title: Gold Atoms Supported on Gas-Phase Cerium Oxide Cluster Ions: Stable Stoichiometry and Reactivity with CO.
abstract: The stability and reactivity of cationic gold-cerium oxide clusters, AumCenO2n+x+(m ≤ 4, n ≤ 7, -1 ≤ x ≤ 2), were examined experimentally and computationally. These clusters were generated by simultaneous laser ablation of gold and cerium oxide targets and analyzed by time-of-flight mass spectrometry combined with gas-phase temperature-programmed desorption. Stable compositions of gold-cerium oxide clusters were identified as AumCenO2n+and AumCenO2n+1+for m ≥ 1, containing one oxygen atom more than the stable gold-free cerium oxide clusters CenO2n-1+and CenO2n+. In either case, the stable clusters mainly consisted of Ce4+and O2-, and the gold atoms had an oxidation state of +1. The reactivity of cerium oxide clusters toward CO was modified by gold atoms, which hindered CO oxidation while efficiently promoting its adsorption. According to density functional theory calculations, the oxygen-centered radical of cerium oxide clusters, considered to be the reactive site, was geometrically and electronically inactivated by gold atoms, which functioned as a CO adsorption site.
authors.affiliation: Department of Basic Science, School of Arts and Sciences, The University of Tokyo , Komaba, Meguro, Tokyo 153-8902, Japan.
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Nagata
authors.affiliation: Department of Basic Science, School of Arts and Sciences, The University of Tokyo , Komaba, Meguro, Tokyo 153-8902, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Miyajima
authors.affiliation: Department of Basic Science, School of Arts and Sciences, The University of Tokyo , Komaba, Meguro, Tokyo 153-8902, Japan.
authors.forename: Fumitaka
authors.initials: F
authors.lastname: Mafuné