Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China.
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China; Shunde Graduate School, University of Science and Technology Beijing, Shunde 528399, P. R. China.
J Colloid Interface Sci. 2023 Mar;633:291-302. doi: 10.1016/j.jcis.2022.10.113. Epub 2022 Nov 12.
Titanosilicate-1 zeolites (TS-1) as one of the most commonly used catalysts for alkene epoxidation, construction of hierarchical pores as well as elimination of anatase to promote mass transportation and avoid invalid decomposition of hydrogen peroxide are always desirable yet challenging goals. Here, a novel and unique Ti-based metal organic frameworks (MOFs)-induced synthetic strategy for fabricating anatase-free hierarchical TS-1 was first proposed. All the components of MOFs perform different functions: the uniformly distributed Ti nodes replace conventional tetrabutyl titanate (TBOT) to serve as sole Ti source for constructing zeolite crystal; the separated ligands can be embedded in the zeolite framework and act as template to in situ build hierarchical pore structure; the coordination interaction between Ti nodes and ligands can efficiently avoid the anatase generation by balancing the forming rates of Ti-OH and Si-OH. This synthetic strategy is of general applicability, and two different synthetic routes including traditional hydrothermal process and steam assisted crystallization (SAC) procedure are successfully adopted. The obtained hydrothermal TS-1 and SAC anatase-free samples all possess abundant intercrystalline mesopores of 20-50 nm and even macropores between 50 and 150 nm, improving the conversion over 25 % for 1‑hexene epoxidation than TS-1 sample prepared by conventional route. The influences of the amount of Ti MOFs precursor and the crystallization process are studied in detail, and possible synthesis mechanisms are proposed. This MOFs-induced strategy might open up an avenue for the rational design of ideal and hierarchical zeolite to boost the catalytic efficiency.
钛硅酸盐-1 沸石 (TS-1) 作为最常用的烯烃环氧化催化剂之一,构建分级孔道以及消除锐钛矿以促进质量传递并避免过氧化氢无效分解一直是理想但具有挑战性的目标。在这里,首次提出了一种新颖独特的基于钛的金属有机骨架 (MOFs) 诱导合成无锐钛矿分级 TS-1 的方法。MOFs 的所有成分都发挥不同的作用:均匀分布的 Ti 节点取代传统的四丁氧基钛 (TBOT),作为构建沸石晶体的唯一 Ti 源;分离的配体可以嵌入沸石骨架并作为模板原位构建分级孔结构;Ti 节点和配体之间的配位相互作用可以通过平衡 Ti-OH 和 Si-OH 的形成速率来有效避免锐钛矿的生成。这种合成策略具有普遍适用性,成功采用了两种不同的合成路线,包括传统的水热过程和蒸汽辅助结晶 (SAC) 过程。所得的水热 TS-1 和 SAC 无锐钛矿样品均具有丰富的 20-50nm 间的晶间介孔甚至 50-150nm 的大孔,使 1-己烯环氧化的转化率提高了 25%以上,优于通过传统路线制备的 TS-1 样品。详细研究了 Ti MOFs 前体的用量和结晶过程的影响,并提出了可能的合成机制。这种 MOFs 诱导策略可能为理想和分级沸石的合理设计开辟了一条途径,以提高催化效率。