127881 20231023120953.0 doi 10.1021/acsanm.9b02398 sideral 117656 ART-2020-117656 eng Sanchez-Page, B. (orcid)0000-0001-6675-7450 Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation 2020 Thermally partially reduced graphene oxide has been covalently modified with 3-methyl-4-phenyl-1, 2, 3-triazolium salts making use of the epoxy functionalities on the carbon nanomaterial. Characterization of the functionalized materials through adequate solid characterization techniques, particularly X-ray photoelectron spectroscopy (XPS), allows one to follow the stepwise building up of the triazolium fragments on the graphene oxide attached to the wall via covalent C-N linkage. The hydroxyl-triazolium-functionalized materials have been used to prepare rhodium hybrid materials containing either alkoxo or triazolylidene molecular rhodium(I) complexes depending on the protection of the hydroxyl groups present in the material. Characterization of the heterogeneous systems, especially by means of XPS and extended X-ray absorption fine structure (EXAFS) spectroscopy, has evidenced the coordination sphere of the supported rhodium(I) complexes in both rhodium hybrid materials. The graphene-oxide-supported rhodium triazolylidene hybrid catalysts show excellent activity, comparable to that of the homogeneous [RhI(cod)(Triaz)] (Triaz = 1, 4-diphenyl-3-methyl-1, 2, 3-triazol-5-ylidene) catalyst, for the hydrosilylation of terminal and internal alkynes. In addition, these catalysts have shown good selectivity to the beta-(Z) vinylsilane isomers (for the not hindered terminal substrates) or syn-additions (for the internal substrates). In contrast to the rhodium(I)-alkoxo-based hybrid material, the silyl-protected rhodium(I)-triazolylidene-based hybrid catalyst can be reused in consecutive cycles without loss of activity maintaining the selectivity. The lack of leaching of active rhodium species demonstrates the strength of the C-N covalent bond of the triazolylidene linker to the graphitic wall. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA/E12-R17 info:eu-repo/grantAgreement/ES/DGA-FSE/Building Europe from Aragon info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R info:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-P info:eu-repo/grantAgreement/ES/MICINN-FEDER/RTI2018-098537-B-C22 info:eu-repo/semantics/openAccess by-nc-nd http://creativecommons.org/licenses/by-nc-nd/3.0/es/ 5.097 2020 NANOSCIENCE & NANOTECHNOLOGY 48 / 106 = 0.453 2020 Q2 T2 MATERIALS SCIENCE, MULTIDISCIPLINARY 101 / 333 = 0.303 2020 Q2 T1 1.227 2020 Materials Science (miscellaneous) 2020 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Jimenez, M.V. Universidad de Zaragoza (orcid)0000-0002-0545-9107 Perez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Passarelli, V. Universidad de Zaragoza (orcid)0000-0002-1735-6439 Blasco, J. Universidad de Zaragoza (orcid)0000-0002-9706-3272 Subias, G. Universidad de Zaragoza (orcid)0000-0002-9029-1977 Granda, M. Alvarez, P. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2003 395 Universidad de Zaragoza Dpto. Física Materia Condensa. Área Física Materia Condensada 3, 2 (2020), 1640-1655 ACS appl. nano mater. ACS APPLIED NANO MATERIALS 2574-0970 2315343 http://zaguan.unizar.es/record/127881/files/texto_completo.pdf Postprint 887810 http://zaguan.unizar.es/record/127881/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:127881 articulos driver 2023-10-23-11:03:37 ARTICLE