title: Consecutive oxygen-for-sulfur exchange reactions between vanadium oxide cluster anions and hydrogen sulfide.
abstract: Vanadium oxide cluster anions Vm(16)On(-) and Vm(18)On(-) were prepared by laser ablation and reacted with hydrogen sulfide (H2S) in a fast flow reactor under thermal collision conditions. A time-of-flight mass spectrometer was used to detect the cluster distributions before and after the interactions with H2S. The experiments suggest that the oxygen-for-sulfur (O/S) exchange reaction to release water was evidenced in the reactor for most of the cluster anions: VmOn(-) + H2S → VmOn-1S(-) + H2O. For reactions of clusters VO3(-) and VO4(-) with H2S, consecutive O/S exchange reactions led to the generation of sulfur containing vanadium oxide cluster anions VO3-kSk(-) (k = 1-3) and VO4-kSk(-) (k = 1-4). Density functional theory calculations were performed for the reactions of VO3-4(-) with H2S, and the results indicate that the O/S exchange reactions are both thermodynamically and kinetically favorable, which supports the experimental observations. The reactions of VmOn(+) cluster cations with H2S have been reported previously (Jia, M.-Y.; Xu, B.; Ding, X.-L.; Zhao, Y.-X.; He, S.-G.; Ge, M.-F. J. Phys. Chem. C 2012, 116, 9043), and this study of cluster anions provides further new insights into the transformations of H2S over vanadium oxides at the molecular level.
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 .
authors.forename: Mei-Ye
authors.initials: MY
authors.lastname: Jia
authors.forename: Bo
authors.initials: B
authors.lastname: Xu
authors.forename: Ke
authors.initials: K
authors.lastname: Deng
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He
authors.forename: Mao-Fa
authors.initials: MF
authors.lastname: Ge