Dai Heng, Shen Yufeng, Yang Taimin, Lee Choongsze, Fu Donglong, Agarwal Ankur, Le Thuy Thanh, Tsapatsis Michael, Palmer Jeremy C, Weckhuysen Bert M, Dauenhauer Paul J, Zou Xiaodong, Rimer Jeffrey D
Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX, USA.
Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden.
Nat Mater. 2020 Oct;19(10):1074-1080. doi: 10.1038/s41563-020-0753-1. Epub 2020 Aug 10.
There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.
越来越多的证据表明,合成具有显著降低的内扩散限制的纳米级沸石,对于提高催化和吸附性能具有优势。然而,制备尺寸小于100纳米的沸石晶体并非易事,通常需要使用复杂的有机物,且产品收率通常较低。在此,我们提出一种替代的简便方法,通过在晶种上外延生长鳍状突起物来增强沸石的传质性能。我们在两种常见的沸石上验证了这种可推广的方法,并确认鳍状物与下层晶种在晶体学上是对齐的,且二次生长不会阻碍进入微孔。鳍状沸石的分子建模和时间分辨滴定实验探究了内扩散,并揭示了传质的显著改善,这与模型反应的催化测试结果一致,表明这些结构表现为尺寸与鳍状物相当的准纳米晶体。这种方法可扩展到其他沸石和硅铝酸盐材料的合理合成。