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 and Dupont, Jairton (2016) Challenging thermodynamics: hydrogenation of benzene to 1,3- cyclohexadiene by Ru@Pt nanoparticles. Chemcatchem, 9 (1). pp. 204-211. ISSN 1867-3899

Full text not available from this repository.


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.

Item Type: Article
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.
Keywords: nanoparticles, ionic liquids, hydrogenation, nonequilibrium, arenes
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number:
Depositing User: Bramwell, Roseanna
Date Deposited: 04 Oct 2016 12:10
Last Modified: 04 May 2020 18:09

Actions (Archive Staff Only)

Edit View Edit View