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

Gao-Lei Hou*, Endre Faragó, Dániel Buzsáki, László Nyulászi, Tibor Höltzl*, Ewald Janssens, “Observation of the Reaction Intermediates of Methanol Dehydrogenation by Cationic Vanadium Clusters” Angewandte Chemie International Edition, vol. 60, iss. 9, 4756-4763 (2020).
[Bibtex]

@article{
	author = {Gao-Lei Hou*, Endre Faragó, Dániel Buzsáki, László Nyulászi, Tibor Höltzl*, Ewald Janssens},
	title = {Observation of the Reaction Intermediates of Methanol Dehydrogenation by Cationic Vanadium Clusters},
	journal = {Angewandte Chemie International Edition},
	volume = {60},
	number = {4756-4763},
	abstract = {},
	year = {2020},
	type= {Article},
}

Detection and characterization of fleeting reaction intermediates and active sites are crucial for molecular-level knowledge of catalysis; insight that is required to understand the catalytic mechanisms, and to design novel high performance catalysts. We recently reported a mass spectrometric study of the reactions of 3d early transition metal (vanadium, [Ar]3d34s2) cationic clusters with methanol in a low-pressure collision cell. For comparison, the reaction of methanol with 3d late transition metal (cobalt, [Ar]3d74s2) cationic clusters were studied as well.

In the vanadium case, 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; while no dehydrogenation products have been observed for cobalt clusters. That demonstrates the strikingly different reactivity of vanadium and Co cationic clusters towards methanol. Quantum chemical calculations explored the reaction pathways and revealed that the fully dehydrogenation products of the reaction between Vn+ and methanol are Vn(C)(O)+, in which C and O are separated due to the high oxophilicity of vanadium.

The partial dehydrogenation and non-dehydrogenation species observed in the experiment are verified to be reaction intermediates along the reaction pathway, and their most probable structures have been proposed.

Figure 1. Reaction pathways and products