Methanol decomposition on Ni(111) and O/Ni(111)

Methanol decomposition on Ni(111) surfaces has been studied in the presence and absence of oxygen using temperature-programmed desorption and temperature-dependent sum frequency generation spectroscopy. Under both conditions the C-H and O-H bonds break, forming carbon monoxide and atomic hydrogen on the surface. No C-O bond scission was observed, limiting the number of reaction pathways. The O-H bonds break first (>150 K), forming surface methoxy, followed by C-H bond breakage (>250 K). All atomic hydrogen desorbs from the surface as H₂ through H+H recombinative desorption. H₂ desorbs at a higher temperature in the presence of oxygen (>300 K) than the absence of oxygen (>250 K) as the oxygen on the surface stabilizes the H atoms, forming surface hydroxide (OH). The surface oxygen also appears to stabilize the O-H and C-H bonds, leading to slightly higher dissociation temperatures. The CO molecules occupy both the bridge sites and the top sites of the Ni atoms as surface H appears to force the CO molecules to the top sites. There is a slight blueshift in the C-O bond vibration for both the O covered and O free surfaces due to CO being more mobile. On the O free surface, the C-O peak width broadens as low-frequency modes are activated. Finally, CO desorbs between 350 and 400 K.