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handle: 10261/210196
[EN] Ruthenium nanoparticles (Ru NPs) supported on reduced-graphene oxide doped with N (NH2-rGO) was synthesized and used for the selective hydrogenation of fatty acids to alcohols, being the hydrogenation of palmitic acid selected as model. Ru was stabilized forming uniform nanometer size particles on N-doped graphene (Ru/NH2-rGO). The resultant catalyst was very selective for the carbonyl reduction giving 93% of the aliphatic alcohol at 99% conversion. The Ru/NH2-rGO catalysts was more active and selective than the corresponding Ru on non-doped graphene (Ru/rGO) or Ru on carbon (Ru/C). Mechanistic studies points to a dual mechanism for H-2 dissociation, i.e. homolytic and heterolytic cleavage exists on the Ru/NH2-rGO, while only the homolytic H-2 dissociation occurs on Ru/rGO. This heterolytic splitting, which activates the carbonyl groups and facilitates the hydrogenation of aliphatic acids, is due to the presence of basic centres next to the Ru atoms. The presence of N atoms also increases the stability of the catalyst, allowing a reuse up to four times. (C) 2019 Elsevier Inc. All rights reserved.
The authors thank Institute de Tecnologia Quimica (ITQ), Consejo Superior de Investigaciones Cientificas (CSIC) and Universitat Politecnica de Valencia (UPV) for the facilities and Severo Ochoa excellence programme, "Juan de la Cierva" programme and Primeros Proyectos de Investigacion (PAID-06-18) for financial support. We gratefully acknowledge Prof. A. Corma for his invaluable contribution to this research. We also thank the Electron Microscopy Service of the UPV for TEM facilities, Jose A. Vidal-Moya (ITQ CSIC-UPV) for NMR measurements and J. Gaona and C. Morales for their assistance in catalytic reactions.
QUIMICA ORGANICA, [CHIM] Chemical Sciences, Hydrogenation, Dual-site mechanism, Fatty acids, Heterolytic hydrogen splitting, Ru nanoparticles, N-doped graphene
QUIMICA ORGANICA, [CHIM] Chemical Sciences, Hydrogenation, Dual-site mechanism, Fatty acids, Heterolytic hydrogen splitting, Ru nanoparticles, N-doped graphene
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