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Cu-exchanged zeolites activate dioxygen to form active sites for partial methane oxidation (PMO), nitrogen oxide decomposition, and carbon monoxide oxidation. Apparent rates of O2 activation depend both on the intrinsic kinetics of distinct Cu site types and the distributions of such sites within a given zeolite, which depend on the density and arrangement of the framework Al atoms. Here, we use hydrothermal synthesis methods to control the arrangement of framework Al sites in chabazite (CHA) zeolites and, in turn, the distinct Cu site types formed. Time-resolved in situ resonance Raman spectroscopy reveals the kinetics of O2 adsorption and activation within these well-defined Cu-CHA materials and the concomitant structural evolution of copper-oxygen (CuxOy) complexes, which are interpreted alongside Cu(I) oxidation kinetics extracted from in situ X-ray absorption spectroscopy (XAS). Raman spectra of several plausible CuxOy species simulated using density functional theory suggest that experimental spectra (λex = 532 nm) capture the formation of mono(μ-oxo)dicopper species (ZCuOCuZ). Transient experiments show that the timescales required to form CuxOy structures that no longer change in Ra-man spectra correspond to the durations of oxidative treatments that maximize CH3OH yields in stoichiometric PMO cycles (approximately 2 h). Yet, these periods extend well beyond the timescales for the complete conversion of the initial Cu(I) intermediates to their Cu(II) states ( |
