Activation and Transformation of Methane on Boron-Doped Cobalt Oxide Cluster Cations CoBO₂⁺

The cleavage of inert C-H bonds in methane at room temperature and the subsequent conversion into value-added products are quite challenging. Herein, the reactivity of boron-doped cobalt oxide cluster cations CoBO₂⁺ toward methane under thermal collision conditions was studied by mass spectrometry experiments and quantum-chemical calculations. In this reaction, one H atom and the CH₃ unit of methane were transformed separately to generate the product metaboric acid (HBO₂) and one CoCH₃⁺ ion, respectively. Theoretical calculations strongly suggest that a catalytic cycle can be completed by the recovery of CoBO₂⁺ through the reaction of CoCH₃⁺ with sodium perborate (NaBO₃), and this reaction generates sodium methoxide (CH₃ONa) as the other value-added product. This study shows that boron-doped cobalt oxide species are highly reactive to facilitate thermal methane transformation and may open a way to develop more effective approaches for methane (CH₄) activation and conversion under mild conditions.