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用于发现金属有机框架中旋转节点结构的实空间成像

Real-space imaging for discovering a rotated node structure in metal-organic framework.

作者信息

Feng Jiale, Feng Zhipeng, Xu Liang, Meng Haibing, Chen Xiao, Ma Mengmeng, Wang Lei, Song Bin, Tang Xuan, Dai Sheng, Wei Fei, Cheng Tao, Shen Boyuan

机构信息

Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, 215123, Jiangsu, PR China.

Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou, 215123, China.

出版信息

Nat Commun. 2024 Aug 13;15(1):6962. doi: 10.1038/s41467-024-51384-9.

Abstract

Resolving the detailed structures of metal organic frameworks is of great significance for understanding their structure-property relation. Real-space imaging methods could exhibit superiority in revealing not only the local structure but also the bulk symmetry of these complex porous materials, compared to reciprocal-space diffraction methods, despite the technical challenges. Here we apply a low-dose imaging technique to clearly resolve the atomic structures of building units in a metal-organic framework, MIL-125. An unexpected node structure is discovered by directly imaging the rotation of Ti-O nodes, different from the unrotated structure predicted by previous X-ray diffraction. The imaged structure and symmetry can be confirmed by the structural simulations and energy calculations. Then, the distribution of node rotation from the edge to the center of a MIL-125 particle is revealed by the image analysis of Ti-O rotation. The related defects and surface terminations in MIL-125 are also investigated in the real-space images. These results not only unraveled the node symmetry in MIL-125 with atomic resolution but also inspired further studies on discovering more unpredicted structural changes in other porous materials by real-space imaging methods.

摘要

解析金属有机框架的详细结构对于理解其结构-性能关系具有重要意义。与倒易空间衍射方法相比,实空间成像方法在揭示这些复杂多孔材料的局部结构和整体对称性方面可能具有优势,尽管存在技术挑战。在这里,我们应用低剂量成像技术来清晰地解析金属有机框架MIL-125中构建单元的原子结构。通过直接成像Ti-O节点的旋转,发现了一种意想不到的节点结构,这与先前X射线衍射预测的未旋转结构不同。成像结构和对称性可以通过结构模拟和能量计算得到证实。然后,通过对Ti-O旋转的图像分析揭示了MIL-125颗粒从边缘到中心的节点旋转分布。在实空间图像中还研究了MIL-125中相关的缺陷和表面终止情况。这些结果不仅以原子分辨率揭示了MIL-125中的节点对称性,还激发了通过实空间成像方法在其他多孔材料中发现更多未预测结构变化的进一步研究。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7972/11322488/cb89b6fd11a7/41467_2024_51384_Fig1_HTML.jpg

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