Crystal engineering of hierarchical zeolite in dynamically maintained Pickering emulsion

[Display omitted] •Hierarchical ZSM-5 has been synthesized in a toluene/water biphasic media.•Pickering emulsion structure formed under tumbling crystallization conditions.•Non-classical oriented attachment growth was the dominant crystallization pathway.•Improvements in catalyst lifetime and light olefin yields were achieved in dimethylether-to-olefin conversion. Crystal engineering of hierarchical zeolites is regarded as a promising way to enhance diffusion-dependent catalytic properties of zeolitic materials. Crystallization process control on crystal size and pore-structure is desirable over porogen based protocols and post-synthetic methods for the low cost, high yield and potential scalability. Herein, a tumbling crystallization of hierarchical ZSM-5 zeolite in immiscible water/toluene Pickering emulsion inspired by energy dissipating structure occurring in nature is presented. The structure and acid properties of the obtained hierarchical material have been revealed using a panoply of characterization techniques such as powder X-ray diffraction, N2 physisorption isotherms, SEM, TEM, mercury protrusion measurements, NH3-TPD and pyridine IR spectroscopy, showing that the material contains high crystallinity, and penetrating macropores. Crystallization is found to proceed through a Pickering emulsion structure maintained by emulsifying effect of constant tumbling. Such an emulsion structure has hindered attachment growth of primary nanocrystals formed at the nucleation stage to further grow into larger size via coalescense. The hierarchical zeolite exhibits architecture-dependent prolonged catalyst lifetime and light olefin yield in dimethylether-to-olefin conversion. This process control to generate hierarchical zeolites opens up new ways toward inexpensive, high level control and efficient engineering of zeolite morphology.