The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance

Abstract

Hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios (Hier-ZSM-5-x, where x = 50, 100, 150 and 200) were synthesized using an ordered mesoporous carbon-silica composite as hard template. Hier-ZSM-5-x exhibits improved mass transport properties, excellent mechanical and hydrothermal stability, and higher catalytic activity than commercial bulk zeolites in the benzyl alcohol self-etherification reaction. Results show that a decrease in the Si/Al ratio in hierarchical single-crystal ZSM-5 zeolites leads to a significant increase in the acidity and the density of micropores, which increases the final catalytic conversion. The effect of porous hierarchy on the diffusion of active sites and the final catalytic activity was also studied by comparing the catalytic conversion after selectively designed poisoned acid sites. These poisoned Hier-ZSM-5-x shows much higher catalytic conversion than the poisoned commercial ZSM-5 zeolite, which indicates that the numerous intracrystalline mesopores significantly reduce the diffusion path of the reactant, leading to the faster diffusion inside the zeolite to contact with the acid sites in the micropores predominating in ZSM-5 zeolites. This study can be extended to develop a series of hierarchical single-crystal zeolites with expected catalytic performance.

Graphical abstract

Keywords

hierarchical zeolites / single crystalline / interconnected pores / improved diffusion performance / benzyl alcohol self-etherification reaction

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Acknowledgments

This work was supported by Innovative Research Team in University (IRT_15R52) of the Chinese Ministry of Education. B.-L. Su acknowledges a Clare Hall Life Membership at the Clare Hall College and the financial support of the Department of Chemistry, University of Cambridge. L.H. Chen acknowledges the Hubei Provincial Department of Education for the “Chutian Scholar” program. This work was also financially supported by the National Natural Science Foundation of China (Grant Nos. 21671155, U1663225, 21805216, 21902122), Major programs of technical innovation in Hubei (No. 2018AAA012) and Hubei Provincial Natural Science Foundation (No. 2018CFA054), Postdoctoral Science Foundation of China (No. 2019M652723).ƒ

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