466460 Tandem Catalysis in a New, Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
Here, we show that the hydrogenated DA adducts can also be conveniently converted to renewable aromatics in a solid-phase reaction (i.e., without any solvent), using only H-Y zeolites . The remarkable performance of these catalysts in the solid-phase can still be further enhanced upon the addition of a small amount of a dehydrogenation catalyst (e.g., 1 wt. % Pd/C or Pt/C) or by the use of bifunctional catalysts (e.g., 1 wt. % Pd/H-Y or Pt/H-Y). Monitoring the evolution of H2, H2O, and CO2 as a function of temperature and time provided valuable insights into the mechanism of aromatization and decarboxylation. The effects of various experimental parameters, different concentrations of H-Y zeolites and dehydrogenation catalysts, on the reactivity of MFMA[H] were studied to effectively control the reaction rate and product selectivity. The use of Pt/H-Y (Si/Al=30) resulted in an excellent yield of 94% total aromatics, which is the highest reported to date. The bifunctional catalysts were also found highly selective for the aromatization of other hydrogenated DA furan derivatives. The development of new heterogeneous catalysts for the production of aromatic chemicals from biomass-derived furanics can therefore be guided by taking into account the influence of the acidic and textural properties of H-Y zeolites on selectivity.
 S. Thiyagarajan, H. C. Genuino, M. Śliwa, J. C. van der Waal, E. de Jong, J. van Haveren, B. M. Weckhuysen, P. C. A. Bruijnincx, D. S. van Es. Substituted phthalic anhydrides from bio-based furanics: A new approach to renewable aromatics, ChemSusChem 2015, 8, 3052-3056.
 H. C. Genuino, S. Thiyagarajan, J. C. van der Waal, E. de Jong, J. van Haveren, D. S. van Es, B. M. Weckhuysen, P. C. A. Bruijnincx. Selectivity control in solid acid and Pd-catalyzed tandem aromatization of bio-based furanics, Manuscript in preparation.
 S. Thiyagarajan, H. C. Genuino, J. C. van der Waal, E. de Jong, B. M. Weckhuysen, J. van Haveren, P. C. A. Bruijnincx, D. S. van Es. A facile solid-phase route to renewable aromatic chemicals from biobased furanics, Angew. Chem. Int. Ed. 2016, 55, 1368-1371.