Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes

The hydrogenation of nitro compounds is an industrial process that has experienced a renovated interest in the last 10 years due to the discovery of highly selective and environmentally friendly solid catalysts. Particularly, the performance of chemoselective reactions in the presence of very sensit...

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Autores: Serna Merino, Pedro, Corma, Avelino
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/162220
Acceso en línea:http://hdl.handle.net/10261/162220
Access Level:acceso abierto
Palabra clave:Selective hydrogenation
Strong metal−support interactions
Supported nanoparticles design
Reduction of nitro compounds
Green hydrogenation chemistry
Gold catalysis
Cascade reactions
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oai_identifier_str oai:digital.csic.es:10261/162220
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
title Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
spellingShingle Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
Serna Merino, Pedro
Selective hydrogenation
Strong metal−support interactions
Supported nanoparticles design
Reduction of nitro compounds
Green hydrogenation chemistry
Gold catalysis
Cascade reactions
title_short Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
title_full Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
title_fullStr Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
title_full_unstemmed Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
title_sort Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes
dc.creator.none.fl_str_mv Serna Merino, Pedro
Corma, Avelino
author Serna Merino, Pedro
author_facet Serna Merino, Pedro
Corma, Avelino
author_role author
author2 Corma, Avelino
author2_role author
dc.contributor.none.fl_str_mv European Research Council
European Commission
Ministerio de Ciencia e Innovación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Selective hydrogenation
Strong metal−support interactions
Supported nanoparticles design
Reduction of nitro compounds
Green hydrogenation chemistry
Gold catalysis
Cascade reactions
topic Selective hydrogenation
Strong metal−support interactions
Supported nanoparticles design
Reduction of nitro compounds
Green hydrogenation chemistry
Gold catalysis
Cascade reactions
description The hydrogenation of nitro compounds is an industrial process that has experienced a renovated interest in the last 10 years due to the discovery of highly selective and environmentally friendly solid catalysts. Particularly, the performance of chemoselective reactions in the presence of very sensitive groups such as double and triple CC bonds, with H2 as reductant and no soluble additives needed, had been elusive for decades. The discovery that gold nanoparticles on solid supports could carry out such a reaction very selectively invigorated this area of research and claimed gold as an outstanding catalyst beyond oxidation processes. Subsequent work, devoted to understand how gold catalysts operate, established a strong basis for the design of more efficient materials and the development of new routes for the synthesis of nitro derivatives. Here, we present three generations of materials that allowed improving the performance of the original gold catalysts. The relatively low activity of the initial Au/TiO2 catalysts could be first boosted, without practical loss of selectivity, by the design of a material that incorporated two catalytic functions on the support: small amounts of platinum to enhance H2 dissociation and a greater amount of gold to activate the −NO2 group. Later, we learned how to control the catalytic structures and induce chemoselectivity to traditionally unselective metals such as platinum, ruthenium, and nickel nanoparticles. Recently, Fe2O3 nanoparticles surrounded by a nitrogen-doped carbon layer have erupted as a promising alternative. A remarkable outcome from all that work is that the final pool of catalytic alternatives has been markedly expanded. Diversity is important because different solutions may open new gates to different catalytic processes, and we summarize here how the scope of new reactions and products could be expanded by means of properly designed metal catalysts in which the support and metal work in a concerted way to direct the reaction toward the desired product. For example, whereas Au/TiO2 is a chemoselective catalyst that drives the reaction efficiently to the fully reduced reaction product (aniline), the reaction could be tuned to obtain azocompounds in high yields by using nanoparticulated ceria to support the gold nanoparticles. On the other hand, whereas nitrobenzenes and aldehydes react in H2 to afford imines in the presence of Au/TiO2, the product distribution can be switched toward a more oxidized condensation product (a nitrone) using a chemoselective Pt/C catalyst, or to produce cyclohexanone oxime directly from nitrobenzene by means of supported Au and Pd metal catalysts. These and other examples represent some notable achievements, which are possibly, just the tip of the iceberg.
publishDate 2015
dc.date.none.fl_str_mv 2015
2018
2018
2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/162220
url http://hdl.handle.net/10261/162220
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/EC/H2020/671093
https://doi.org/10.1021/acscatal.5b01846
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenesSerna Merino, PedroCorma, AvelinoSelective hydrogenationStrong metal−support interactionsSupported nanoparticles designReduction of nitro compoundsGreen hydrogenation chemistryGold catalysisCascade reactionsThe hydrogenation of nitro compounds is an industrial process that has experienced a renovated interest in the last 10 years due to the discovery of highly selective and environmentally friendly solid catalysts. Particularly, the performance of chemoselective reactions in the presence of very sensitive groups such as double and triple CC bonds, with H2 as reductant and no soluble additives needed, had been elusive for decades. The discovery that gold nanoparticles on solid supports could carry out such a reaction very selectively invigorated this area of research and claimed gold as an outstanding catalyst beyond oxidation processes. Subsequent work, devoted to understand how gold catalysts operate, established a strong basis for the design of more efficient materials and the development of new routes for the synthesis of nitro derivatives. Here, we present three generations of materials that allowed improving the performance of the original gold catalysts. The relatively low activity of the initial Au/TiO2 catalysts could be first boosted, without practical loss of selectivity, by the design of a material that incorporated two catalytic functions on the support: small amounts of platinum to enhance H2 dissociation and a greater amount of gold to activate the −NO2 group. Later, we learned how to control the catalytic structures and induce chemoselectivity to traditionally unselective metals such as platinum, ruthenium, and nickel nanoparticles. Recently, Fe2O3 nanoparticles surrounded by a nitrogen-doped carbon layer have erupted as a promising alternative. A remarkable outcome from all that work is that the final pool of catalytic alternatives has been markedly expanded. Diversity is important because different solutions may open new gates to different catalytic processes, and we summarize here how the scope of new reactions and products could be expanded by means of properly designed metal catalysts in which the support and metal work in a concerted way to direct the reaction toward the desired product. For example, whereas Au/TiO2 is a chemoselective catalyst that drives the reaction efficiently to the fully reduced reaction product (aniline), the reaction could be tuned to obtain azocompounds in high yields by using nanoparticulated ceria to support the gold nanoparticles. On the other hand, whereas nitrobenzenes and aldehydes react in H2 to afford imines in the presence of Au/TiO2, the product distribution can be switched toward a more oxidized condensation product (a nitrone) using a chemoselective Pt/C catalyst, or to produce cyclohexanone oxime directly from nitrobenzene by means of supported Au and Pd metal catalysts. These and other examples represent some notable achievements, which are possibly, just the tip of the iceberg.The research was supported by Project CONSOLIDER INGENIO (MULTICAT), PROMETEO, the SEVERO OCHOA Program for centers of excellence. P.S. thanks the “Subprograma Ramon y Cajal” for the contract RYC-2012-10662. The European Union is also acknowledged by ERCAdG-2014-671093 - SynCatMatch.Peer ReviewedAmerican Chemical SocietyEuropean Research CouncilEuropean CommissionMinisterio de Ciencia e Innovación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2018201820152018info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/162220reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/H2020/671093https://doi.org/10.1021/acscatal.5b01846Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1622202026-05-22T06:33:51Z
score 15,811543

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