The direct conversion of methane to methanol using oxygen is a challenging but potentially rewarding pathway towards utilizing methane. By using a stepwise chemical looping approach, copper-exchanged zeolites can convert methane to methanol, but productivity is still too low for viable implementation. However, if the nature of the active site could be elucidated, that information could be used to design more effective catalysts. By employing anomalous X-ray powder diffraction with support from theory and other X-ray techniques, we have derived a quantitative and spatial description of the highly selective, active copper sites in zeolite omega (Cu-omega). This is the first comprehensive description of the structure of non-copper-oxo active species and will provide a pivotal model for future development for materials for methane to methanol conversion.@en

Copper-containing zeolites exhibit high activity in the direct partial oxidation of methane into methanol at relatively low temperatures. Di- and tricopper species have been proposed as active catalytic sites, with recent experimental evidence also suggesting the possibility of the formation of larger copper oxide species. Using density functional theory based global geometry optimization, we were able to identify a general trend of the copper oxide cluster stability increasing with size. For instance, the identified ground-state structures of tetra- and pentamer copper clusters of CunOn2+ and CunOn-12+ stoichiometries embedded in an 8-ring channel of mordenite exhibit higher relative stability compared to smaller clusters. Moreover, the aluminium content and localization in the zeolite pore influence the cluster's stability and its geometrical motif, which offers a perspective of tuning the properties of copper-exchanged zeolites by creating copper oxide clusters of a given structure and size. With the activity of the cluster towards methane being connected to its stability, such tuning will potentially allow the design of catalysts with engineered properties.@en

The application and quantification of in situ copper K-edge X-ray absorption near-edge structure (XANES), when linked to independently made reactor-based studies of methanol production, result in a majority relation between the production of CuI and methanol from methane that complies with the expectations of a two-electron mechanism founded upon CuII/CuI redox couples.@en

Direct methane functionalization and, in particular, the selective partial oxidation to methanol, remains an eminent challenge and a field of competitive research. The conversion of methane to methanol over transition-metal-containing zeolites using molecular oxygen is a promising and extensively studied process. Herein, we scrutinize some oft-cited assumptions in this topic—which include the labelling of the process as biomimetic, the debate regarding the industrial viability of direct methane-oxidation systems and the claim that methane is difficult to activate—and delineate the extent to which these are scientifically robust. We highlight both the merits and pitfalls of such statements and point out the hazards associated with their improper use. By examining these misconceptions, we build an outlook for future research, highlighting the need to optimize materials and process conditions for the stepwise approach and to further explore catalytic processes that explicitly employ strategies for the preservation of methanol.@en