Abstract: The reaction mechanism for 2-methylfuran formation during hydrogenation of furfuryl alcohol on Cu(111) plane was investigated by the density functional theory generalized gradient approximation calculations with the slab model. The adsorption energy of furfuryl alcohol was calculated to obtain preferred adsorption sites on Cu(111) plane. Three possible reaction mechanisms were characterized and the reaction potential energy surfaces were computed. The transition states (TSs) were searched with the linear and quadratic synchronous transit (LST/QST) complete search. The results show that the furfuryl alcohol molecule adsorbed on the Cu(111) plane via –OH, and the intermediate ψCH₂ and ψCH₂O can be obtained by the furfuryl alcohol decomposition. The mechanism for 2-methylfuran formation according to the mechanism C is more probable. The energy barrier of furfuryl alcohol decomposition to form ψCH₂ can be significantly reduced by the participation of hydrogen radical. The intermediate of ψCH₂ is much easier to obtain the H atom from the furfuryl alcohol, that is the formation routine of the product 2-methylfuran. In the mechanism C, the calculated barrier for the rate-determining step ψCH₂O* → ψCHO* + H* is 199.0 kJ/mol. The general reaction is 2ψCH₂OH = ψCH₃ + ψCHO + H₂O.

Key words: Cu(111) surface, densityfunctional theory, 2-methylfuran, reaction mechanism, furfuryl alcohol