Interaction of vanadium oxide cluster anions with water: an experimental and theoretical study on reactivity and mechanism

Vanadium oxide cluster anions (VxOy-, x = 2-3; y = 3-7) are produced by laser ablation and reacted with water in a fast flow reactor. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. Reaction channels of molecular hydrogen elimination (for V2,3O3-), water association (for V2O5- and V3O6,7-) and the coexistence of both channels (for V2O4- and V3O4,5-) are observed. V2O6- and V3O8- are nearly inert toward water. Density functional theory (DFT) calculations are performed to study the reaction mechanism of V2O3- in different spin states with water and the results support the experimental observation. The reaction mechanism of V2O3+ with water is also studied, which is in agreement with the experimental report in previous literature [Eur. J. Inorg. Chem., 2008, 4961] that molecular hydrogen elimination is a minor reaction channel for V2O3+ + H2O. The influence of cluster charge states and oxidation states of vanadium atoms on the cluster reactivity are presented based on the experimental and theoretical studies.