Tailoring hierarchical zeolite composites with two distinct frameworks for fine-tuning the product distribution in benzene alkylation with ethanol.

A hierarchical zeolite composite, MOR@ZSM-5, with two distinct frameworks has been successfully fabricated via the repeated crystallization of ZSM-5 nanocrystals on mordenite surfaces. To avoid their phase separation, the surface of mordenite was pretreated with tetra( n -butyl)ammonium hydroxide (TBAOH) to induce the formation of the ZSM-5 nuclei, and it was subsequently modified by the continuous growth of nanocrystalline ZSM-5 on the entire area of the mordenite surfaces. Interestingly, the fully overgrown MOR@ZSM-5 composite exhibits a remarkable improvement in the ethylbenzene selectivity (>60%) obtained from the alkylation of benzene with ethanol with respect to isolated zeolites and their physical mixture due to the enhanced external surface area and hierarchical porosity as well as the reasonable acidity provided by the fully dispersed ZSM-5 nanocrystals on the mordenite surfaces. Moreover, coke species deposited on the designed composites are likely located at the external surfaces and do not considerably deteriorate the catalytic performance, whereas they are deposited predominantly in the micropores over the incompletely overgrown MOR@ZSM-5 composite. The present study illustrates the advantages of the overgrown zeolite composites of two incompatible frameworks in tailoring the hierarchical porosity, adjusting the acidic properties, and eventually controlling the product selectivity in acid-catalyzed reactions such as the alkylation of benzene with ethanol.