CC Bond\nHydrogenation vs C–O Bond Hydrogenolysis\nof Furfuryl Alcohol on Ru: A DFT Study

Periodic density functional theory (DFT) simulations\nwere used\nto thoroughly study the complete reaction network for the hydrogenation\nand hydrogenolysis of furfuryl alcohol (FA) on the Ru (0001) surface.\nThe reaction pathways for the formation of tetrahydrofurfuryl alcohol\n(THFA), 1,2-pentanediol (1,2-PeD), 1,5-pentanediol (1,5-PeD), and\n2-methyl furan (2-MF) from FA were established. In the most stable\nconfiguration, the FA ring was adsorbed parallel to the surface and\ncentered over a hollow site with a binding energy of −180 kJ/mol.\nHydrogenation of the FA ring was found to be the kinetically facile\npathway for the formation of THFA. The byproducts 1,2-PeD and 1,5-PeD\ncould be attributed to the outstanding C<sub>ring</sub>–O bond\ncleavage ability of the Ru metal. However, high activation barriers\nfor further hydrogenation of the ring-opened products and alkyl C–O\nbond cleavage kinetically limited the formation of 1,2-PeD, 1,5-PeD,\nand 2-MF on Ru surface during the vapor-phase hydrodeoxygenation of\nFA.