One-pot cascade conversion of fructose to 2,5-diformylfuran enabled by a polyionic liquid-based porous catalyst†

One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly desirable to achieve hundreds-fold value-increase and high atomic economy, yet it is still challenging due to the lack of suitable catalysts with cascade conversion ability. In this work, we developed a porous hybrid catalyst (i.e. PMo₁₀V₂@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in the one-pot conversion of fructose to DFF. The integration of PMo₁₀V₂ with 2Br-PIL can impart both Brønsted acid and oxidation sites in the porous structure, thereby enabling the one-pot cascade conversion. As a result, PMo₁₀V₂@2Br-PIL demonstrated a remarkable DFF yield (95% yield), satisfying stability, recyclability and scale-up production ability (≈12.3 g in a batch experiment), demonstrating great potential for industrial production of DFF from fructose. Theoretical calculations revealed a synergistic effect of Brønsted acid sites and oxidation sites in PMo₁₀V₂@2Br-PIL, which promoted the one-pot conversion of fructose to DFF. This study enhances the understanding of biomass transformation over hybrid catalysts through synergetic acidic/oxidative catalysis, contributing to the development of highly active, selective, and multifunctional catalysts for one-pot biomass conversion.