In
recent years, 2,5-dihydroxymethylfuran (DHMF), which can be
produced by the selective hydrogenation of biomass-derived 5-hydroxymethylfurfural
(HMF), has attracted great attention and interest of many scientists
because of its peculiar symmetrical structure and wide potential applications.
At present, studies of the production of DHMF are quickly progressing,
with productive approaches being increasingly developed, and many
crucial achievements have been continually obtained. However, to date,
a special and real-time review of this research area is still lacking.
To gain more insight into the current research situation, this review
comprehensively summarizes and discusses state-of-the-art advancements
of the production of DHMF from HMF via various chemocatalytic pathways,
such as conventional hydrogenation, transfer hydrogenation, electrocatalytic
hydrogenation, photocatalytic hydrogenation, disproportionation reaction,
and biocatalytic pathways. Meanwhile, this review also systematically
outlines the latest results on the further transformation of DHMF
into value-added derivatives via etherification, polymerization, and
rearrangement.
A simple and efficient process was presented for the selective hydrogenation of 5-hydroxymethylfurfural (HMF) into the high-quality liquid fuel 2,5-dimethylfuran (DMF) in the presence of tetrahydrofuran (THF). Among the employed metal catalysts, the relatively inexpensive carbon-supported ruthenium (Ru/C) displayed the highest catalytic performance, which led to 94.7% DMF yield with 100% HMF conversion at a relatively mild reaction temperature of 200 °C for only 2 h. Although Ru/ C had a little loss in the catalytic activity when it was used for five successive reaction runs, the partially deactivated Ru/C could be easily regenerated by heating at a mixed flow of H 2 and N 2 . Moreover, the plausible mechanism involving an aldehyde group, a hydroxyl group, and a furan ring for the selective hydrogenation of HMF into DMF was also proposed. Subsequently, DMF was separated from the crude hydrogenation mixture according to their various boiling points by the combination of atmospheric distillation and vacuum distillation, and then, the chemical structures and physical properties of the separated DMF were confirmed to be consistent with the authentic DMF. More gratifyingly, Ru/C and THF were also found to be a good combination for the direct hydrogenation of carbohydrate-derived HMF into DMF, which is very important for the practical production of DMF from a variety of biomass-derived carbohydrates such as fructose, glucose, sucrose, maltose, cellobiose, starch, and cellulose.
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