Experimental and Theoretical Study of the Reactions between Vanadium Oxide Cluster Cations and Hydrogen Sulfide

• Published in: Journal of physical chemistry. C 2012-04, Vol.116 (16), p.9043-9048
• Main Authors: Jia, Mei-Ye, Xu, Bo, Ding, Xun-Lei, Zhao, Yan-Xia, He, Sheng-Gui, Ge, Mao-Fa
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp3005458

Vanadium oxide cluster cations (V m 16O n + and V m 18O n +) are 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 is used to detect the cluster distributions before and after the interactions with H2S. The experiments suggest that, in addition to H2S adsorption to form association products V m O n H2S+, three types of reactions are evidenced in the reactor: (1) V m O n + + H2S → V m O n H+ + SH, (2) V m O n + + H2S → V m O n H2 + + S, and (3) V m O n + + H2S → V m O n–1S+ + H2O. Density functional theory calculations are performed for reaction of VO2 + with H2S, and the results indicate that the above three types of reaction channels are both thermodynamically and kinetically favorable, which supports the experimental observations. This gas-phase cluster study may provide insights into selective oxidation of H2S to elemental sulfur over vanadium-based oxide catalysts.