Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts

[EN] The development of a circular economy is a key target to reduce our dependence on fossil fuels and create more sustainable processes. Concerning hydrogen as an energy vector, the use of liquid organic hydrogen carriers is a promising strategy, but most of them present limitations for hydrogen r...

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Authors: Gutiérrez-Tarriño, Silvia, Oña-Burgos, Pascual|||0000-0002-2341-7867, Rojas-Buzo, Sergio, Ortuño, Manuel A.
Format: article
Publication Date:2022
Country:España
Institution:Universitat Politècnica de València (UPV)
Repository:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Language:English
OAI Identifier:oai:riunet.upv.es:10251/193544
Online Access:https://riunet.upv.es/handle/10251/193544
Access Level:Open access
Keyword:Hydrogen delivery
Green hydrogen
Alkene hydrosilylation
Dehydrogenative coupling
Cobalt complex
Homogeneous catalysis
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dc.title.none.fl_str_mv Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
title Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
spellingShingle Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
Gutiérrez-Tarriño, Silvia
Hydrogen delivery
Green hydrogen
Alkene hydrosilylation
Dehydrogenative coupling
Cobalt complex
Homogeneous catalysis
title_short Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
title_full Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
title_fullStr Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
title_full_unstemmed Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
title_sort Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts
dc.creator.none.fl_str_mv Gutiérrez-Tarriño, Silvia
Oña-Burgos, Pascual|||0000-0002-2341-7867
Rojas-Buzo, Sergio
Ortuño, Manuel A.
author Gutiérrez-Tarriño, Silvia
author_facet Gutiérrez-Tarriño, Silvia
Oña-Burgos, Pascual|||0000-0002-2341-7867
Rojas-Buzo, Sergio
Ortuño, Manuel A.
author_role author
author2 Oña-Burgos, Pascual|||0000-0002-2341-7867
Rojas-Buzo, Sergio
Ortuño, Manuel A.
author2_role author
author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Departamento de Química
Escuela Técnica Superior de Ingeniería Industrial
Xunta de Galicia
Junta de Andalucía
Agencia Estatal de Investigación
European Regional Development Fund
Universitat Politècnica de València
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Hydrogen delivery
Green hydrogen
Alkene hydrosilylation
Dehydrogenative coupling
Cobalt complex
Homogeneous catalysis
topic Hydrogen delivery
Green hydrogen
Alkene hydrosilylation
Dehydrogenative coupling
Cobalt complex
Homogeneous catalysis
description [EN] The development of a circular economy is a key target to reduce our dependence on fossil fuels and create more sustainable processes. Concerning hydrogen as an energy vector, the use of liquid organic hydrogen carriers is a promising strategy, but most of them present limitations for hydrogen release, such as harsh reaction conditions, poor recyclability, and low-value byproducts. Herein, we present a novel sustainable methodology to produce value-added silicon precursors and concomitant hydrogen via dehydrogenative coupling by using an air- and water-stable cobalt-based catalyst synthesized from dieap and commercially available starting materials. This methodology is applied to the one-pot synthesis of a wide range of alkoxy- substituted silanes using different hydrosilanes and terminal alkenes as reactants in alcohols as green solvents under mild reaction conditions (room temperature and 0.1 mol % cobalt loading). We also demonstrate that the selectivity toward hydrosilylation/hydroalkoxysilylation can be fully controlled by varying the alcohol/water ratio. This implies the development of a circular approach for hydrosilylation/hydroalkoxysilylation reactions, which is unprecedented in this research field up to date. Kinetic and in situ spectroscopic studies (electron paramagnetic resonance, nuclear magnetic resonance, and electrospray ionization mass spectrometry), together with density functional theory simulations, further provide a detailed mechanistic picture of the dehydrogenative coupling and subsequent hydrosilylation. Finally, we illustrate the application of our catalytic system in the synthesis of an industrially relevant polymer precursor coupled with the production of green hydrogen on demand.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022-12-19
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/193544
url https://riunet.upv.es/handle/10251/193544
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2020-119116RA-I00 REDES METAL ORGANICAS PARA LA VALORIZACION DE BIOMASA A TRAVES DE SIMULACIONES DE SISTEMAS CATALITICOS
