The Link between ZSM-5 Zeolite Crystallization and Mesopore Formation by Leaching.

Acid or base leaching are well-established tools in the synthesis of mesoporous zeolites. Previous studies suggest an inherent link between the structure-property relationship of mesoporous zeolites, that is, chemical resistance, pore diameter and distribution, with zeolite synthesis or crystallization conditions. The exact nature and/or origin of this link is currently however, poorly established. Here, we provide evidence how zeolite crystallization conditions influence the leaching behavior and thus structure of mesoporous zeolites. Electron microscopy and in situ small angle X-ray scattering both confirmed the crystallization of ZSM-5 to utilize both nanoparticles and oligomers as elemental building blocks. Utilization of these species is highly depended on supersaturation. The precursor solution of decreased water content favored a faster consumption of nanoparticles compared to its oligomers at the early stage of crystallization. Then the addition of oligomers can heal the surface imperfections and thus the resulting zeolite showed a higher resistance against acid leaching. In contrast, within the precursor solution of increased water content the slower consumption of nanoparticles led to crystals with a less robust rim. Defects existed in the rim due to limited healing by oligomers and, as such, mesopores can be created by the following post-treatment. Precise control over selected crystallization conditions can therefore further aid the design of optimized mesoporous zeolites.