High-efficiency synthesis of 5-hydroxymethylfurfural and 2,5-diformylfuran from fructose over magnetic separable catalysts

In this work, a sulfonic acid-functionalized magnetic separable solid acid (Fe3O4@SiO2-SO3H) was synthesized, characterized, and tested for fructose conversion to 5-hydroxymethylfurfural (HMF). Results indicated that the prepared catalyst had a good efficacy for fructose dehydration to HMF due to its larger specific surface area, appropriate acid amount and homogeneous acid distribution. The maximum HMF yield of this work was 96.1 mol%. It was obtained at 120 °C for 1.5 h with 100 mol% fructose conversion. More importantly, the produced HMF could be further in-situ oxidized into 2,5-diformylfuran (DFF) after the replacing of the Fe3O4@SiO2-SO3H with a ZnFeRuO4 catalyst, and the highest DFF yield of 90.2 mol% (based on initial fructose) was obtained after reaction another 8.5 h. The production of DFF from fructose through the above two consecutive steps avoids the intermediate HMF separation, which saves time and energy. In addition, both Fe3O4@SiO2-SO3H and ZnFeRuO4 catalysts exhibited satisfied stability in the recycling experiments, which can be reused at least for five times with the HMF and DFF yield loss<5.3% and 3.3%, respectively. Finally, the plausible reaction mechanisms for fructose conversion to HMF or DFF over Fe3O4@SiO2-SO3H or/and ZnFeRuO4 catalysts were also proposed in this work.