4.8 Article

Direct TEM Observation of Vacancy-Mediated Heteroatom Incorporation into a Zeolite Framework: Towards Microscopic Design of Zeolite Catalysts

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 48, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211196

Keywords

Direct Imaging; Hetero-Metal-Atoms; Point Defects; Transmission Electron Microscopy; Zeolites

Funding

  1. SPST, ShanghaiTech University [EM02161943]
  2. National Natural Science Foundation of China [NSFC-21850410448, NSFC-21835002]
  3. 111 project of China [B17020]
  4. Spanish Ministry of Science and Innovation [RYC2018-024561-I]
  5. regional government of Aragon [DGA E13_20R]
  6. European Union [823717-ESTEEM3]
  7. Japan Science and Technology Agency (JST) [JPMJSC18C4]
  8. Japan Society for the Promotion of Science (JSPS) [19H02513, 22K04825]

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Incorporating hetero-metal atoms into zeolite structures can enhance catalytic activity and selectivity in oxidation reactions. However, the rational design of zeolites with specific titanium sites is challenging due to the unclear atomic structure during synthesis. This study successfully synthesized a titanosilicate with predictable titanium distribution by mediating vacancies in a defective MSE-type zeolite precursor.
Incorporating hetero-metal-atom, e.g., titanium, into zeolite frameworks can enhance the catalytic activity and selectivity in oxidation reactions. However, the rational design of zeolites containing titanium at specific sites is difficult because the precise atomic structure during synthesis process remained unclear. Here, a titanosilicate with predictable titanium distribution was synthesized by mediating vacancies in a defective MSE-type zeolite precursor, based on a pre-designed synthetic route including modification of vacancies followed by titanium insertion, where electron microscopy (EM) plays a key role at each step resolving the atomic structure. Point defects including vacancies in the precursor and titanium incorporated into the vacancy-related positions have been directly observed. The results provide insights into the role of point defects in zeolites towards the rational synthesis of zeolites with desired microscopic arrangement of catalytically active sites.

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