One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process

Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerizat...

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Autores: Sarma, Bidyut B., Kim, Jonglack, Amsler, Jonas, Agostini, Giovanni, Weidenthaler, Claudia, Pfänder, Norbert, Arenal, Raúl, Concepción, Patricia, Plessow, Philipp, Studt, Felix, Prieto, Gonzalo
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/226827
Acceso en línea:http://hdl.handle.net/10261/226827
Access Level:acceso abierto
Palabra clave:ddc:600
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network_name_str España
repository_id_str
dc.title.none.fl_str_mv One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
title One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
spellingShingle One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
Sarma, Bidyut B.
ddc:600
title_short One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
title_full One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
title_fullStr One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
title_full_unstemmed One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
title_sort One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
dc.creator.none.fl_str_mv Sarma, Bidyut B.
Kim, Jonglack
Amsler, Jonas
Agostini, Giovanni
Weidenthaler, Claudia
Pfänder, Norbert
Arenal, Raúl
Concepción, Patricia
Plessow, Philipp
Studt, Felix
Prieto, Gonzalo
author Sarma, Bidyut B.
author_facet Sarma, Bidyut B.
Kim, Jonglack
Amsler, Jonas
Agostini, Giovanni
Weidenthaler, Claudia
Pfänder, Norbert
Arenal, Raúl
Concepción, Patricia
Plessow, Philipp
Studt, Felix
Prieto, Gonzalo
author_role author
author2 Kim, Jonglack
Amsler, Jonas
Agostini, Giovanni
Weidenthaler, Claudia
Pfänder, Norbert
Arenal, Raúl
Concepción, Patricia
Plessow, Philipp
Studt, Felix
Prieto, Gonzalo
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
Ministerio de Economía y Competitividad (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv ddc:600
topic ddc:600
description Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.
publishDate 2020
dc.date.none.fl_str_mv 2020
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/226827
url http://hdl.handle.net/10261/226827
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
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#PLACEHOLDER_PARENT_METADATA_VALUE#
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info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-79776-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683
info:eu-repo/grantAgreement/EC/H2020/823717
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-096399-A-I00
https://doi.org/10.1002/ange.201915255
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
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
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spelling One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation ProcessSarma, Bidyut B.Kim, JonglackAmsler, JonasAgostini, GiovanniWeidenthaler, ClaudiaPfänder, NorbertArenal, RaúlConcepción, PatriciaPlessow, PhilippStudt, FelixPrieto, Gonzaloddc:600Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.X‐ray absorption experiments were performed at the ALBA Synchrotron Light Source (Spain), experiments 2018082961 and 2019023278. L. Simonelli and C. Marini (CLAESS‐ALBA beamline) are thanked for beamline setup. E. Andrés, M. E. Martínez, M. García, and I. López (ITQ), are acknowledged for their assistance with XAS experiments. J. Büscher, J. Ternedien, B. Spliethoff, and C. Wirtz (MPI‐KOFO) are acknowledged for the performance of XPS, XRD, BF‐TEM and 2H NMR experiments, respectively. I. C. de Freitas (MPI‐KOFO) is thanked for assistance with Raman spectroscopy. J. M. Salas (ITQ) is gratefully acknowledged for his contribution to CO‐FTIR experiments. J. J. Barnes and Shell (Amsterdam) are acknowledged for kindly providing an industrial olefin mixture as feed. Authors are thankful to F. Schüth for the provision of lab space and continued support. Part of the HRSTEM and EDX‐STEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. R.A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016‐79776‐P (AEI/FEDER, UE) and from the European Union H2020 programs “ESTEEM3” (823717). The authors acknowledge support by the state of Baden‐Württemberg through bwHPC (bwUnicluster and JUSTUS, RV bw17D01), by the GRK 2450 and by the Helmholtz Association. This research received funding from the Max Planck Society, and the Fonds der Chemische Industrie of Germany. Funding from the Spanish Ministry of Science, Innovation and Universities (Severo Ochoa program SEV‐2016‐0683 and grant RTI2018‐096399‐A‐I00) is also acknowledged. B.B.S. acknowledges the Alexander von Humboldt Foundation for a postdoctoral scholarship. Open Access funding is provided by the Max Planck Society.Peer reviewedJohn Wiley & SonsEuropean CommissionMinisterio de Economía y Competitividad (España)Ministerio de Ciencia, Innovación y Universidades (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202120212020info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/226827reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-79776-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683info:eu-repo/grantAgreement/EC/H2020/823717info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-096399-A-I00https://doi.org/10.1002/ange.201915255Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2268272026-05-22T06:33:51Z
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