Hydrothermally Stable Ruthenium–Zirconium–Tungsten Catalyst for Cellulose Hydrogenolysis to Polyols

Abstract

In this work, we describe a catalytic material based on a zirconium–tungsten oxide with ruthenium for the hydrogenolysis of microcrystalline cellulose under hydrothermal conditions. With these catalysts, polyols can be produced with high yields. High and stable polyol yields were also achieved in recycling tests. A catalyst with 4.5 wt % ruthenium in total achieved a carbon efficiency of almost 100 %. The prepared Zr‐W oxide is mesoporous and largely stable under hydrothermal conditions (493 K and 65 bar hydrogen). Decomposition into the components ZrO2 and WO3 could be observed at temperatures of 1050 K in air.

Supported MoOx and WOx Solid Acids for Biomass Valorization: Interplay of Coordination Chemistry, Acidity, and Catalysis

“…Further improvement in EG selectivity was noticed when these materials were impregnated with a Ru/carbon catalyst, indicating the importance of acid-redox sites for the cellulose-to-EG process. A similar effect (improved EG selectivity) was noticed when Ru was added to a mesoporous WO 3 /ZrO 2 solid acid . The mesoporous WO 3 /ZrO 2 solid acid exhibited remarkable hydrothermal stability at 220 °C and 65 bar H 2 pressure, which might be due to the strong WO 3 –ZrO 2 interaction enabled by the mesoporous structure.…”

“…A similar effect (improved EG selectivity) was noticed when Ru was added to a mesoporous WO 3 /ZrO 2 solid acid. 200 The mesoporous WO 3 /ZrO 2 solid acid exhibited remarkable hydrothermal stability at 220 °C and 65 bar H 2 pressure, which might be due to the strong WO 3 −ZrO 2 interaction enabled by the mesoporous structure. This WO 3 /ZrO 2 solid acid may find potential applications for the aqueous-phase reactions.…”

Hydrothermally synthesized poorly-crystalline binary oxides with ZrW2O8composition: preparation, structural analysis, and catalytic activity for the alkylation of anisole with benzyl alcohol

“…In the current solid acid catalyst, the Zr edge EXAFS analysis is expected to provide information about the boundary structure between the tungsten and zirconium species. The XRD pattern identical to the ZWO-I phase has been reported by Xing et al, 27 Ando et al, 28 and Lucas et al 29 Because of the wide lines in the powder X-ray diffraction patterns, the phase was identied as amorphous, and the precise structural characterization has not been performed. Ando et al reported that the phase acts as a solid acid catalyst to promote the alkylation of anisole with benzyl alcohol.…”

Advances in porous and nanoscale catalysts for viable biomass conversion

“…In view of these benefits, Ru/Zr-W-O catalysts, which exhibit high hydrothermal stability at 220 1C and 65 bar H 2 , were developed for the liquid phase hydrogenolysis of cellulose. 310 About 31.9% and 4.5% yields of EG and 1,2-PG, respectively, were obtained over 4.5 wt% Ru/Zr-W-O catalyst at optimized reaction conditions.…”

“…The coordination of a metal with another metal or metal oxide is an attractive strategy, not only to achieve enhanced structure-activity properties, but also to improve hydrothermal stability of nanostructured metal/metal oxide catalysts. For instance, mixed oxide supported metal particles (e.g., Ru/Zr-W-O) 310 and metal oxide supported bimetallic particles (e.g., Pd-Cu/ZrO 2 ) 326 were found to be highly active for cellulose hydrogenolysis and levulinic acid hydrogenation in aqueous phase, respectively, compared to the pristine counterparts, which was attributed to strong metal-metal and metal-support interactions. Such synergistic interactions were also observed in unsupported mixed oxides, namely SiO 2 -Al 2 O 3 , 269 and La 2 O 3 -ZrO 2 .…”