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Glucose conversion to 5-hydroxymethylfurfural (HMF) is important to the success of a biorefinery. Herein, metal–organic frameworks (MOFs) with the UiO-66 structure were synthesised with decanoic acid as the modulator and used as the catalyst to optimise HMF yield. PXRD, FTIR, and TGA/DSC techniques were applied to characterise the materials. The analysis results show that the materials assembled from the ligand 2-nitroterephthalic acid and hexameric Zr-oxo clusters contain decanoic acid chemically bound in the framework that influences porosity, Lewis acidity, and hydrophobicity. The materials exhibit excellent catalytic performance for HMF production from glucose in DMSO as solvent, attributed to their abundant defects and high hydrophobicity due to the addition of the decanoic acid modulator. Influences of catalyst dosages, reaction duration, and temperature were comprehensively investigated, leading to 98.1% conversion of glucose and 54.5% HMF yield under optimised reaction conditions. The catalytic conversion shows some deterioration after four cycles, yet the reaction selectivity displays no significant decline. [ABSTRACT FROM AUTHOR]

The catalytic characteristics of metal ions for glucose isomerization and dehydration were investigated with metal chloride as catalyst. The influences of metal ion category, content and temperature on reaction process were studied. The reaction kinetic model was applied to correlate experimental data to analyze catalytic characteristics quantitatively. The process of glucose to HMF was a tandem reaction, and the kinetic model based on this mechanism could simulate the reaction accurately. Ni2+, Cr3+ and Sn4+ possessed good catalytic activity for glucose conversion, among which the catalyst activity of Sn4+ was the highest, and that of Ni2+ was the lowest. The kinetic constant of side reaction of Sn4+ was about 20 times of that of Ni2+ . For Ni2+, reaction rate of glucose isomerization and side reaction increased, yet the catalytic activity for fructose dehydration to HMF was negligible with the increasing of Ni2+ content. Increasing of Cr3+ could enhance reaction rate of glucose isomerization significantly, and almost had no effect on other reactions. With the increasing of Sn4+ content, reaction rate of all steps increased, yet the intensity of side reaction would decrease. The influence of temperature on reaction constants followed the Arrhenius model. Higher temperature was beneficial to the side reaction, fructose dehydration and glucose isomerization respectively, when Ni2+, Cr3+ and Sn4+ were used, respectively. [ABSTRACT FROM AUTHOR]