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

Abstract

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.