Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

Yihan Zhu; Jim Ciston; Bin Zheng; Xiaohe Miao; Cory Czarnik; Yichang Pan; Rachid Sougrat; Zhiping Lai; Chia-En Hsiung; Kexin Yao; Ingo Pinnau; Ming Pan; Yu Han

doi:10.1038/nmat4852

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

Yihan Zhu, Jim Ciston, Bin Zheng, Xiaohe Miao, Cory Czarnik, Yichang Pan, Rachid Sougrat, Zhiping Lai, Chia-En Hsiung, Kexin Yao, Ingo Pinnau, Ming Pan, Yu Han

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315 Scopus citations

Abstract

Metal–organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis1, 2, 3. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation4, 5, 6, 7. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

Original language	English (US)
Pages (from-to)	532-536
Number of pages	5
Journal	Nature Materials
Volume	16
Issue number	5
DOIs	https://doi.org/10.1038/nmat4852
State	Published - Feb 20 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): FCC/1/1972-19, URF/1/2570-01-01
Acknowledgements: This research was supported by competitive research funds (FCC/1/1972-19 and URF/1/2570-01-01) to Y.H. from King Abdullah University of Science and Technology. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. Additional support for B.Z. was provided by the NSF of China (Grant 21503165). We thank C. T. Koch from Humboldt-Universität zu Berlin and C. Ophus from Lawrence Berkeley National Laboratory for helpful discussions.

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@article{487f69d75a3b4c1da2444e2750856397,

title = "Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy",

abstract = "Metal–organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis1, 2, 3. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation4, 5, 6, 7. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square {\aa}ngstr{\"o}m to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 {\AA}, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.",

author = "Yihan Zhu and Jim Ciston and Bin Zheng and Xiaohe Miao and Cory Czarnik and Yichang Pan and Rachid Sougrat and Zhiping Lai and Chia-En Hsiung and Kexin Yao and Ingo Pinnau and Ming Pan and Yu Han",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): FCC/1/1972-19, URF/1/2570-01-01 Acknowledgements: This research was supported by competitive research funds (FCC/1/1972-19 and URF/1/2570-01-01) to Y.H. from King Abdullah University of Science and Technology. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. Additional support for B.Z. was provided by the NSF of China (Grant 21503165). We thank C. T. Koch from Humboldt-Universit{\"a}t zu Berlin and C. Ophus from Lawrence Berkeley National Laboratory for helpful discussions.",

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doi = "10.1038/nmat4852",

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AU - Zhu, Yihan

AU - Ciston, Jim

AU - Zheng, Bin

AU - Miao, Xiaohe

AU - Czarnik, Cory

AU - Pan, Yichang

AU - Sougrat, Rachid

AU - Lai, Zhiping

AU - Hsiung, Chia-En

AU - Yao, Kexin

AU - Pinnau, Ingo

AU - Pan, Ming

AU - Han, Yu

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): FCC/1/1972-19, URF/1/2570-01-01 Acknowledgements: This research was supported by competitive research funds (FCC/1/1972-19 and URF/1/2570-01-01) to Y.H. from King Abdullah University of Science and Technology. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. Additional support for B.Z. was provided by the NSF of China (Grant 21503165). We thank C. T. Koch from Humboldt-Universität zu Berlin and C. Ophus from Lawrence Berkeley National Laboratory for helpful discussions.

PY - 2017/2/20

Y1 - 2017/2/20

N2 - Metal–organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis1, 2, 3. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation4, 5, 6, 7. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

AB - Metal–organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis1, 2, 3. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation4, 5, 6, 7. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

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DO - 10.1038/nmat4852

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SP - 532

EP - 536

JO - Nature Materials

JF - Nature Materials

IS - 5

ER -

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

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