Junta de Andalucía http://dx.doi.org/10.13039/501100011011 P20_01027
Junta de Andalucía http://dx.doi.org/10.13039/501100011011 PYC 20 RE 060 UAL
Xunta de Galicia http://dx.doi.org/10.13039/501100010801 ED431H 2020%2F21
Xunta de Galicia http://dx.doi.org/10.13039/501100010801 ED431G 2019%2F03
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 RTI2018-096399-A-I00 CLUSTERES MULTIMETALICOS Y SUBNANOMETRICOS SOPORTADOS: SINTESIS, ESTRUCTURA Y DINAMISMO ATOMICO, Y EMPLEO COMO CATALIZADORES EN LA VALORIZACION DE METANO Y ALCANOS LIGEROS
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 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:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
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spelling Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based CatalystsGutiérrez-Tarriño, SilviaOña-Burgos, Pascual|||0000-0002-2341-7867Rojas-Buzo, SergioOrtuño, Manuel A.Hydrogen deliveryGreen hydrogenAlkene hydrosilylationDehydrogenative couplingCobalt complexHomogeneous catalysis[EN] The development of a circular economy is a key target to reduce our dependence on fossil fuels and create more sustainable processes. Concerning hydrogen as an energy vector, the use of liquid organic hydrogen carriers is a promising strategy, but most of them present limitations for hydrogen release, such as harsh reaction conditions, poor recyclability, and low-value byproducts. Herein, we present a novel sustainable methodology to produce value-added silicon precursors and concomitant hydrogen via dehydrogenative coupling by using an air- and water-stable cobalt-based catalyst synthesized from dieap and commercially available starting materials. This methodology is applied to the one-pot synthesis of a wide range of alkoxy- substituted silanes using different hydrosilanes and terminal alkenes as reactants in alcohols as green solvents under mild reaction conditions (room temperature and 0.1 mol % cobalt loading). We also demonstrate that the selectivity toward hydrosilylation/hydroalkoxysilylation can be fully controlled by varying the alcohol/water ratio. This implies the development of a circular approach for hydrosilylation/hydroalkoxysilylation reactions, which is unprecedented in this research field up to date. Kinetic and in situ spectroscopic studies (electron paramagnetic resonance, nuclear magnetic resonance, and electrospray ionization mass spectrometry), together with density functional theory simulations, further provide a detailed mechanistic picture of the dehydrogenative coupling and subsequent hydrosilylation. Finally, we illustrate the application of our catalytic system in the synthesis of an industrially relevant polymer precursor coupled with the production of green hydrogen on demand.This work has received financial support from Spanish Government (RTI2018-096399-A-I00 and PID2020-119116RA-I00), Junta de Andalucia (P20_01027 and PYC 20 RE 060 UAL), Xunta Distinguished Researcher program (ED431H 2020/21), the Xunta de Galicia (Centro singular de investigacion de Galicia accreditation 2019-2022, ED431G 2019/03), and the European Union (European Regional Development Fund, ERDF). S.R.-B. acknowledges the Margarita Salas grant financed by Ministerio de Universidades, Spain, and funded by the European Union-Next Generation EU. M.A.O. acknowledges CESGA ("Centro de Super-computacion de Galicia") for providing generous computa-tional resources.American Chemical SocietyInstituto Universitario Mixto de Tecnología QuímicaDepartamento de QuímicaEscuela Técnica Superior de Ingeniería IndustrialXunta de GaliciaJunta de AndalucíaAgencia Estatal de InvestigaciónEuropean Regional Development FundUniversitat Politècnica de ValènciaRepositorio Institucional de la Universitat Politècnica de València Riunet20222022-12-19journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/193544reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2020-119116RA-I00 REDES METAL ORGANICAS PARA LA VALORIZACION DE BIOMASA A TRAVES DE SIMULACIONES DE SISTEMAS CATALITICOSJunta de Andalucía http://dx.doi.org/10.13039/501100011011 P20_01027Junta de Andalucía http://dx.doi.org/10.13039/501100011011 PYC 20 RE 060 UALXunta de Galicia http://dx.doi.org/10.13039/501100010801 ED431H 2020%2F21Xunta de Galicia http://dx.doi.org/10.13039/501100010801 ED431G 2019%2F03Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 RTI2018-096399-A-I00 CLUSTERES MULTIMETALICOS Y SUBNANOMETRICOS SOPORTADOS: SINTESIS, ESTRUCTURA Y DINAMISMO ATOMICO, Y EMPLEO COMO CATALIZADORES EN LA VALORIZACION DE METANO Y ALCANOS LIGEROSopen accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento (by)http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1935442026-06-13T07:49:27Z
score 15.300724

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