Using renewable biomass such as carbohydrates for the production of high value bio-based chemicals and high volume fuels is an opportunity to break free from a petroleum-dependent economy with significant environmental benefits. Selective oxidation of 5-hydroxymethylfurfural (HMF), considered a key platform chemical accessible by dehydration of fructose [1], leads to 2,5-diformylfuran (DFF) or/and 2,5-furandicarboxylic acid (FDCA). The latter is considered one of the 12 top value-added bio-based chemicals by the US DOE, and may be used as a replacement for petroleum-based terephthalic and isophthalic acids in the production of various polymers [2]. There are few reports devoted to HMF oxidation into DFF or FDCA using heterogeneous catalysts, mostly supported metal nanoparticles. The reactions typically require harsh conditions (strong base, high pressure) and can suffer from a lack of selectivity [3,4]. A series of catalysts consisting of bis(acetylacetonato)vanadium(IV) supported on silica was prepared following different immobilization strategies. Physical and chemical characterization of the materials was performed to elucidate the nature of the immobilized vanadyl species. Insight into their reactivity was obtained by studying the stoichiometric oxidation of model compounds such as benzylalcohol and benzaldehyde. Finally, their catalytic activity for HMF oxidation was evaluated under mild conditions. Notably, DFF was successfully obtained under ambient pressure and without requiring the presence of a base in the reaction medium.[1] M. H. Tucker, A. J. Crisci, B. N. Wigington, N.Phadke, R. Alamillo, J. Zhang, S.L. Scott, J. A. Dumesic, ACS Catal. 2 (2012 ) 1865[2] T. Werpy, G. Petersen, Top Value Added Chemicals from Biomass. Volume I � Results of Screening for potential candidates from sugars and synthesis gas, U.S. D.O.E., 2004 [3]  Y.Y. Gorbanev, S. K. Klitgaard, J. M. Woodley, C. H. Christensen, A. Riisager,  ChemSusChem 2 (2009 ) 67[4] S. E. Davis, B. N. Zope, R. J. Davis, Green Chem. 14 (2012 ) 143

Oxidation of 5-hydroxymethylfurfural catalyzed by vanadyl immobilized on silica

248th National Meeting (2014)

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