Methane conversion by transition metal-doped vanadium oxide clusters

Efficient catalysis of CH4 conversion to liquid oxygenates has long been pursued but remains challenging. A deep understanding of the reaction mechanism and fundamental rule for tailoring the activity of catalysts is highly imperative. By ab initio calculations, we show that magnetic [V2O5](n) (n = 2, 3, 4) clusters doped with Ti/Zr/Hf possess unique activity for CH4 oxidation to CH3COOH and CH3OH. The active O atoms bonded with dopants have spin multiplets that govern electron transfer and C-H cleavage. The adsorption energy of CH4 is linearly correlated with the p band centre difference between the majority and minority spin channels of the active O atoms.