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Challenging thermodynamics: hydrogenation of benzene to 1,3- cyclohexadiene by Ru@Pt nanoparticles

Weilhard, Andreas; Abarca, Gabriel A.; Viscardi, Janine; Prechtl, Martin H.G.; Scholten, Jackson D.; Bernandi, Fabiano; Baptista, Daniel; Dupont, Jairton

Challenging thermodynamics: hydrogenation of benzene to 1,3- cyclohexadiene by Ru@Pt nanoparticles Thumbnail


Andreas Weilhard

Gabriel A. Abarca

Janine Viscardi

Martin H.G. Prechtl

Jackson D. Scholten

Fabiano Bernandi

Daniel Baptista

Jairton Dupont


Since the earliest reports on catalytic benzene hydrogenation, 1,3-cyclohexadiene and cyclohexene have been proposed as key intermediates. However, the former has never been obtained with remarkable selectivity. Herein we report the first partial hydrogenation of benzene towards 1,3 cyclohexadiene under mild conditions in a catalytic biphasic system consisting of Ru@Pt nanoparticles (NPs) in ionic liquid (IL). The tandem reduction of [Ru(COD)(2-methylallyl)2] (COD = 1,5 cyclooctadiene) followed by decomposition of [Pt2(dba)3] (dba = dibenzylideneacetone) in 1-nbutyl- 3 methylimidazolium hexafluorophosphate (BMI.PF6) IL under hydrogen affords core-shell Ru@Pt NPs of 2.9 ± 0.2 nm. The hydrogenation of benzene (60 ºC, 6 bar of H2) dissolved in nheptane by these bimetallic NPs in BMI.PF6 affords 1,3- cyclohexadiene in unprecedented 21% selectivity at 5% benzene conversion. On opposition, almost no 1,3-cyclohexadiene was observed using monometallic Pt(0) or Ru(0) NPs under the same reaction conditions and benzene conversions. The study reveals that the selectivity is related to synergetic effects of the bimetallic composition of the catalyst material as well as the performance under biphasic reaction conditions. It is proposed that colloidal metal catalysts in ILs and under multiphase conditions (“dynamic asymmetric mixture”) can operate far from the thermodynamic equilibrium akin to chemically active membranes.

Journal Article Type Article
Acceptance Date Sep 27, 2016
Online Publication Date Sep 27, 2016
Deposit Date Oct 4, 2016
Publicly Available Date Oct 4, 2016
Journal Chemcatchem
Print ISSN 1867-3880
Electronic ISSN 1867-3899
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 9
Issue 1
Keywords nanoparticles, ionic liquids, hydrogenation, nonequilibrium, arenes
Public URL
Publisher URL
Additional Information This is the peer reviewed version of the following article: A. Weilhard, G. Abarca, J. Viscardi, M. H. G. Prechtl, J. D. Scholten, F. Bernardi, D. L. Baptista, J. Dupont, ChemCatChem 2017, 9, 204., which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.


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