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Imaging defects and their evolution in a metal–organic framework at sub-unit-cell resolution

Liu, Lingmei; Chen, Zhijie; Wang, Jianjian; Zhang, Daliang; Zhu, Yihan; Ling, Sanliang; Huang, Kuo Wei; Belmabkhout, Youssef; Adil, Karim; Zhang, Yuxin; Slater, Ben; Eddaoudi, Mohamed; Han, Yu


Lingmei Liu

Zhijie Chen

Jianjian Wang

Daliang Zhang

Yihan Zhu

Kuo Wei Huang

Youssef Belmabkhout

Karim Adil

Yuxin Zhang

Ben Slater

Mohamed Eddaoudi

Yu Han


© 2019, The Author(s), under exclusive licence to Springer Nature Limited. Defect engineering of metal–organic frameworks (MOFs) offers promising opportunities for tailoring their properties to specific functions and applications. However, determining the structures of defects in MOFs—either point defects or extended ones—has proved challenging owing to the difficulty of directly probing local structures in these typically fragile crystals. Here we report the real-space observation, with sub-unit-cell resolution, of structural defects in the catalytic MOF UiO-66 using a combination of low-dose transmission electron microscopy and electron crystallography. Ordered ‘missing linker’ and ‘missing cluster’ defects were found to coexist. The missing-linker defects, reconstructed three-dimensionally with high precision, were attributed to terminating formate groups. The crystallization of the MOF was found to undergo an Ostwald ripening process, during which the defects also evolve: on prolonged crystallization, only the missing-linker defects remained. These observations were rationalized through density functional theory calculations. Finally, the missing-cluster defects were shown to be more catalytically active than their missing-linker counterparts for the isomerization of glucose to fructose.


Liu, L., Chen, Z., Wang, J., Zhang, D., Zhu, Y., Ling, S., …Han, Y. (2019). Imaging defects and their evolution in a metal–organic framework at sub-unit-cell resolution. Nature Chemistry, 11(7), 622-628.

Journal Article Type Article
Acceptance Date Mar 26, 2019
Online Publication Date May 13, 2019
Publication Date 2019-07
Deposit Date Jul 31, 2019
Publicly Available Date Nov 14, 2019
Journal Nature Chemistry
Print ISSN 1755-4330
Electronic ISSN 1755-4349
Publisher Nature Publishing Group
Peer Reviewed Peer Reviewed
Volume 11
Issue 7
Pages 622-628
Keywords General Chemistry; General Chemical Engineering
Public URL
Publisher URL
Additional Information Received: 4 July 2018; Accepted: 26 March 2019; First Online: 13 May 2019; : The authors declare no competing interests.


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