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

Nature Materials volume 16, pages 532–536 (2017)Cite this article

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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.

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Figure 1: Atomic-resolution imaging of the ZIF-8 crystal lattice.
Figure 2: Surface termination of ZIF-8 crystals.
Figure 3: Coherent interface formed between two assembled ZIF-8 crystals.
Figure 4: Formation of interfacial cavities between assembled ZIF-8 crystals and their influences on gas diffusion.

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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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Authors and Affiliations

  1. Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Advanced Membranes and Porous Materials Center, Thuwal 23955-6900, Saudi Arabia

    Yihan Zhu, Yichang Pan, Zhiping Lai, Chia-En Hsiung, Kexin Yao, Ingo Pinnau & Yu Han

  2. National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Jim Ciston

  3. School of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an 710054, China

    Bin Zheng

  4. King Abdullah University of Science and Technology (KAUST), Imaging and Characterization Core Lab, Thuwal 23955-6900, Saudi Arabia

    Xiaohe Miao & Rachid Sougrat

  5. Gatan, Inc., Pleasanton, California 94588, USA

    Cory Czarnik & Ming Pan

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  1. Yihan Zhu
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Contributions

Y.Z. and Y.H. conceived and designed the experiments. J.C. and M.P. performed the low-dose high-resolution TEM image acquisition. Y.Z., J.C., M.P. and Y.H. carried out the TEM image processing, analysis and simulation. Y.Z., B.Z. and X.M. performed the theoretical simulations. Y.P., Z.L. and R.S. prepared the samples for imaging. C.-E.H. synthesized the ZIF-8 samples of various sizes and shapes. K.Y. and I.P. performed kinetic vapour adsorption experiments. Y.Z. drafted the manuscript and Y.H., J.C., M.P. and C.C. revised it. All authors commented on the manuscript.

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Correspondence to Yihan Zhu, Ming Pan or Yu Han.

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The authors declare no competing financial interests.

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Zhu, Y., Ciston, J., Zheng, B. et al. Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy. Nature Mater 16, 532–536 (2017). https://doi.org/10.1038/nmat4852

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