Yury Y. Gorbanev

Gold-catalyzed aerobic oxidation of 5-hydroxymethylfurfural in water at ambient temperature.

The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 °C). The selectivity of the reaction towards 2,5-furandicarboxylic acid and the intermediate oxidation product 5-hydroxymethyl-2-furancarboxylic acid is found to depend on the amount of added base and the oxygen pressure, suggesting that the reaction proceeds via initial oxidation of the aldehyde moiety followed by oxidation of the hydroxymethyl group of 5-hydroxymethylfurfural. Under optimized reaction conditions, a 71% yield of 2,5-furandicarboxylic acid is obtained at full 5-hydroxymethylfurfural conversion in the presence of excess base.

Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

The catalytic performance of zeolite‐supported vanadia catalysts was examined for the aerobic oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) in organic solvents such as N,N‐dimethylformamide (DMF), methyl isobutyl ketone, toluene, trifluorotoluene and DMSO. Catalysts based on the four different zeolite supports H‐beta, H‐Y, H‐mordenite, and H‐ZSM‐5 with 1–10 wt % vanadia loading were prepared and characterized by nitrogen physisorption, X‐ray powder diffraction, scanning electron microscopy, ammonia temperature‐programmed desorption, Raman spectroscopy and UV/Vis spectrophotometry. The H‐beta zeolite catalysts were found to contain highly dispersed vanadium oxide species at all loadings, and provided the highest reaction selectivity towards DFF and the lowest metal leaching of the examined systems. In particular, 1 wt % V2O5/H‐beta was found to be a stable, recyclable, and non‐leaching catalyst for the production of DFF under mild conditions in DMF as solvent, although with low DFF yield. To increase the yield, oxidation of HMF at elevated pressures was also investigated with this catalyst. Under optimized conditions, a reaction selectivity towards DFF of >99 % at 84 % HMF conversion was obtained, albeit with some contribution from lixiviated species to the total catalyst activity.

Magnesium and nickel(II) furan‐2,5‐dicarboxylate

The salts hexaaquamagnesium furan-2,5-dicarboxylate, [Mg(H(2)O)(6)](C(6)H(2)O(5)), (I), and hexaaquanickel furan-2,5-dicarboxylate, [Ni(H(2)O)(6)](C(6)H(2)O(5)), (II), provide the first crystallographic characterization of the furan-2,5-dicarboxylate dianion. Both structures exhibit extensive three-dimensional hydrogen-bonding networks between the octahedral coordinated hexaaquametal(II) ions and the dicarboxylate anions. Although the two structures are not isomorphous, they contain essentially identical two-dimensional slabs. The distinction between the structures is that these slabs are related by translation in (II), whereas adjacent slabs in (I) are reflected relative to each other by the action of a glide plane. The reflection occurs so that the local contacts between slabs are not changed, and thus the hydrogen-bond networks are identical except for the orientation of the water molecules at the interface between slabs.