Experimental and theoretical study of the reactions between MO2- (M = Fe, Co, Ni, Cu, and Zn) cluster anions and hydrogen sulfide.
Transition metal oxide cluster anions M(m)(18)O(n)(-) (M = Fe, Co, Ni, Cu, and Zn) were prepared by laser ablation and reacted with 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 reveal a suite of oxygen/sulfur (O/S) exchange and oxygen/sulfydryl (O/SH) exchange reactions. The O/S exchange reaction to release water was evidenced for all of the MO2(-) cluster anions: MO2(-) + H2S → MOS(-) + H2O, whereas the O/SH exchange reaction to derive MOSH(-) and OH species was only observed for reactions of NiO2(-), CuO2(-), and ZnO2(-). Density functional theory calculations were performed for reaction mechanisms of MO2(-) + H2S (M = Fe, Co, Ni, Cu, and Zn). The computational results are generally in good agreement with the experimental results. This gas-phase study provides an insight into the metal dependent reactivity in the removal of H2S over metal oxides.
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Mei-Ye
MY
Jia
Xun-Lei
XL
Ding
Sheng-Gui
SG
He
Mao-Fa
MF
Ge