Hollow STW‐Type Zeolite Single Crystals with Aluminum Gradient for Highly Selective Production of p‐Xylene from Methanol‐Toluene Alkylation

Zeolites with uniform micropores are important shape-selective catalysts. However, the external acid sites of zeolites have a negative impact on shape-selective catalysis, and the microporosity may lead to serious diffusion limitation. Herein, we report on the direct synthesis of hierarchical hollow STW-type zeolite single crystals with a siliceous exterior. In an alkalinous fluoride medium, the nucleation of highly siliceous STW zeolites takes place first, and the nanocrystals are preferentially aligned on the outer surface of the gel agglomerates to grow into single crystalline shells upon crystallization. The lagged crystallization of the internal Al-rich amorphous gels onto the inner surface of nanocrystalline zeolite shells leads to the formation of hollow cavities in the core of the zeolite crystals. The hollow zeolite single crystals possess a low-to-high aluminum gradient from the surface to the core, resulting in an intrinsic inert external surface, and exhibit superior catalytic performance in toluene methylation reactions.