Identification of Kinetic and Spectroscopic Signatures of Copper Sites for Direct Oxidation of Methane to Methanol.

Copper-exchanged zeolites of different topologies possess high activity in the direct conversion of methane to methanol via the chemical looping approach. Despite a large number of studies, identification of the active sites, and especially their intrinsic kinetic characteristics remain incomplete and ambiguous. In the present work, we collate the kinetic behavior of different copper species with their spectroscopic identities and track the evolution of various copper motifs during the reaction. Using time-resolved UV/Vis and in situ EPR, XAS, and FTIR spectroscopies, two types of copper monomers were identified, one of which is active in the reaction with methane, in addition to a copper dimeric species with the mono-μ-oxo structure. Kinetic measurements showed that the reaction rate of the copper monomers is somewhat slower than that of the dicopper mono-μ-oxo species, while the activation energy is two times lower.