Pronounced cluster-size effects: gas-phase reactivity of bare vanadium cluster cations V(n)+ (n = 1-7) toward methanol.
Mass spectrometric experiments are used to examine the size-dependent interactions of bare vanadium cluster cations V(n)(+) (n = 1-7) with methanol. The reactivity patterns exhibit enormous size effects throughout the range of clusters investigated. For example, dehydrogenation of methanol to produce V(n)OC(+) is only brought about by clusters with n > or = 3. Atomic vanadium cation V(+) also is reactive, but instead of dehydrogenation of the alcohol, expulsions of either methane or a methyl radical take place. In marked contrast, the reaction efficiency of the dinuclear cluster V(2)(+) is extremely low. For the cluster cations V(n)(+) (n = 3-7), complete and efficient dehydrogenation of methanol to produce V(n)OC(+) and two hydrogen molecules prevails. DFT calculations shed light on the mechanism of the dehydrogenation of methanol by the smallest reactive cluster cation V(3)(+) and propose the occurrence of chemisorption concomitant with C-O bond cleavage rather than adsorption of an intact carbon monoxide molecule by the cluster.
Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany.
Sandra
S
Feyel
Detlef
D
Schröder
Helmut
H
Schwarz