Universität zu Köln

Weilhard, Andreas, Abarca, Gabriel ORCID: 0000-0001-8477-2275, Viscardi, Janine, Prechtl, Martin H. G. ORCID: 0000-0003-2155-8006, Scholten, Jackson D., Bernardi, Fabiano ORCID: 0000-0001-6817-6860, Baptista, Daniel L. and Dupont, Jairton ORCID: 0000-0003-3237-0770 (2017). Challenging Thermodynamics: Hydrogenation of Benzene to 1,3-Cyclohexadiene by Ru@Pt Nanoparticles. ChemCatChem, 9 (1). S. 204 - 212. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1867-3899

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Abstract

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 [Pt-2(dba)(3)] (dba = dibenzylideneacetone) in 1-n-butyl-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 degrees C, 6 bar of H-2) dissolved in n-heptane by these bimetallic NPs in BMI.PF6 affords 1,3-cyclohexadiene with an unprecedented 21% selectivity at 5% benzene conversion. Conversely, almost no 1,3-cyclohexadiene was observed when using monometallic Pt-0 or Ru-0 NPs under the same reaction conditions and benzene conversions. This study reveals that the selectivity is related to synergetic effects of the bimetallic composition of the catalyst material as well as to the performance under biphasic reaction conditions. It is proposed that colloidal metal catalysts in ILs and under multiphase conditions (dynamic asymmetric mixtures) can operate far from the thermodynamic equilibrium akin to chemically active membranes.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Weilhard, Andreas UNSPECIFIED UNSPECIFIED UNSPECIFIED Abarca, Gabriel UNSPECIFIED orcid.org/0000-0001-8477-2275 UNSPECIFIED Viscardi, Janine UNSPECIFIED UNSPECIFIED UNSPECIFIED Prechtl, Martin H. G. UNSPECIFIED orcid.org/0000-0003-2155-8006 UNSPECIFIED Scholten, Jackson D. UNSPECIFIED UNSPECIFIED UNSPECIFIED Bernardi, Fabiano UNSPECIFIED orcid.org/0000-0001-6817-6860 UNSPECIFIED Baptista, Daniel L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Dupont, Jairton UNSPECIFIED orcid.org/0000-0003-3237-0770 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-243079
DOI:	10.1002/cctc.201601196
Journal or Publication Title:	ChemCatChem
Volume:	9
Number:	1
Page Range:	S. 204 - 212
Date:	2017
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1867-3899
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language IMIDAZOLIUM IONIC LIQUIDS; SELECTIVE HYDROGENATION; ARENE HYDROGENATION; NONEQUILIBRIUM THERMODYNAMICS; HETEROGENEOUS CATALYSIS; CYCLOHEXENE; RUTHENIUM; PT(111); DEHYDROGENATION; 1,3-BUTADIENE Multiple languages Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/24307