Hydrogen Exchange through Hydrogen Bonding between Methanol and Water in the Adsorbed State on Cu(111)

The interaction between submonolayers of methanol and water on Cu(111) is studied at 95-160 K temperature range with surface-sensitive infrared spectroscopy using isotopically labeled molecules. The initial interaction of methanol with the preadsorbed amorphous solid water at 95 K is through hydrogen-bonding with the dangling hydroxyl groups of water. Upon increasing the temperature up to 140 K, methanol and deuterated water form H-bonded structures which allow hydrogen-deuterium exchange between the hydroxyl group of methanol and the deuterated water. The evolution of the O-D and O-H stretching bands indicate that the hydrogen transfer is dominant at around 120-130 K, slightly below the desorption temperature of methanol. Above 140 K, methanol desorbs and a mixture of hydrogen-related water isotopologues remains on the surface. The isotopic composition of this mixture versus the initial D₂O:CH₃OH ratio supports a potential exchange mechanism via hydrogen hopping between alternating methanol and water molecules in a hydrogen-bonded network.