Investigating Reaction Mechanisms for Furfural Hydrodeoxygenation on Ni and the Effect of Boron Doping on the Activity and Selectivity of the Catalyst

Abstract

Fast pyrolysis is a promising route for the production of fuels and high value chemicals from non-fossil fuel resources like biomass. However, the design of active and inexpensive catalysts that can selectively convert furfural, an important component in pyrolysis derived bio-oil, to target chemicals remains a challenge. In this context, Ni-based catalysts are potential candidates for the vapor phase activation of furfural in the presence of H2. In this paper, mechanisms and energetics (kinetics and thermodynamics) of the catalytic conversion of furfural to furans, furfuryl alcohol, and C4 products in the presence of H2 on Ni(111) are established, and the experimentally observed change in the selectivity with temperature is explained, using first-principles density functional theory. Hydrogen adsorbs stronger than furfural on the Ni surface. At low operating temperatures, hydrogen adsorption is spontaneous, leading to high hydrogen surface coverages that favor furfural hydrogenation and decarbonylation ov...