The interactions of methanol with well-defined Cu films on the oxygen-
terminated ZnO(0001BAR)-O surface have been studied, mainly using temp
erature programmed desorption (TPD). The Cu films, which were from sub
monolayer to multilayer in coverage, had been structurally characteriz
ed in previous studies using XPS, LEIS, ARXPS, LEED and work function
measurements, and by CO, H2O and formic acid adsorption. On clean Cu f
ilms methanol is adsorbed reversibly, desorbing at 200-260 K from atom
-thick Cu islands, and at approximately 155 K from multilayer islands
preannealed to approximately 550 K. In this respect, the atom-thin isl
ands resemble Cu(110) sites and multilayer islands resemble Cu(111), c
onsistent with behavior of other adsorbates. On oxygen-predosed multil
ayer films (preannealed to approximately 600 K), methanol reacts to fo
rm methoxy species which decompose at 395 K to yield formaldehyde and
hydrogen in TPD, also like Cu(111). Multilayer films preannealed to >
750 K show a decrease in the peak area for methoxy decomposition which
correlates with the loss of Cu area due to severe clustering. Oxygen-
predosed Cu islands which are but one Cu atom thick show no clear evid
ence for a methoxy state in TPD. This suggests that oxygen atoms on su
ch atom-thin Cu islands are poor Bronsted bases relative to O(a) on bu
lk Cu surfaces, consistent with results for adsorbed water. Results on
high-area Cu/ZnO catalysts are discussed in the light of these new re
sults.