Micron-sized zeolite Beta single crystals featuring intracrystal interconnected ordered macro-meso-microporosity displaying superior catalytic performance.

Serious diffusional limitations are frequently observed for the conversion of bulky molecules over conventional zeolite Beta crystals, which invoke for hierarchical structure to improve the mass transportation property and the accessibility to reactive sites. Zeolite single crystals with intracrystalline hierarchical porosity at macro-, meso- and micro-length scales is of great significance and provides the best solution . However, the construction of large zeolite Beta single crystals with such intracrystalline hierarchical porosity remains a critical challenge. We report here the successful synthesis of hierarchically ordered macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta) with a rare micron-scale crystal size by an in-situ bottom-up confined zeolite crystallization strategy. The fully interconnected intracrystalline macro-meso-microporous hierarchy and the unique micron-sized single crystalline nature of OMMS-Beta lead to highly improved accessibility to active sites and outstanding (hydro)thermal stability, contributing to unprecedentedly high catalytic performances in both gas-phase and liquid-phase acid-catalyzed reactions involving bulky molecules compared to commercial Beta and nanosized Beta zeolites. All these unprecedented properties of our hierarchically porous micron-scale zeolite Beta single crystals with excellent stability can be fully exploited in various catalytic reactions with high catalytic activity, selectivity and reusability. Most importantly, our in-situ bottom-up confined crystallization strategy to hierarchically porous zeolite single crystal is highly universal and has been extended to the successful synthesis of other zeolitic materials, including ZSM-5, TS-1 and SAPO-34. Such novel zeolite single crystals with excellent properties can be applied to many other industrial catalytic reactions.