Carbocation chemistry confined in zeolites: spectroscopic and theoretical characterizations

Acid-catalyzed reactions inside zeolites are one type of broadly applied industrial reactions, where carbocations are the most common intermediates of these reaction processes, including methanol to olefins, alkene/aromatic alkylation, and hydrocarbon cracking/isomerization. The fundamental research on these acid-catalyzed reactions is focused on the stability, evolution, and lifetime of carbocations under the zeolite confinement effect, which greatly affects the efficiency, selectivity and deactivation of zeolite catalysts. Therefore, a profound understanding of the carbocations confined in zeolites is not only beneficial to explain the reaction mechanism but also drive the design of new zeolite catalysts with ideal acidity and cages/channels. In this review, we provide both an in-depth understanding of the stabilization of carbocations by the pore confinement effect and summary of the advanced characterization methods to capture carbocations in zeolites, including UV-vis spectroscopy, solid-state NMR, fluorescence microscopy, IR spectroscopy and Raman spectroscopy. Also, we clarify the relationship between the activity and stability of carbocations in zeolite-catalyzed reactions, and further highlight the role of carbocations in various hydrocarbon conversion reactions inside zeolites with diverse frameworks and varying acidic properties.