Construction of diverse hollow MFI zeolites through regulating the micropore filling agents

Constructing hollow structure into microporous zeolites can improve the accessibility of acid sites located at the inner part and the diffusion property. Hence, the development of an efficient synthesis strategy to acquire zeolites with tunable hollow structures and acidity has attracted much attention. In this work, an innovative tandem synthesis route was proposed to prepare MFI zeolites with diverse hollow structure while maintaining solid yields exceeding 90 %. The substitution of ethanol molecules, which previously occupied the micropores, with tetrapropylammonium cations was proved to be the key factor to construct hollow structure. And a crystallization-driven particle dissolution mechanism was proposed. The dimension of the hollow cavity, particle size, and Si/Al ratio can be flexibly regulated. Interestingly, hollow MFI samples featuring the common cavity structure, "eye-like" cavity structure, or double-cavity structure can be directly synthesized by controlling the dissolution of core parts. In the 1-butene catalytic cracking reactions, a much higher conversion of 67.2 % was acquired over hollow ZSM-5 compared with that over conventional ZSM-5 (35.8 %) after 64 h of reaction. This improvement can be attributed to the eightfold increase of diffusivity in hollow ZSM-5. This facile and efficient synthesis method endows accurate regulation of the hollow structure, which is meaningful for both fundamental research and industrial applications of hollow zeolites.