Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage

Graphene oxide (GO) and thermally reduced graphene oxide (TRGO) were covalently modified with imidazolium salts through their hydroxyl surface groups. The selective reaction of the -OH groups with p-nitrophenylchloroformate produced labile intermediate organic carbonate functions which were used for the covalent anchoring of a hydroxy-functionalized imidazolium salt. Nanohybrid materials containing iridium N-heterocyclic carbene (NHC)-type organometallic complexes were prepared by causing the imidazolium-functionalized materials to react with [Ir(μ-OMe)(cod)]2. The iridium content of the graphene-based hybrid catalysts, as determined by XPS and ICP-MS was the order of ∼5 and 10 wt.%, for the TRGO and GO-based materials, respectively. The graphene-supported iridium hybrid materials were active in the heterogeneous hydrogen-transfer reduction of cyclohexanone to cyclohexanol with 2-propanol/KOH as the hydrogen source. The thermally reduced graphene-NHC-iridium hybrid catalyst showed the best catalytic performance with an initial TOF of 11.500 h-1, slightly better than the related acetoxy-functionalized NHC iridium homogeneous catalyst. A good catalyst recyclability and stability were achieved.

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Main Authors: Blanco, Matías, Álvarez Rodríguez, Patricia, Blanco Rodríguez, Clara, Jiménez, M. Victoria, Fernández-Tornos, Javier, Pérez-Torrente, Jesús J., Oro, Luis A., Menéndez López, Rosa María
Other Authors: Ministerio de Economía y Competitividad (España)
Format: artículo biblioteca
Published: Elsevier 2015
Online Access:http://hdl.handle.net/10261/111888
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100004837
http://dx.doi.org/10.13039/501100003176
http://dx.doi.org/10.13039/501100003339
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spelling dig-incar-es-10261-1118882018-11-15T07:54:08Z Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage Blanco, Matías Álvarez Rodríguez, Patricia Blanco Rodríguez, Clara Jiménez, M. Victoria Fernández-Tornos, Javier Pérez-Torrente, Jesús J. Oro, Luis A. Menéndez López, Rosa María Ministerio de Economía y Competitividad (España) European Commission Diputación General de Aragón Ministerio de Ciencia e Innovación (España) Ministerio de Educación, Cultura y Deporte (España) Consejo Superior de Investigaciones Científicas (España) Graphene oxide (GO) and thermally reduced graphene oxide (TRGO) were covalently modified with imidazolium salts through their hydroxyl surface groups. The selective reaction of the -OH groups with p-nitrophenylchloroformate produced labile intermediate organic carbonate functions which were used for the covalent anchoring of a hydroxy-functionalized imidazolium salt. Nanohybrid materials containing iridium N-heterocyclic carbene (NHC)-type organometallic complexes were prepared by causing the imidazolium-functionalized materials to react with [Ir(μ-OMe)(cod)]2. The iridium content of the graphene-based hybrid catalysts, as determined by XPS and ICP-MS was the order of ∼5 and 10 wt.%, for the TRGO and GO-based materials, respectively. The graphene-supported iridium hybrid materials were active in the heterogeneous hydrogen-transfer reduction of cyclohexanone to cyclohexanol with 2-propanol/KOH as the hydrogen source. The thermally reduced graphene-NHC-iridium hybrid catalyst showed the best catalytic performance with an initial TOF of 11.500 h-1, slightly better than the related acetoxy-functionalized NHC iridium homogeneous catalyst. A good catalyst recyclability and stability were achieved. The authors thank the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) (Projects Consolider Ingenio 2010 CSD2009-00050 and CTQ 2013-42532-P), and the Diputación General de Aragón (E07) for their financial support. Dr. P. A. thanks MICINN for a Ramón y Cajal contract. J. F-T. and M. B. acknowledge their fellowships from MINECO and MECD (AP2010-0025). Peer Reviewed 2015-03-05T12:32:23Z 2015-03-05T12:32:23Z 2015 2015-03-05T12:32:23Z artículo http://purl.org/coar/resource_type/c_6501 doi: 10.1016/j.carbon.2014.11.016 issn: 0008-6223 Carbon 83: 21-31 (2015) http://hdl.handle.net/10261/111888 10.1016/j.carbon.2014.11.016 http://dx.doi.org/10.13039/501100003329 http://dx.doi.org/10.13039/501100000780 http://dx.doi.org/10.13039/501100004837 http://dx.doi.org/10.13039/501100003176 http://dx.doi.org/10.13039/501100003339 #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-42532-P Preprint http://dx.doi.org/10.1016/j.carbon.2014.11.016 Sí open Elsevier
institution INCAR ES
collection DSpace
country España
countrycode ES
component Bibliográfico
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databasecode dig-incar-es
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libraryname Biblioteca del INCAR España
description Graphene oxide (GO) and thermally reduced graphene oxide (TRGO) were covalently modified with imidazolium salts through their hydroxyl surface groups. The selective reaction of the -OH groups with p-nitrophenylchloroformate produced labile intermediate organic carbonate functions which were used for the covalent anchoring of a hydroxy-functionalized imidazolium salt. Nanohybrid materials containing iridium N-heterocyclic carbene (NHC)-type organometallic complexes were prepared by causing the imidazolium-functionalized materials to react with [Ir(μ-OMe)(cod)]2. The iridium content of the graphene-based hybrid catalysts, as determined by XPS and ICP-MS was the order of ∼5 and 10 wt.%, for the TRGO and GO-based materials, respectively. The graphene-supported iridium hybrid materials were active in the heterogeneous hydrogen-transfer reduction of cyclohexanone to cyclohexanol with 2-propanol/KOH as the hydrogen source. The thermally reduced graphene-NHC-iridium hybrid catalyst showed the best catalytic performance with an initial TOF of 11.500 h-1, slightly better than the related acetoxy-functionalized NHC iridium homogeneous catalyst. A good catalyst recyclability and stability were achieved.
author2 Ministerio de Economía y Competitividad (España)
author_facet Ministerio de Economía y Competitividad (España)
Blanco, Matías
Álvarez Rodríguez, Patricia
Blanco Rodríguez, Clara
Jiménez, M. Victoria
Fernández-Tornos, Javier
Pérez-Torrente, Jesús J.
Oro, Luis A.
Menéndez López, Rosa María
format artículo
author Blanco, Matías
Álvarez Rodríguez, Patricia
Blanco Rodríguez, Clara
Jiménez, M. Victoria
Fernández-Tornos, Javier
Pérez-Torrente, Jesús J.
Oro, Luis A.
Menéndez López, Rosa María
spellingShingle Blanco, Matías
Álvarez Rodríguez, Patricia
Blanco Rodríguez, Clara
Jiménez, M. Victoria
Fernández-Tornos, Javier
Pérez-Torrente, Jesús J.
Oro, Luis A.
Menéndez López, Rosa María
Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
author_sort Blanco, Matías
title Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
title_short Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
title_full Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
title_fullStr Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
title_full_unstemmed Graphene-NHC-iridium hybrid catalysts built through -OH covalent linkage
title_sort graphene-nhc-iridium hybrid catalysts built through -oh covalent linkage
publisher Elsevier
publishDate 2015
url http://hdl.handle.net/10261/111888
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100004837
http://dx.doi.org/10.13039/501100003176
http://dx.doi.org/10.13039/501100003339
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