Activity of Cu-Al-Oxo Extra-Framework Clusters for Selective Methane Oxidation on Cu-Exchanged Zeolites

Cu-zeolites are able to directly convert methane to methanol via a three-step process using O₂ as oxidant. Among the different zeolite topologies, Cu-exchanged mordenite (MOR) shows the highest methanol yields, attributed to a preferential formation of active Cu-oxo species in its 8-MR pores. The presence of extra-framework or partially detached Al species entrained in the micropores of MOR leads to the formation of nearly homotopic redox active Cu-Al-oxo nanoclusters with the ability to activate CH₄. Studies of the activity of these sites together with characterization by ²⁷Al NMR and IR spectroscopy leads to the conclusion that the active species are located in the 8-MR side pockets of MOR, and it consists of two Cu ions and one Al linked by O. This Cu-Al-oxo cluster shows an activity per Cu in methane oxidation significantly higher than of any previously reported active Cu-oxo species. In order to determine unambiguously the structure of the active Cu-Al-oxo cluster, we combine experimental XANES of Cu K- and L-edges, Cu K-edge HERFD-XANES, and Cu K-edge EXAFS with TDDFT and AIMD-assisted simulations. Our results provide evidence of a [Cu₂AlO₃]²⁺ cluster exchanged on MOR Al pairs that is able to oxidize up to two methane molecules per cluster at ambient pressure.