One-Pot Synthesis of 2,5-Diformylfuran from Fructose by Bifunctional Polyaniline-Supported Heteropolyacid Hybrid Catalysts

We report the preparation of bifunctional hybrid catalysts by supporting H3PMo12O40 (PMo12) heteropolyacid (HPA) on polyaniline (PAN) or formyl-functionalized PAN (F-PAN) for the one-pot and one-step synthesis of 2,5-diformylfuran (DFF) from fructose via 5-hydroxymethylfurfural (HMF) intermediate. We show that the PMo12 HPA is the main active species for both fructose dehydration and HMF oxidation owing to its BrOnsted acidic and redox characters. However, the anchoring of PMo12 on PAN reduces the BrOnsted acidity by acid-base interaction between protons in HPA and quinoid diimine structure in PAN, thereby reducing the dehydration performance. We demonstrate that the catalytic dehydration performance of the hybrid catalyst could be strengthened by grafting formyl groups on PAN before HPA anchoring. The highest DFF yield of 76.7% is obtained by conducting the one-pot reaction over the 40-PMo12/F-3-PAN catalyst at 413 K for 7 h in air, wherein the side-reactions of fructose or HMF degradation and HMF rehydration have been significantly reduced. This hybrid catalyst is reusable without significant activity loss, highlighting the designing of stable inorganic-organic hybrid catalysts for producing valuable hexose-derived platform chemicals.