from first principles PP-I-1

OP-IV-2Deoxygenation of Biomass-Derived Molecules over MultifunctionalPolyoxometalate Catalysts in the Gas PhaseAlotaibi M., Kozhevnikova E.F, Kozhevnikov I.V.Department of Chemistry, University of Liverpool, Liverpool, UKkozhev@liverpool.ac.ukBiomass-derived oxygenates are attractive as renewable raw materials for the production ofvalue-added chemicals and biofuel components. For fuel applications, they require reductionin their oxygen content, i.e., deoxygenation. Here we discuss various reaction pathways of(hydro)deoxygenation of carboxylic acids and ketones in the gas phase over multifunctionalcatalysts based on polyoxometalates (POMs). Among the substrates are C3-C6 carboxylicacids, representing the carboxylic acids derived from carbohydrate feedctocks, andmethylisobutyl and diisobutyl ketones (MIBK and DIBK) obtained by condensation ofacetone, the byproduct of biobutanol production. The catalysts and catalyst precursors understudy involve bulk and supported Keggin-type POMs comprising P-Mo, P-Mo-V and P-Wpolyanions. Their acid properties are modified by Cs + -for-H + substitution and a metalfunctionality is provided by doping with Pd, Pt, Ru and Cu.Deoxygenation/hydrodeoxygenation reaction pathways, such as ketonisation,decarboxylation, decarbonylation and hydrogenation for carboxylic acids and hydrogenationand hydrogenation/dehydration for ketones, are identified and related to metal-acidmultifunctional catalysis.78