DFT and RAIRS Investigations of Methanol on Cu(110) and on Oxygen-Modified Cu(110)

Abstract

The adsorption and subsequent reaction of methanol on Cu(110) and on the oxygen stripe phase on Cu(110) was investigated using reflection absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD) and density functional theory (DFT) calculations. It was shown that during high methanol exposures water can coadsorb and it is incorporated into the methanol rows formed in the chemisorbed layer. The RAIR spectra of adsorbed methanol are very similar with and without coadsorbed oxygen. This is due to the fact that the ν(CO) vibration is at the same frequency for both methanol and methoxy adsorbed in the more stable short-bridge site. However, methoxy adsorbed in the long-bridge site shows the ν(CO) vibration at lower wavenumbers and is found with increasing surface temperature. With coadsorbed oxygen the reaction products are formaldehyde, H 2, and CO 2 . DFT and RAIRS results suggest that the intermediate leading to CO 2 is an η 2 -formaldehyde and OH species on the surface, rather than formate.