title: Selectivity Control in the Tandem Aromatization of Bio-Based Furanics Catalyzed by Solid Acids and Palladium.
abstract: Bio-based furanics can be aromatized efficiently by sequential Diels-Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H-Y and Pd/C, the hydrogenated DA adduct of 2-methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3-methylphthalic anhydride and o- and m-toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3-methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H-Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite-to-Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3-methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H-Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations.
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Homer C
authors.initials: HC
authors.lastname: Genuino
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.|Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA, Wageningen, The Netherlands.
authors.forename: Shanmugam
authors.initials: S
authors.lastname: Thiyagarajan
authors.affiliation: Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands.
authors.forename: Jan C
authors.initials: JC
authors.lastname: van der Waal
authors.affiliation: Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands.
authors.forename: Ed
authors.initials: E
authors.lastname: de Jong
authors.affiliation: Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA, Wageningen, The Netherlands.
authors.forename: Jacco
authors.initials: J
authors.lastname: van Haveren
authors.affiliation: Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA, Wageningen, The Netherlands.
authors.forename: Daan S
authors.initials: DS
authors.lastname: van Es
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
authors.forename: Pieter C A
authors.identifier: http://orcid.org/0000-0001-8134-0530
authors.initials: PC
authors.lastname: Bruijnincx
mesh_terms: D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D005663:Furans / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D010165:Palladium / Q000737:chemistry*; D013227:Steam; D017641:Zeolites / Q000737:chemistry
chemical_list: D005663:Furans; D013227:Steam; D017641:Zeolites; C029060:2-methylfuran; D010165:Palladium; D002244:Carbon
keywords: acidity; biomass; hydrogenation; palladium; zeolites