title: Generation of Hydroxyl Radicals in the Reaction of Dihydrogen with AuNbO4+Cluster Cations.
abstract: A molecular-level insight into the nature of reactive oxygen species involved in dihydrogen (H2) dissociation is of great importance to understand gold catalysis. In this study, laser ablation generated and mass-selected AuNbO4+oxide cluster cations could dissociate H2in an ion-trap reactor. The reaction has been characterized by time-of-flight mass spectrometric experiments and density functional calculations. The lowest energy isomer of AuNbO4+contains two lattice oxygen (O2-) and one superoxide (O2.-) species. The gold atom anchors the H2molecule in the first step and then delivers one hydrogen atom to the O2-ion in H2dissociation. At the same time, O2.-is reduced into a peroxide unit that can accept the second hydrogen atom of H2with the generation of a hydroxyl radical as the main product. In this study, the important roles of the O2.-unit in the dissociation of H2have been identified.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of, Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.|University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
authors.forename: Li-Xue
authors.initials: LX
authors.lastname: Jiang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of, Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China. lxn@iccas.ac.cn.
authors.forename: Xiao-Na
authors.initials: XN
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of, Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.|University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
authors.forename: Hai-Fang
authors.initials: HF
authors.lastname: Li
authors.affiliation: School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, P.R. China.
authors.forename: Zhen-Xun
authors.initials: ZX
authors.lastname: Zhou
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of, Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China. shengguihe@iccas.ac.cn.
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He
keywords: cluster compounds; density functional calculations; hydrogen; radicals; reaction mechanisms