Aerobic oxidation of biomass derived 5-hydroxymethylfurfural into 5-hydroxymethyl-2-furancarboxylic acid catalyzed by a montmorillonite K-10 clay immobilized molybdenum acetylacetonate complex

Abstract

In this study, we have successfully prepared a heterogeneous catalyst (K-10 clay-Mo) by the immobilization of bis(acetylacetonato) dioxo-molybdenum(VI) [MoO₂(acac)₂] on montmorillonite K-10 clay. The structure of the resultant catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electronic microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The catalytic activity of K-10 clay-Mo was tested in the aerobic oxidation of 5-hydroxymethylfurfural (HMF). Although a molecule of HMF contains one hydroxyl group and one aldehyde group, to our surprise, the catalyst showed high catalytic activity for the oxidation of the aldehyde group of HMF into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). A variety of important reaction parameters such as the reaction temperature, catalyst amount, and solvent were explored. HMFCA could be obtained in a high yield of 86.9% with a HMF conversion of 100% after a short reaction time of 3 h in toluene. More importantly, the catalyst K-10 clay-Mo could be reused several times without a significant loss of its catalytic activity.