Synthesis of heteroatom zeolite subcrystals as catalytic materials and structural building blocks

Recent advancements in zeolite synthesis techniques have facilitated the synthesis of heteroatom zeolites with customized acidity and redox properties. However, challenges remain in controlling the content, accessibility and distribution of active center. A new zeolite construction strategy is still desired for the design of effective heteroatom zeolite catalysts. In this work, we synthesized and extracted a series of highly short-range ordered heteroatom-containing MFI zeolite subcrystals (Al, Ga, Ti, Zn, and Sn) with open framework structures and tunable acidic properties. These heteroatom-containing zeolite subcrystals not only acted as catalyst materials with diverse catalytic activity and high active site accessibility, but also served as versatile building blocks for customized zeolite synthesis and active site modulation via non-classical aggregation and cross-aggregation crystallization processes. Notably, we demonstrated that the catalytic performance of the unique subcrystals and their aggregated products were tailored to meet the specific requirements of reactions such as olefin epoxidation and macromolecular cracking. Furthermore, this synthesis strategy was also applicable to the synthesis of MEL zeolite subcrystals. The continuous expansion of subcrystal category opens new avenues for the design of multifunctional zeolite catalysts, contributing valuable insights into zeolite synthesis and active site regulation.