Exploiting H-transfer as a tool for the catalytic reduction of bio-based building blocks: the gas-phase production of 2-methylfurfural using a FeVO4 catalyst

Abstract

Over the past decade, a great deal of effort has been devoted to developing reductive processes in the field of biomass valorisation for the sustainable production of bio-fuel additives and chemicals. Catalytic transfer hydrogenation, which uses alcohol as the hydrogen source, is an interesting approach that avoids the use of both high H₂ pressure and precious metal catalysts. In this work, the vapour-phase production of 2-methylfuran from biomass-derived furfural (FU), using methanol as the H-transfer agent and FeVO₄ catalyst, was studied. At a temperature of 320 °C it was possible to achieve 80% yield of 2-methylfuran, with small amounts of 2,5-dimethylfuran and 2-vinylfuran as by-products. Catalyst characterization highlighted that FeVO₄ reduction took place under the studied conditions, leading to the in situ development of a true active phase. The study of the reaction network permitted us to infer on the relative contribution of H-transfer and hydrogenation, the latter from the in situ generated formaldehyde and H₂, to 2-methylfuran, formation. The reported results indicate the potential application of H-transfer with FeVO₄ catalysts as an efficient process for the selective de-oxygenation of biomass-derived molecules.