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Zeolites are important inorganic crystalline microporous materials with a broad range of applications in the areas of catalysis, ion exchange, and adsorption/separations. Solid-state nuclear magnetic resonance (NMR) spectroscopy has proven to be a powerful tool in the study of zeolites and relevant catalytic reactions because of its advantage in providing atomic-level insights into molecular structure and dynamic behavior. In this review, we provide a brief discussion on the recent progress in exploring framework structures, catalytically active sites and intermolecular interactions in zeolites and metal-containing ones by using various solid-state NMR methods. Advances in the mechanistic understanding of zeolite-catalysed reactions including methanol and ethanol conversions are presented as selected examples. Finally, we discuss the prospect of the solid-state NMR technique for its application in zeolites. [ABSTRACT FROM AUTHOR]

Methane dehydroaromatization (MDA) on Mo/ZSM‐5 zeolite catalyst is promising for direct transformation of natural gas. Understanding the nature of active sites on Mo/ZSM‐5 is a challenge for applications. Herein, using 1H{95Mo} double‐resonance solid‐state NMR spectroscopy, we identify proximate dual active sites on Mo/ZSM‐5 catalyst by direct observation of internuclear spatial interaction between Brønsted acid site and Mo species in zeolite channels. The acidic proton–Mo spatial interaction is correlated with methane conversion and aromatics formation in the MDA process, an important factor in determining the catalyst activity and lifetime. The evolution of olefins and aromatics in Mo/ZSM‐5 channels is monitored by detecting their host–guest interactions with both active Mo sites and Brønsted acid sites via 1H{95Mo} double‐resonance and two‐dimensional 1H–1H correlation NMR spectroscopy, revealing the intermediate role of olefins in hydrocarbon pool process during the MDA reaction. [ABSTRACT FROM AUTHOR]

Hydrocarbon-pool chemistry is important in methanol to olefins (MTO) conversion on acidic zeolite catalysts. The hydrocarbon-pool (HP) species, such as methylbenzenes and cyclic carbocations, confined in zeolite channels during the reaction are essential in determining the reaction pathway. Herein, we experimentally demonstrate the formation of supramolecular reaction centers composed of organic hydrocarbon species and the inorganic zeolite framework in H-ZSM-5 zeolite by advanced 13C-27Al double-resonance solid-state NMR spectroscopy. Methylbenzenes and cyclic carbocations located near Brønsted acid/base sites form the supramolecular reaction centers in the zeolite channel. The internuclear spatial interaction/proximity between the 13C nuclei (associated with HP species) and the 27Al nuclei (associated with Brønsted acid/base sites) determines the reactivity of the HP species. The closer the HP species are to the zeolite framework Al, the higher their reactivity in the MTO reaction. [ABSTRACT FROM AUTHOR]

The carbonylation reaction of ethane with CO to produce carboxylic acid was studied over zinc-modified ZSM-5 zeolite (denoted as Zn/ZSM-5) using in situ solid-state NMR spectroscopy. 13 C-isotope-labeled reactants were alternatively used to monitor the co-reaction at temperatures of 298–623 K. The NMR experimental results demonstrated that surface zinc-ethyl and methoxy species were formed and identified as key intermediates in the reaction. The reactivity of these intermediates was further explored under both oxidizing and reducing conditions by adding O 2 and H 2 into the reaction system. It was found that ethane was initially activated into zinc–ethyl species that show reactivity similar to that of organometallic compounds such as diethyl zinc. The interaction of zinc–ethyl species with CO 2 resulting from the oxidation of CO produces propanoic acid. Side products such as aromatics were formed by dehydrogenation of zinc–ethyl species via the formed ethene intermediates. We also found that hydrogenolysis of ethane occurred and gave rise to byproduct methane, which led to the formation of acetic acid by carboxylation with CO 2 . Additionally, CO was converted into surface methoxy species, which could react with CO to produce acetic acid via a Koch-type carbonylation reaction. [ABSTRACT FROM AUTHOR]