Thermal activation of methane by vanadium boride cluster cations VB_n⁺ (n = 3-6)

Investigation on the reactivity of atomic clusters represents an important approach to discover new species to activate and transform methane, the most stable alkane molecule. While a few types of transition metal species have been found to be capable of cleaving the C-H bond of methane, methane activation by the transition metal boride species has not been explored yet. This study reports that vanadium boride cluster cations VB_n⁺ (n = 3-6) can dehydrogenate methane under thermal collision conditions. The mechanistic details of the efficient reactions have been elucidated by quantum chemistry calculations on the VB₃⁺ reaction system. Compared to the non-polar bare B₃ cluster, the B₃ moiety in VB₃⁺ can be polarized by the V⁺ cation and thus its reactivity toward methane can be much enhanced. This study provides new insights into the rational design of boron-based catalysts for methane activation.