Application of Polyoxometalates as Efficient and Green Catalyst for Catalytic Upgrading of Cellulosic Biomass

Abstract

In recent years, the research on the sustainable production of energy, transportation fuels, and materials has been incentivized. Non-food and preferably waste biomass has been identified as a commercially-feasible renewable alternative to fossilized carbons for producing fuels and chemicals. The chemocatalytic value addition of biomass, where the oxygen-rich biopolymers are selectively deconstructed into functionally-rich small organic molecules, is of particular interest. A new generation of robust, inexpensive, and environment-friendly catalysts are crucial for the chemocatalytic route. Over the past years, heteropolyacids (HPAs) are increasingly being used as a catalyst in the chemistry of renewables and biomass value addition. HPAs have been used in the hydrolysis and dehydration of pentose and hexose sugars in biomass into furfural and 5- (hydroxymethyl)furfural (HMF), respectively. Furfural, levulinic acid, and HMF act as renewable chemical building blocks that can be converted into commodity chemicals and materials via chemical or catalytic transformations. The proposed work is intended to explore the efficiency of various homogenous and heterogeneous HPA catalysts for the catalytic upgrading of biomass-derived chemical intermediates into value-added chemicals. HPA-based homogeneous and heterogeneous catalysts were used for the acetalization, esterification, and Baeyer-Villiger oxidation reactions of various biomass-derived chemical intermediates. The reaction conditions were optimized on various parameters such as temperature, duration, loading of reactant, and loading of catalyst. The cyclic acetals of biomass-derived furfural were prepared in high isolated yields in refluxing benzene in the presence of the phosphotungstic acid (PTA) catalyst. The PTA catalyst was successfully recovered and reused several times without significant loss in mass or activity. The esterification of saturated and unsaturated free fatty acids such as oleic acid and stearic acid were conducted in the presence of PTA catalyst as an efficient and recyclable catalyst. 2-Furanone was prepared by the selective oxidation of furfural using hydrogen peroxide as an inexpensive oxidant and PTA supported on ammonium zeolites as the catalyst. A scalable and high yielding preparation of alkyl benzoates and alkyl 2-furoates has also been reported.