Direct Detection of Paired Aluminum Heteroatoms in Chabazite Zeolite Catalysts and Their Significance for Methanol Dehydration Reactivity.

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The distributions of heteroatoms within zeolite frameworks have important influences on the locations of exchangeable cations, which account for the diverse adsorption and reaction properties of zeolite catalysts. In particular for aluminosilicate zeolites, paired configurations of aluminum atoms separated by one or two tetrahedrally coordinated silicon atoms are important for charge-balancing pairs of H+ cations, which are active for methanol dehydration, or divalent metal cations, such as Cu2+, which selectively catalyze the reduction of NOx, both technologically important reactions. Such paired heteroatom configurations, however, are challenging to detect and probe, due to the typically nonstoichiometric compositions and nonperiodic distributions of aluminum atoms within aluminosilicate zeolite frameworks. Nevertheless, distinct configurations of paired framework aluminum atoms are unambiguously detected and resolved in solid-state 2D 27Al-29Si and 29Si-29Si NMR spectra, which are sensitive to the local environments of covalently bonded 27Al-O-29Si and 29Si-O-29Si moieties, respectively. Specifically, two H+-chabazite zeolites with the same bulk framework aluminum contents are shown to have different types and populations of closely paired aluminum species, which correlate with higher activity for methanol dehydration. The methodologies and insights are expected to be broadly applicable to analyses of heteroatom sites, their distributions, and adsorption and reaction properties in other zeolite framework types.