Three-dimensional inhomogeneity of zeolite structure and composition revealed by electron ptychography

Hui Zhang; Guanxing Li; Jiaxing Zhang; Daliang Zhang; Zhen Chen; Xiaona Liu; Peng Guo; Yihan Zhu; Cailing Chen; Lingmei Liu; Xinwen Guo; Yu Han

doi:10.1126/science.adg3183

Three-dimensional inhomogeneity of zeolite structure and composition revealed by electron ptychography

Science. 2023 May 12;380(6645):633-638. doi: 10.1126/science.adg3183. Epub 2023 May 11.

Authors

Hui Zhang^#^{1

2

3}, Guanxing Li^#³, Jiaxing Zhang⁴, Daliang Zhang^{5

6}, Zhen Chen⁷, Xiaona Liu⁸, Peng Guo⁸, Yihan Zhu^{9

10}, Cailing Chen³, Lingmei Liu^{5

6}, Xinwen Guo⁴, Yu Han³

Affiliations

¹ Electron Microscopy Center, South China University of Technology, Guangzhou 510640, China.
² School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China.
³ Advanced Membranes and Porous Materials Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
⁴ State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
⁵ Multi-scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing 400044, China.
⁶ School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China.
⁷ School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.
⁸ National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁹ Center for Electron Microscopy, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
¹⁰ Institute for Frontier and Interdisciplinary Sciences, Zhejiang University of Technology, Hangzhou 310014, China.

^# Contributed equally.

PMID: 37167385
DOI: 10.1126/science.adg3183

Abstract

Structural and compositional inhomogeneity is common in zeolites and considerably affects their properties. Thickness-limited lateral resolution, lack of depth resolution, and electron dose-constrained focusing limit local structural studies of zeolites in conventional transmission electron microscopy (TEM). We demonstrate that a multislice ptychography method based on four-dimensional scanning TEM (4D-STEM) data can overcome these limitations. Images obtained from a ~40-nanometer-thick MFI zeolite exhibited a lateral resolution of ~0.85 angstrom that enabled the identification of individual framework oxygen (O) atoms and the precise determination of the orientations of adsorbed molecules. Furthermore, a depth resolution of ~6.6 nanometers allowed probing of the three-dimensional distribution of O vacancies, as well as the phase boundaries in intergrown MFI and MEL zeolites. The 4D-STEM ptychography can be generally applied to other materials with similar high electron-beam sensitivity.