Construction of Single‐Crystalline Hierarchical ZSM‐5 with Open Nanoarchitectures via Anisotropic‐Kinetics Transformation for the Methanol‐to‐Hydrocarbons Reaction

We report an anisotropic‐kinetics transformation strategy to prepare single‐crystalline aluminosilicate MFI zeolites (ZSM‐5) with highly open nanoarchitectures and hierarchical porosities. The methodology relies on the cooperative effect of in situ etching and recrystallization on the evolution of pure‐silica MFI zeolite (silicalite‐1) nanotemplates under hydrothermal conditions. The strategy enables a controllable preparation of ZSM‐5 nanostructures with diverse open geometries by tuning the relative rate difference between etching and recrystallization processes. Meanwhile, it can also be extended to synthesize other heteroatom‐substituted MFI zeolite nanocages. Compared with conventional ZSM‐5 microcrystals, nanocrystals, and nanoboxes, the ZSM‐5 nanocages with single‐crystalline nature, highly open nanoarchitectures, and hierarchical porosities exhibit remarkably enhanced catalytic lifetime and low coking rate in the methanol‐to‐hydrocarbons (MTH) reaction. An anisotropic‐kinetics transformation strategy is developed to synthesize single‐crystalline hierarchical ZSM‐5 zeolites with highly open nanoarchitectures and different compositions. The as‐prepared ZSM‐5 nanocages exhibit remarkably improved catalytic lifetime and reduced coke formation rate in the methanol‐to‐hydrocarbons reaction.