Print Email Facebook Twitter An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene Title An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene Author Rohling, Roderigh Y. (Eindhoven University of Technology) Uslamin, Evgeny (Eindhoven University of Technology) Zijlstra, Bart (Eindhoven University of Technology) Tranca, Ionut C. (Eindhoven University of Technology) Filot, Ivo A.W. (Eindhoven University of Technology) Hensen, Emiel J.M. (Eindhoven University of Technology) Pidko, E.A. (TU Delft ChemE/Algemeen; Eindhoven University of Technology; TheoMAT group) Date 2018 Abstract The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p-xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents. Subject biomassconfinement effectsDFT calculationsDiels-Alderstructure-activity relations To reference this document use: http://resolver.tudelft.nl/uuid:3280dcee-4d0e-4a84-935f-4d3acdbc0fe6 DOI https://doi.org/10.1021/acscatal.7b03343 ISSN 2155-5435 Source ACS Catalysis, 8 (2), 760-769 Part of collection Institutional Repository Document type journal article Rights © 2018 Roderigh Y. Rohling, Evgeny Uslamin, Bart Zijlstra, Ionut C. Tranca, Ivo A.W. Filot, Emiel J.M. Hensen, E.A. Pidko Files PDF acscatal.7b03343.pdf 4.42 MB Close viewer /islandora/object/uuid:3280dcee-4d0e-4a84-935f-4d3acdbc0fe6/datastream/OBJ/view