10.1002/anie.201904366
Angewandte Chemie International Edition
COMMUNICATION
The authors thank ERC Advanced Grant (MONACAT 2015-
694159) and IDEX/Chaires d’attractivité de l’Université Fédérale
de Toulouse Midi-Pyrénées for financial support.
(a)
Keywords: biomass • catalysis in solution • hydrodeoxygenation
• magnetic hyperthermia • nanoparticles
(b)
(c)
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Scheme 2. Hydrodeoxygenation of biomass platform molecules catalyzed by
NPs 1. Hydrodeoxygenation of furfural using (a) 0.25 mol% and (b) 1.0 mol %
of Ru loading. (c) Hydrodeoxygenation of HMF.
In this paper, we demonstrate that magnetic heating allows the
performance of catalytic reactions in solution that are otherwise
carried out at a gas-solid interphase involving high temperatures
and high H2 pressures. As a proof of concept, selective
hydrodeoxygenation of acetophenone has been performed using
FeC@Ru NPs which combine the high heating power of the
Fe2.2C NPs with the high activities of Ru. Remarkably, the close
contact between the heating agent and the catalyst promotes the
reaction and considerably increases the activity of the catalyst.
The reaction is highly selective and occurs without the
hydrogenation of the aromatic ring, which may be explained by
the high temperatures and/or the formation of the Fe-Ru alloy
during the catalysis. Magnetic heating has allowed us to perform
hydrodeoxygenation reactions using low catalyst loadings and
very low pressures of H2 (3 bar in all the cases studied), which
can be of interest in terms of scalability of the process. Finally,
furfural and HMF, two platform molecules derived from biomass,
were successfully and very selectively transformed into the
corresponding alkylfurans 2-MF and 2,5-DMF respectively. This
may be of further interest to perform selective oxygen removal
avoiding ring-opening of heterocyclic molecules. In conclusion,
these results prove the high potential of magnetic heating of
magnetic NPs for catalysis in solution and, in the context of
biomass valorization, demonstrate that using this new approach,
the reactions can be performed very selectively under much
milder conditions, and remarkably, very low pressures of H2.
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