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The isomerization of 1,3-dihydroxyactone and d-glucose over Sn-Beta zeolite was investigated by in situ 13C NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn-Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co-solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomass, a cheap and plentiful resource, could play a key role in the production of sustainable chemicals. The simple sugars contained in the renewable lignocellulosic biomass can be converted into commercially valuable products such as 5-hydroxymethyl furfural (HMF). A platform molecule, HMF can be transformed into numerous chemical products with potential applications in a wide variety of industries. Of the hexoses contained in the lignocellulosic biomass, the successful production of HMF from glucose has been a challenge. Various heterogeneous catalysts have been proposed over the last decade, ranging from zeolites to metal organic frameworks. The reaction conditions vary in the reports in the literature, which makes it difficult to compare catalysts reported in different studies. In addition, the slight variations in the synthesis of the same material in different laboratories may affect the activity results, because the selectivity towards desired products in this transformation strongly depends on the nature of the active sites. This poses another difficulty for the comparison of different reports. Furthermore, over the last decade the new catalytic systems proposed have increased profoundly. In this article, we summarize the heterogeneous catalysts: Metal Organic Frameworks (MOFs), zeolites and conventional supported catalysts, that have been reported in the recent literature and provide an overview of the observed catalytic activity, in order to provide a comparison. [ABSTRACT FROM AUTHOR]

Herein, Zeolitic imidazolate framework-8 (ZIF-8) is considered as an easy and cheap to prepare alternative catalyst for the isomerization of glucose and production of 5-hydroxymethyl furfural (HMF). For the synthesis of the ZIF-8 catalysts two preparation methods were evaluated, being room temperature and hydrothermal synthesis at 140 °C. Of these, the hydrothermal synthesis method yields a material with exceptionally high surface area (1967 m2·g−1). As a catalyst, the ZIF-8 materials generated excellent fructose yields. Specifically, ZIF-8 prepared by hydrothermal synthesis yielded a fructose selectivity of 65% with a glucose conversion of 24% at 100 °C in aqueous reaction medium. However, this selectivity dropped dramatically when the reactions were repeated at higher temperatures (~140 °C). Interestingly, greater quantities of mannose were produced at higher temperatures too. The lack of strong Brønsted acidity in both ZIF-8 materials resulted in poor HMF yields. In order to improve HMF yields, reactions were performed at a lower pH of 1.0. At 140 °C the lower pH was found to drive the reaction towards HMF and double its yield. Despite the excellent performance of ZIF-8 catalysts in batch reactions, their activity did not translate well to the flow reactor over a continuous run of 8 h, which was operating with a residence time of 6 min. The activity of ZIF-8 halved in the flow reactor at 100 °C in ~3 h, which implies that the catalyst's stability was not maintained in the long run. [ABSTRACT FROM AUTHOR]