Observation of the Reaction Intermediates of Methanol Dehydrogenation by Cationic Vanadium Clusters

A mass spectrometric study of the reactions of vanadium cationic clusters with methanol in a low-pressure collision cell is reported. For comparison, the reaction of methanol with cobalt cationic clusters was studied. For vanadium, the main reaction products are fully dehydrogenated species, and partial dehydrogenation and non-dehydrogenation species are observed as minors, for which the relative intensities increase with cluster size and also at low cluster source temperature cooled by liquid nitrogen; no dehydrogenation products were observed for cobalt clusters. Quantum chemical calculations explored the reaction pathways and revealed that the fully dehydrogenation products of the reaction between V-n(+) and methanol are V-n(C)(O)(+), in which C and O are separated owing to the high oxophilicity of vanadium. The partial dehydrogenation and non-dehydrogenation species were verified to be reaction intermediates along the reaction pathway, and their most probable structures were proposed.

Automated summary

In a low-pressure collision cell, a mass spectrometric study of the reactions between vanadium cationic clusters and methanol was reported. The main reaction products for vanadium are fully dehydrogenated species, with partial dehydrogenation and non-dehydrogenation species observed as minors. In comparison, no dehydrogenation products were observed for cobalt clusters.