title: From Biomass-Derived Furans to Aromatics with Ethanol over Zeolite.
abstract: We report a novel catalytic conversion of biomass-derived furans and alcohols to aromatics over zeolite catalysts. Aromatics are formed via Diels-Alder cycloaddition with ethylene, which is produced in situ from ethanol dehydration. The use of liquid ethanol instead of gaseous ethylene, as the source of dienophile in this one-pot synthesis, makes the aromatics production much simpler and renewable, circumventing the use of ethylene at high pressure. More importantly, both our experiments and theoretical studies demonstrate that the use of ethanol instead of ethylene, results in significantly higher rates and higher selectivity to aromatics, due to lower activation barriers over the solid acid sites. Synchrotron-diffraction experiments and proton-affinity calculations clearly suggest that a preferred protonation of ethanol over the furan is a key step facilitating the Diels-Alder and dehydration reactions in the acid sites of the zeolite.
authors.affiliation: Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, OX1 3QR, UK.
authors.forename: Ivo F
authors.identifier: 0000-0002-4356-061X
authors.initials: IF
authors.lastname: Teixeira
authors.affiliation: Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, OX1 3QR, UK.
authors.forename: Benedict T W
authors.identifier: 0000-0002-4853-0196
authors.initials: BT
authors.lastname: Lo
authors.affiliation: Department of Chemical Engineering, University of Pittsburgh, Pittsburgh, PA, 15261, USA.
authors.forename: Pavlo
authors.initials: P
authors.lastname: Kostetskyy
authors.affiliation: Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK.
authors.forename: Michail
authors.identifier: 0000-0001-8338-8706
authors.initials: M
authors.lastname: Stamatakis
authors.affiliation: Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, OX1 3QR, UK.
authors.forename: Lin
authors.initials: L
authors.lastname: Ye
authors.affiliation: Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, UK.
authors.forename: Chiu C
authors.initials: CC
authors.lastname: Tang
authors.affiliation: Department of Chemical Engineering, University of Pittsburgh, Pittsburgh, PA, 15261, USA. gmpourmp@pitt.edu.
authors.forename: Giannis
authors.identifier: 0000-0002-3063-0607
authors.initials: G
authors.lastname: Mpourmpakis
authors.affiliation: Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, OX1 3QR, UK. edman.tsang@chem.ox.ac.uk.
authors.forename: Shik Chi Edman
authors.identifier: 0000-0002-8796-3146
authors.initials: SC
authors.lastname: Tsang
keywords: biomass; cycloaddition; ethanol; structure elucidation; zeolites