Epitaxial Growth of Two-Dimensional MWW Zeolite.

Two-dimensional (2D) zeolite, with a high aspect ratio, has more open skeletons and accessible active sites than its three-dimensional (3D) counterpart. However, traditional methods of obtaining 2D zeolites often cause structural damage and widespread skeleton defects, hindering efficient selectivity in molecular separation. In this study, we present, for the first time, a direct epitaxial synthesis of 2D zeolite (Epi-MWW) guided by hexagonal boron nitride (h-BN) with a coincidence matching of site lattices to MWW zeolite. The as-grown Epi-MWW zeolite possesses a high crystallinity and intact hexagonal 2D morphology, with an average thickness of 10 nm and an aspect ratio of over 50. Thanks to its excellent molecular accessibility, the diffusion time constants of o-xylene (OX) and p-xylene (PX) are as 12 and 133 times higher than those of conventional MCM-22, respectively; the PX/OX selectivity of Epi-MWW is 7.4 times better than MCM-22 as calculated by the ideal adsorbed solution theory.

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

HYPOTHESIS: 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. EXPERIMENTS: 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. FINDINGS: 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.