Generating Assembled MFI Nanocrystals with Reduced b-Axis through Structure-Directing Agent Exchange Induced Recrystallization

Angew Chem Int Ed Engl. 2021 Jun 14;60(25):13959-13968. doi: 10.1002/anie.202017031. Epub 2021 May 17.

Abstract

Controlling crystal size and shape of zeolitic materials is an effective way to promote their mass transport and catalytic properties. Herein, we report a single step, Na+ - and porogen- free crystallization of MFI hierarchical architecture made up of aligned nanocrystals with reduced b-axis thickness (5-23 nm) and adjustable Si/Al ratios between 35 to 120, employing the commonly used tetrapropylammonium hydroxide (TPAOH) and tetrabutylammonium hydroxide (TBAOH) as structure-directing agents (SDAs). Homogeneous nucleation driven by both SDAs and subsequent SDA-exchange induced dissolution-recrystallization are responsible for the formation of such structure. The enhanced textural and diffusion properties account for a notable exaggeration of propene selectivity and catalyst lifetime in dimethyl ether-to-olefins (DTO) conversion. This protocol is extendable to the rational synthesis of other hierarchical zeolites through crystallization process control.

Keywords: MFI zeolite; dimethylether-to-olefin; hierarchical architecture; recrystallization; reduced b-axis thickness.