Theoretical Study of the Mechanism of Furfural Conversion on the NiCuCu(111) Surface

[Image: see text] The full potential energy surface for the hydrodeoxygenation of furfural to furan and other ring-opening products has been systematically investigated using periodic density functional theory including dispersion corrections (PBE-D3) on the bimetallic NiCuCu(111) surface. For furan formation, the most favorable first step is the dehydrogenation of furfural into furoyl (F-CHO + H = F-CO + 2H), the successive step is decarbonylation of furoyl into furanyl (F-CO + H = F + CO + 2H), and the third step of furan formation from the hydrogenation of furanyl (F + CO + 2H = FA + CO + H) is the rate-determining step. In addition, on the basis of the most stably adsorbed furan and H, the ring opening of furan was found to be more favorable for producing many chemicals such as propane, butanal, butanol, and butene. In summary, furan is the main product of furfural conversion on the NiCuCu(111) surface. Since results have been obtained only for the NiCuCu(111) surface constructed by replacing the topmost Cu atoms by Ni atoms, the entire experimentally observed reactivity and selectivity of bimetallic CuNi catalysts for different construction methods cannot be fully rationalized. Nevertheless, the results provide the basis for investigating the intrinsic activity of CuNi catalysts in the hydrodeoxygenation of oxygenates involved in the refining of biomass-derived oils.