Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity

Three metal-organic frameworks with the general formula Co(BPZX) (BPZX = 3-X-4,4′-bipyrazolate, X = H, NH, NO) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O as oxidant...

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Autores: Nowacka, Anna, Vismara, R., Mercuri, G, Moroni, M., Palomino, Miguel, Domasevitch, K.V., Di Nicola, C., Pettinari, Claudio, Giambastiani, Giuliano, Llabrés i Xamena, Francesc X., Galli, Simona, Rossin, Andrea
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
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:10261/226613
Acceso en línea:http://hdl.handle.net/10261/226613
Access Level:acceso abierto
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spelling Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent SelectivityNowacka, AnnaVismara, R.Mercuri, GMoroni, M.Palomino, MiguelDomasevitch, K.V.Di Nicola, C.Pettinari, ClaudioGiambastiani, GiulianoLlabrés i Xamena, Francesc X.Galli, SimonaRossin, AndreaThree metal-organic frameworks with the general formula Co(BPZX) (BPZX = 3-X-4,4′-bipyrazolate, X = H, NH, NO) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O as oxidant. O adsorption isotherms collected at p = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O)), in line with its highest BET specific surface area (926 m/g) in comparison with those of Co(BPZNH) (317 m/g) and Co(BPZNO) (645 m/g). The O isosteric heat of adsorption (Q) trend follows the order Co(BPZ) > Co(BPZNH) > Co(BPZNO). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: While cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH) as the catalyst (69% selectivity to PP under the same experimental conditions).S.G., R.V., and M.M. acknowledge Università dell’Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 × 9ATP_002). This project has also received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. The authors are also grateful to Dr. Giulia Tuci (CNR-ICCOM Florence, Italy) for help with the XPS curve fitting. The Microscopy Service of the Universitat Politècnica de València is gratefully acknowledged for the electron microscopy measurements.ACS PublicationsEuropean CommissionMinisterio de Economía y Competitividad (España)Ministerio de Ciencia, Innovación y Universidades (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2021202120202021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/226613reponame: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#info:eu-repo/grantAgreement/EC/H2020/641887info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/MAT2017-82288-C2-1-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683http://dx.doi.org/10.1021/acs.inorgchem.0c00481Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2266132026-05-22T06:33:51Z
dc.title.none.fl_str_mv Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
title Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
spellingShingle Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
Nowacka, Anna
title_short Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
title_full Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
title_fullStr Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
title_full_unstemmed Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
title_sort Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
dc.creator.none.fl_str_mv Nowacka, Anna
Vismara, R.
Mercuri, G
Moroni, M.
Palomino, Miguel
Domasevitch, K.V.
Di Nicola, C.
Pettinari, Claudio
Giambastiani, Giuliano
Llabrés i Xamena, Francesc X.
Galli, Simona
Rossin, Andrea
author Nowacka, Anna
author_facet Nowacka, Anna
Vismara, R.
Mercuri, G
Moroni, M.
Palomino, Miguel
Domasevitch, K.V.
Di Nicola, C.
Pettinari, Claudio
Giambastiani, Giuliano
Llabrés i Xamena, Francesc X.
Galli, Simona
Rossin, Andrea
author_role author
author2 Vismara, R.
Mercuri, G
Moroni, M.
Palomino, Miguel
Domasevitch, K.V.
Di Nicola, C.
Pettinari, Claudio
Giambastiani, Giuliano
Llabrés i Xamena, Francesc X.
Galli, Simona
Rossin, Andrea
author2_role author
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]
description Three metal-organic frameworks with the general formula Co(BPZX) (BPZX = 3-X-4,4′-bipyrazolate, X = H, NH, NO) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O as oxidant. O adsorption isotherms collected at p = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O)), in line with its highest BET specific surface area (926 m/g) in comparison with those of Co(BPZNH) (317 m/g) and Co(BPZNO) (645 m/g). The O isosteric heat of adsorption (Q) trend follows the order Co(BPZ) > Co(BPZNH) > Co(BPZNO). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: While cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH) as the catalyst (69% selectivity to PP under the same experimental conditions).
publishDate 2020
dc.date.none.fl_str_mv 2020
2021
2021
2021
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/10261/226613
url http://hdl.handle.net/10261/226613
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/EC/H2020/641887
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/MAT2017-82288-C2-1-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683
http://dx.doi.org/10.1021/acs.inorgchem.0c00481
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
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