnover frequency number (TOF) of 303 mol H 2 mol cat -1 min -1 (606 mol H 2 mol Pt -1 min -1 ) at 20 ± 1 °C. The AB hydrolysis reaction catalyzed by Pt 1 Co 1 1 is boosted by NaOH, the TOF value reaching 476.2 mol H 2 mol cat -1 min -1 (952.4 mol H2 mol Pt -1 min -1 ), one of the very best results ever obtained for this reaction. The presence of ≥25% Pt in the CoPt nanoalloy provides a reaction rate higher than that obtained with the pure PtNP catalyst alone. The kinetics involves in particular a kinetic isotope effect k D k H of 2.46 obtained for the hydrolysis reaction with D 2 O, suggesting that an O-H bond of water is cleaved in the rate-determining step. Tandem reactions were carried out for the hydrogenation of styrene with hydrogen generated from the hydrolysis of AB. Performing this tandem reaction with D 2 O shows deuteration of the ethylbenzene products, confirming O-D bond cleavage and H/D scrambling on the bimetallic NP surface. Finally, a full reaction mechanism is proposed. This dramatic synergy type should also prove to be useful in a number of other catalytic systems.
publishDate 2019
dc.date.none.fl_str_mv 2019-02
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/125351
Wang, Qi; Fu, Fangyu; Yang, Sha; Martinez Moro, Marta; Ramirez, Maria de Los Angeles; et al.; Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane; American Chemical Society; ACS Catalysis; 9; 2; 2-2019; 1110-1119
2155-5435
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125351
identifier_str_mv Wang, Qi; Fu, Fangyu; Yang, Sha; Martinez Moro, Marta; Ramirez, Maria de Los Angeles; et al.; Dramatic synergy in CoPt nanocatalysts stabilized by "click" dendrimers for evolution of hydrogen from hydrolysis of ammonia borane; American Chemical Society; ACS Catalysis; 9; 2; 2-2019; 1110-1119
2155-5435
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.8b04498
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acscatal.8b04498
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
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 reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.22299

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