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Effective hydrodeoxygenation of biomass-derived oxygenates is achieved with MoO3 to produce unsaturated hydrocarbons, converting linear ketones and cyclic ethers to olefins, and cyclic ketones and phenolics to aromatics with high yields. The catalyst is selective for C–O bond cleavage and operates using low H2 pressures (≤1 bar). We show that deactivation can be minimised by tuning hydrogen partial pressure, that original activity can be recovered by calcination, and that catalytic activity can be maintained in the presence of water. Theoretical calculations are used to elucidate reaction pathways and highlight the role of oxygen vacancies in the deoxygenation process.
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