Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 .

Selectively cleaving the C=O bond outside the furan ring of furfural is crucial for converting this important biomass-derived molecule to value-added fuels such as 2-methylfuran. In this work, a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluation identified molybdenum carbide (Mo2 C) as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran. These results indicate the potential application of Mo2 C as an efficient catalyst for the selective deoxygenation of biomass-derived oxygenates including furanics and aromatics.

Controlling the activity and selectivity of hydrodeoxygenation (HDO) of biomassderivatives is critical for the utilization of biomass as renewable sources for chemicals and fuels. Furfural, produced by the hydrolysis and dehydration of xylose from hemicellulose, is a promising biomass-derivative to produce important biofuels like 2-methylfuran. Using a combination of density functional theory (DFT) calculations and surface science measurements on Fe/Ni(111) model surfaces, our results indicate that furfural bonds to the bimetallic surfaces primarily through the C=O bond with the furan ring tilted away from the surface, leading to the production of 2-methylfuran through the HDO reaction with furfuryl alcohol being identified as the likely intermediate. Similar preferential interaction of the C=O group over the furan ring is also confirmed on SiO 2-supported FeNi bimetallic catalysts. The similar trends observed on model surfaces and supported catalysts demonstrate the feasibility of using single crystal surfaces to identify precious-metal-free bimetallic catalysts for biomass conversion.