Mesocrystal morphology regulation by "alkali metals ion switch": Re-examining zeolite nonclassical crystallization in...

It is a Holy Grail to realize the goal-oriented synthesis of zeotype crystals via direct thermodynamic/kinetic control of crystallization in the simplest inorganic system. Especially, the most commonly used counter cations (i.e., Na⁺ and K⁺) are in turn believed to play merely the role of balancing charges and stabilizing frameworks, which make the simple ion-based morphology/porosity control remain big challenges.

We re-examined the role of Na⁺ and K⁺ to fine-tune the classical/nonclassical crystallization process in a seed-induced system with the simplest composition (Si/Al sources, inorganic alkali, and H₂O), and proposed an "ion switch" strategy. By analyzing the multiple growth curves, tracking the precursor evolution, and observing epitaxial crystallization behavior, a distinctive "ion switch"-worked nonclassical mechanism was uncovered.

By the "ion switch" strategy, ZSM-5 mesocrystals were fine-regulated with diverse architecture from single crystal to nanocrystallite assembly and intracrystal mesopore-enriched crystal. Such simple ions-controlled crystallization was achieved through microstructure heterogeneity of zeolitic building-blocks triggered by different counterions and their corresponding assembly behavior from oriented attachment to random deposition. Furthermore, this protocol can be extended to a wider H₂O/SiO₂ range, mixed Na⁺/K⁺ systems, and other alkali metal ions from Li⁺ to Cs⁺, and ZSM-5 mesocrystals with extended morphologies can be obtained.