The catalytic upgrading of bio-oil, which is generated through fast pyrolysis of biomass, to liquid fuel is an attractive, yet challenging, process with significant economic potential. Liquid-phase heterogeneous catalytic upgrading of bio-oil has its advantage such as the tunable activity and selectivity that has been observed when using aprotic, protic or non-polar solvents. Fundamental understanding of the solvent effect will be valuable for further promoting the liquid-phase heterogeneous catalytic upgrading strategy. Here, we focus on two model compounds – Furfural (FAL) and γ-Valerolactone (GVL), which are important platform chemicals in the bio-oil refinery, and discuss the solvent effect on their reactions through a combined experimental and computational study. Our experimental results show high selectivity towards alcohol products from aqueous phase catalytic reactions of furfural and γ-valerolactone on a palladium and a ruthenium surface, respectively. Density functional theory (DFT) calculations are performed to investigate adsorption of furanic compounds on the metal surface as well as study the reaction barriers of the ring opening through O-C hydrogenolysis and hydrogenation of furfural and γ-valerolactone. Moreover, we compare the adsorption and reaction of furanics on different metal surfaces in different solvents, through which the atomic-scale understanding of the role of solvent has been achieved. We find that the solvent can either perturb the molecular adsorption, for example, through formation of hydrogen bonds with water, or participate directly in the reaction through proton transfer. This synergistic combination of experiment, theory and computation thus provides detailed understanding of the reaction mechanism of bio-oil upgrading in a complicated liquid environment. Finally, I will discuss briefly the effect of water on other reactions of biomass-derived compounds.

First-principles reaction engineering at the solid-liquid interface

251st National Meeting (2016)

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