5-Hydroxymethylfurfural (HMF), one of the most important intermediates derived from biomass, was directly produced from monosaccharides (fructose and glucose) and disaccharides (sucrose and cellobiose) by a simple one-pot reaction including hydrolysis, isomerization and dehydration using solid acid and base catalysts under mild conditions.
2,5-Diformylfuran (DFF) was selectively synthesized from 5-hydroxymethylfurfural using a hydrotalcite-supported ruthenium catalyst (Ru/HT) by oxidation with molecular oxygen under mild reaction conditions. A combination of hydrotalcite, Amberlyst-15, and Ru/HT catalysts successfully afforded direct synthesis of DFF from hexoses such as fructose and glucose via isomerization, dehydration, and successive selective oxidation in one pot. Stepwise addition of catalyst improved DFF yield up to 49% from fructose and 25% from glucose, respectively.
A new approach is developed for hydrogenolytic ring opening of biobased 5-hydroxymethylfurfural (HMF), dehydration product of hexoses, towards 1,6-hexanediol (HDO) under atmospheric pressure. The highest yield of HDO, 43%, is achieved over reusable Pd/zirconium phosphate (ZrP) catalyst at 413 K in the presence of formic acid as hydrogen source. In comparison with various Brønsted and/or Lewis acidic supports, the specific Brønsted acidity on ZrP support effectively accelerated the cleavage of C-O bond in a furan ring.
This review is intended to introduce recent progress in the characterization, synthesis and catalysis of hydrotalcite (HT) and HT-related materials. NMR, in situ neutron diffraction and TG-DTA techniques have been used to determine the local structure and structural changes of HT. Various synthetic methods of controlling the morphology of HT are introduced together with the crystal formation mechanism. The preparation methods of magnetic HTs are also included. The HT acts as a heterogeneous base catalyst for efficient transformations of organic compounds such as the synthesis of glycerol carbonate, transesterification of oils (biodiesel production) and carbon-carbon bond formations. The HT has also been used as a support for immobilizing various metal species (Ru, Pd, Ag, Au, Pt, Cu, V, Mn etc.), which enables highly selective organic reactions such as dehydrogenation of alcohols and deoxygenation of epoxides. Cooperative actions between basic sites of the HT surface and supported metal species are introduced. It is also shown that the HT can work together with other solid acids and metal catalysts to promote sequential reactions in a one-pot manner, which gives us a very important methodology for environmentallybenign synthesis of value-added chemicals, especially from biomass-derived compounds.
The presence of a dataset that covers a parametric space
of materials
and process conditions in a process-consistent manner is essential
for the realization of catalyst informatics. Here, an important piece
of progress is demonstrated for the oxidative coupling of methane.
A high-throughput screening instrument is developed for enabling an
automatic performance evaluation of 20 catalysts in 216 reaction conditions.
This affords an oxidative coupling of methane dataset comprised of
12 708 data points for 59 catalysts in three successive operations.
Based on a variety of data visualization analysis, important insights
into catalysis and catalyst design are successfully extracted. In
particular, the simultaneous optimization of the catalyst and reactor
design is found to be essential for improving the C2 yield.
The consistent dataset allows the accurate prediction of the C2 yield with the aid of nonlinear supervised machine learning.
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