Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water

Heterogeneous catalysts are desired for the conversion of glucose, the most abundant sugar in renewable biomass, but presently their synthesis requires highly toxic chemicals with long synthesis times. We report the conversion of glucose into fructose and 5‐hydroxymethylfurfural on a heterogeneous catalyst that is stable and selective and operates in the most environmentally benign solvent, water. We used a bifunctional solid with Lewis and Brønsted acid sites by partially replacing the organic linker of the zirconium organic framework UiO‐66 with 2‐monosulfo‐benzene‐1,4‐dicarboxylate. This catalyst showed high product selectivity (90 %) to 5‐hydroxymethylfurfural and fructose at 140 °C in water after a reaction time of 3 h. It was recyclable and showed only a minor loss in activity after the third recycle, offering a realistic solution for the bottleneck glucose isomerization reaction for scale‐up and industrial application of biomass utilization.