物理化学学报 >> 2020, Vol. 36 >> Issue (1): 1907052.doi: 10.3866/PKU.WHXB201907052

所属专题: 庆祝唐有祺院士百岁华诞专刊

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X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用

黎建,林聪,林建华,孙俊良*()   

  • 收稿日期:2019-07-18 录用日期:2019-09-17 发布日期:2019-09-24
  • 通讯作者: 孙俊良 E-mail:junliang.sun@pku.edu.cn
  • 作者简介:孙俊良研究员,1979年出生。2006年获得北京大学化学与分子工程学院博士学位,师从林建华教授;现为北京大学化学与分子工程学院无机固体材料化学课题组组长,博士生导师,主要研究方向为无机微孔材料的合成和应用、结构解析方法的发展,致密固相化合物。
  • 基金资助:
    国家自然科学基金(21527803);国家自然科学基金(21471009);国家自然科学基金(21621061)

Application of Combining X-ray Diffraction and Electron Crystallography for Determination of Complex Inorganic Crystal Structure

Jian Li,Cong Lin,Jianhua Lin,Junliang Sun*()   

  • Received:2019-07-18 Accepted:2019-09-17 Published:2019-09-24
  • Contact: Junliang Sun E-mail:junliang.sun@pku.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21527803);the National Natural Science Foundation of China(21471009);the National Natural Science Foundation of China(21621061)

摘要:

自然界中的材料,比如无机材料,有机材料,生物材料等等,均有其独特的物理和化学性质。而材料的性能又与材料的结构息息相关,只有充分了解了材料的结构,才能更加深入的研究材料性质。因此,材料结构的确定在化学、物理、生物等学科中的显得尤为重要。X射线晶体学作为传统的结构解析技术仍然是目前最重要的结构解析手段,但是对于复杂结构,X射线衍射晶体学解析结构也存在一些不足,往往需要其他技术手段相补充才能完成复杂结构的结构解析。电子晶体学虽然起步比X射线晶体学晚,但是,经过近几十年的发展,已经是结构解析领域一个非常重要的手段。本文将主要介绍X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用。

关键词: 结构确定, X射线衍射, 电子晶体学, 三维电子衍射, 复杂无机晶体结构

Abstract:

Inorganic, organic, and biological materials have specific natural properties which mostly depend on their atomic structures. The properties of novel materials can be predicted based solely on knowing the structure fully. Thus, structure determination plays a very important role in chemistry, physics, and materials science. X-ray crystallography, including single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), remains an important technique for studying structures. However, SCXRD can only be applied to high-quality large single crystals without disorders/defects, whereas PXRD provides only one-dimensional information and reflections with the similar d-values will overlap, which makes it difficult to determine the unit-cell parameters, space groups, and accurate intensities. Another important technique for structural determination is electron crystallography (EC). As the electron is the probe, EC alone can be used for those crystals which are too small to be studied by SCXRD or too complex to be studied by PXRD. Electrons interact much more strongly with matter than X-rays; therefore, both electron diffractions (ED) patterns and high-resolution transmission electron microscopy (HRTEM) images can be obtained from nano-sized crystals. Although electron crystallography started later than X-ray crystallography, it has become a very important technique for structural analysis after several decades of development. Especially, three dimensional (3D) ED techniques have been developed, automated electron diffraction tomography (ADT) and rotation electron diffraction (RED), which allow for automated data collection without requiring considerable expertise on the operation of electron microscopes. In addition, the intensities of 3D ED data can be extracted and used for structure determination using specialized software developed for SCXRD. However, the strong interactions between electrons and materials also result in dynamic effects and beam damage. Although the dynamic effects in 3D electron diffraction techniques (ADT and RED) can be significantly reduced, some structures still pose problems for obtaining an initial model due to beam damage. Therefore, EC and X-ray crystallography have significant limitations. For many complicated crystals, a single technique is insufficient to solve the crystal structure and different techniques that supply complementary structural information must be used to obtain a complete structural determination. Herein, the application of X-ray crystallography combined with EC for the analysis of complex inorganic crystal structures will be introduced, covering issues associated with peak overlap, impurities, pseudo-symmetry and twinning, disordered frameworks, location guests, and aperiodic structures.

Key words: Structure determination, X-ray diffraction, Electron crystallography, Three-dimensional electron diffraction, Complex inorganic crystal structure

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摘要:

自然界中的材料,比如无机材料,有机材料,生物材料等等,均有其独特的物理和化学性质。而材料的性能又与材料的结构息息相关,只有充分了解了材料的结构,才能更加深入的研究材料性质。因此,材料结构的确定在化学、物理、生物等学科中的显得尤为重要。X射线晶体学作为传统的结构解析技术仍然是目前最重要的结构解析手段,但是对于复杂结构,X射线衍射晶体学解析结构也存在一些不足,往往需要其他技术手段相补充才能完成复杂结构的结构解析。电子晶体学虽然起步比X射线晶体学晚,但是,经过近几十年的发展,已经是结构解析领域一个非常重要的手段。本文将主要介绍X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用。

关键词: 结构确定, X射线衍射, 电子晶体学, 三维电子衍射, 复杂无机晶体结构

Abstract:

Inorganic, organic, and biological materials have specific natural properties which mostly depend on their atomic structures. The properties of novel materials can be predicted based solely on knowing the structure fully. Thus, structure determination plays a very important role in chemistry, physics, and materials science. X-ray crystallography, including single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), remains an important technique for studying structures. However, SCXRD can only be applied to high-quality large single crystals without disorders/defects, whereas PXRD provides only one-dimensional information and reflections with the similar d-values will overlap, which makes it difficult to determine the unit-cell parameters, space groups, and accurate intensities. Another important technique for structural determination is electron crystallography (EC). As the electron is the probe, EC alone canaddition, the intensities of 3D ED data can be extracted and used for structure determination using specialized software developed for SCXRD. However, the strong interactions between electrons and materials also result in dynamic effects and beam damage. Although the dynamic effects in 3D electron diffraction techniques (ADT and RED) can be significantly reduced, some structures still pose problems for obtaining an initial model due to beam damage. Therefore, EC and X-ray crystallography have significant limitations. For many complicated crystals, a single technique is insufficient to solve the crystal structure and different techniques that supply complementary structural information must be used to obtain a complete structural determination. Herein, the application of X-ray crystallography combined with EC for the analysis of complex inorganic crystal structures will be introduced, covering issues associated with peak overlap, impurities, pseudo-symmetry and twinning, disordered frameworks, location guests, and aperiodic structures.

Key words: Structure determination, X-ray diffraction, Electron crystallography, Three-dimensional electron diffraction, Complex inorganic crystal structure

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