LAUSR

Abstract Periodic DFT calculations have been employed to investigate the adsorption and dissociation mechanism of CH 3 OH on Cu (100) surface. For the adsorption, all possible adsorption configurations of relevant intermediates are identified. It is found that CH 3 OH and CHOH prefer to adsorb on the top sites, CH 2 OH and CO adsorb preferentially on the bridge sites, while CH 3 O, CH 2 O, CHO, COH and H occupy the hollow sites. Methanol and formaldehyde are weakly bound on the Cu (100) surface and are easily desorbed. CH 2 OH, CH 3 O, CHOH, CO, CHO, COH and H are adsorbed strongly on the surface. Additionally, four possible pathways of CH 3 OH dissociation initiated through the activation of O H and C H bonds, have been proposed and studied systematically. It is revealed that the breaking of the H O bond is more favorable for CH 3 OH, CH 2 OH and CHOH species. Consequently, the pathway (CH 3 OH CH 3 O CH 2 O CHO CO) is the most probable dehydrogenation route, where the highest energy barrier of CH 3 O dissociation makes it to be the rate-determining step of the whole dehydrogenation reaction.