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.

Direct methane conversion to methanol via chemical looping using copper-exchanged zeolites has attracted considerable attention during the last decades and is one of the most-actively studied processes. Despite the significant progress that has been made in the design of active systems and the elucidation of active sites, the effects of zeolite topology and the structure of copper species on the nature of the reaction products are yet unclear. Herein, we show that oxygen-activated copper-exchanged zeolites of different framework types, namely, MOR, MFI, BEA, and FAU, yield different products, as detected by in situ Fourier-transform infrared and nuclear magnetic resonance spectroscopy. Molecular methanol, methoxy species, and dimethyl ether prevail at lower reaction temperatures (<473–523 K), and CuI carbonyls and gaseous carbon oxides were detected above 573 K. Methane coupling to C2 and C3 hydrocarbons was shown for the first time over CuMOR, CuBEA, and CuFAU. The nature and relative fraction of formed products strongly depend on the structure of the copper active sites, which is governed by the topology of the zeolite host. Several pathways of methane transformation over copper-exchanged zeolites are identified, opening opportunities for tuning the properties of the materials to achieve the best performance.