In this work, a thermo-regulated recyclable catalytic system using ionic liquid [HO2CMMIm]Cl as the catalyst and isopropanol as the solvent has been demonstrated to be effective for the dehydration of fructose to synthesize 5-hydroxymethylfurfural (HMF). The solubility of [HO2CMMIm]Cl ionic liquid in isopropanol is temperature-dependent, being miscible with isopropanol at a temperature range suitable for fructose dehydration (e.g., above 80 °C) while not soluble at lower temperatures such as room temperature. Temperature-responsive solubilization/precipitation of [HO2CMMIm]Cl in isopropanol renders the acidic ionic liquid an appealing thermo-regulated phase-switchable catalyst. Furthermore, the effects of various parameters including catalyst loading, fructose concentration, reaction time and temperature on the catalytic performance of fructose dehydration have been studied systematically. Under optimized reaction conditions, up to 91.2 mol% HMF yield could be obtained. Additionally, when the ionic liquid catalyst precipitated out after the reaction, the solvent can be simply decanted and [HO2CMMIm]Cl could be directly reused for the next run with freshly added solvent and substrate. It was found that [HO2CMMIm]Cl could be reused at least five times without considerable loss of activity. Furthermore, a kinetic analysis was carried out, indicating the activation energy for the reaction to be 62.1 kJ mol−1. This catalytic system can be envisioned to find applications in a wide range of acid-catalyzed reactions with facile, thermo-regulated catalyst recovery features.
A series of Lewis acidic metal salts were used for glucose dehydration to 5-hydroymethylfurfural (HMF) in water. Effect of valence state, ionic radii of Lewis acidic cation, and the type of anions on the catalytic performance have been studied systematically. The experimental results showed that the valence state played an important role in determining catalytic activity and selectivity. It was found that a higher glucose conversion rate and HMF selectivity could be obtained over high valent Lewis acid salts, where the ionic radii of these Lewis acidic metal salts are usually relatively small. Analysis on the effect of the anions of Lewis acid salts on the catalytic activity and the selectivity suggested that a higher glucose conversion and HMF selectivity could be readily obtained with Cl−. Furthermore, the recyclability of high valence state Lewis acid salt was also studied, however, inferior catalytic performance was observed. The deactivation mechanism was speculated to be the fact that high valence state Lewis acid salt was comparatively easier to undergo hydrolysis to yield complicated metal aqua ions with less catalytic activity. The Lewis acidic activity could be recovered by introducing a stoichiometric amount of hydrochloric acid (HCl) to the catalytic before the reaction.
Six Co-Rh/Fe3O4 catalysts with different cobalt loadings were prepared by the co-precipitation of RhCl3, Co(NO3)2, and Fe(NO3)3 using Na2CO3 as the precipitant. These catalysts were tested for dicyclopentadiene (DCPD) hydroformylation to monoformyltricyclodecenes (MFTD) and diformyltricyclodecanes (DFTD). The results showed that the MFTD formation rate increased with increasing cobalt loading, whereas the DFTD formation rate initially increased and then decreased when the cobalt loading was greater than twice that of Rh. The DFTD selectivity was only 21.3% when monometallic Rh/Fe3O4 was used as the catalyst. In contrast, the selectivity was 90.6% at a similar DCPD conversion when the bimetallic 4Co-2Rh/Fe3O4 catalyst was employed. These catalysts were characterized by temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), and thermogravimetric and differential thermal analyses (TG-DTA). The results obtained by these complimentary characterization techniques indicated that adding cobalt to the Rh/Fe3O4 catalyst enhanced the Rh reducibility and dispersion; the Rh reducibility was easily altered, and increasing the cobalt loading improved the Rh dispersion. It was concluded that the enhanced catalytic performance with increasing cobalt loading might be due to the formation of a more reactive Rh species with a different Rh–phosphine interaction strength on the catalyst surface.