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观察具有均匀骨架结构的沸石核(亚晶)及其无单分子添加的定向附着。

Observing a Zeolite Nucleus (Subcrystal) with a Uniform Framework Structure and Its Oriented Attachment without Single-Molecule Addition.

作者信息

Sheng Zhizheng, Li He, Du Ke, Gao Lou, Ju Jing, Zhang Yahong, Tang Yi

机构信息

Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai, 200433, P. R. China.

College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences (BNLMS), Peking University, Beijing, 100871, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2021 Jun 7;60(24):13444-13451. doi: 10.1002/anie.202102621.

Abstract

Multiple and complex crystallization process of zeolite including complementary single-molecule condensation and particle assembly, and alternately dominant nucleation and growth behavior, plays the critical role in zeolite crystallization but meanwhile makes us hard to study the respective effects. Herein, we strip nuclei from the synthetic solution and find that high-ordered nucleus (subcrystal) is the premise to ignite high-speed growth of zeolite crystal. The high-ordered subcrystals with the size of only 6-10 nm possess regular aperture structure and microporous area similar to zeolite nanocrystal. Interestingly, a unitary oriented aggregation process of the subcrystals towards nanosheets is well observed and characterized where single-molecule addition process is greatly repressed. If a wider range of zeotype nuclei can be expanded, a new synthetic strategy of zeotype materials with heterogeneous framework and active sites may be expected, which may novelize zeolite catalytic properties.

摘要

沸石的多重复杂结晶过程,包括互补的单分子缩合和颗粒组装,以及交替占主导的成核和生长行为,在沸石结晶过程中起着关键作用,但同时也使我们难以研究各自的影响。在此,我们从合成溶液中剥离出晶核,发现高阶晶核(亚晶体)是引发沸石晶体高速生长的前提。尺寸仅为6-10纳米的高阶亚晶体具有与沸石纳米晶体相似的规则孔径结构和微孔区域。有趣的是,我们很好地观察并表征了亚晶体向纳米片的单一取向聚集过程,其中单分子添加过程受到极大抑制。如果能够扩展更广泛的沸石型晶核范围,有望开发出一种具有异质骨架和活性位点的沸石型材料的新合成策略,这可能会使沸石的催化性能焕然一新。

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