Thermally and Chemically Stable Mixed Valence Copper Oxide Cluster Ions Revealed by Post Heating

Copper oxide clusters, CunOm+ (n = 5-12), were prepared in the gas phase by laser ablation of a copper metal rod in the presence of oxygen diluted in He as the carrier gas. The stoichiometry of the cluster ions was investigated using mass spectrometry. The number ratio of copper atoms and oxygen atoms in CunOm+ was distributed from n:m = 1:1-3:2, which was not affected significantly by the concentration of oxygen in the carrier gas as long as it exceeded 2%. When the cluster ions were heated up to 573 K downstream of the cluster source (post heating), CunOm+ (n:m approximate to 3:2) clusters were selectively and dominantly formed as a result of thermal dissociation. No further changes in the ratio were observed when the clusters were heated up to 623 K. From the stoichiometry, CunOm+ is considered to comprise both Cu(I) and Cu(II). Hence, the mixed valence states are found to be thermally stable for the small clusters in the gas phase, but they are not stable in the bulk phase. In addition to the thermal stability, we observed reactivity of CunOm+ with CO molecules. It was found that Cu12O8+ hardly binds to CO and that Cu9O6+ and Cu6O4+ along with other clusters with n:m approximate to 3:2 bind to CO very weakly, whereas CO attaches strongly to oxygen-rich clusters with release of an oxygen molecule.