Dehydration of Fructose to 5-HMF over Acidic TiO₂ Catalysts

Different solid sulfonic titania-based catalysts were investigated for the hydrothermal dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The catalytic behavior of the materials was evaluated in terms of fructose conversion and selectivity to 5-HMF. The surface and structural properties of the catalysts were investigated by means of X-ray diffraction (XRD), N₂ adsorption isotherms, thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and acid capacity measurements. Special attention was focused on the reaction conditions, both in terms of 5-HMF selectivity and the sustainability of the process, choosing water as the solvent. Among the various process condition studied, TiO₂-SO₃H catalyzed a complete conversion (99%) of 1.1M fructose and 5-HMF selectivity (50%) and yield (50%) at 165 °C. An important improvement of the HMF selectivity (71%) was achieved when the reaction was carried out by using a lower fructose concentration (0.1M) and lower temperature (140 °C). The catalytic activities of the materials were related to their acid capacities as much as their textural properties. In particular, a counterbalance between the acidity and the structure of the pores in which the catalytic sites are located, results in the key issue for switch the selectivity towards the achievement of 5-HMF.