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

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

doi:10.1038/nmat4852

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

Journal Article · Mon Feb 20 04:00:00 EST 2017 · Nature Materials

DOI:https://doi.org/10.1038/nmat4852· OSTI ID:1379835

Zhu, Yihan ^[1]; Ciston, Jim ^[2]; Zheng, Bin ^[3]; Miao, Xiaohe ^[4]; Czarnik, Cory ^[5]; Pan, Yichang ^[1]; Sougrat, Rachid; ^[1]; Hsiung, Chia-En ^[1]; Yao, Kexin ^[1]; Pinnau, Ingo ^[1]; Pan, Ming ^[5]; ^[1]

King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudia Arabia). Advanced Membranes and Porous Materials Center
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy
Xi'an Univ. of Science and Technology (China). School of Materials Science and Engineering
King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudia Arabia). Imaging and Characterization Core Lab.
Gatan Inc., Pleasanton, CA (United States)

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 catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. 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. Our observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1379835

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 5 Vol. 16; ISSN 1476-1122

Publisher:: Springer Nature

Country of Publication:: United States

Language:: English

References (28)

Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja404514r	journal	May 2013
Directional Self-Assembly of a Colloidal Metal-Organic Framework Yanai, Nobuhiro; Granick, Steve Angewandte Chemie International Edition, Vol. 51, Issue 23 https://doi.org/10.1002/anie.201109132	journal	April 2012
Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst Zhu, Yihan; Wang, Qingxiao; Zhao, Lan Chemistry of Materials, Vol. 24, Issue 16 https://doi.org/10.1021/cm301828n	journal	August 2012
Automated Diffraction Tomography for the Structure Elucidation of Twinned, Sub-micrometer Crystals of a Highly Porous, Catalytically Active Bismuth Metal-Organic Framework Feyand, Mark; Mugnaioli, Enrico; Vermoortele, Frederik Angewandte Chemie International Edition, Vol. 51, Issue 41 https://doi.org/10.1002/anie.201204963	journal	September 2012
Direct evidence for atomic defects in graphene layers Hashimoto, Ayako; Suenaga, Kazu; Gloter, Alexandre Nature, Vol. 430, Issue 7002 https://doi.org/10.1038/nature02817	journal	August 2004
Direct Observation of Surface Reconstruction and Termination on a Complex Metal Oxide Catalyst by Electron Microscopy Zhu, Yihan; Wang, Qingxiao; Zhao, Lan Angewandte Chemie International Edition, Vol. 51, Issue 17 https://doi.org/10.1002/anie.201108532	journal	March 2012
Crystal engineering of lattice metrics of perhalometallate salts and MOFs Adams, C. J.; Haddow, M. F.; Lusi, M. Proceedings of the National Academy of Sciences, Vol. 107, Issue 37 https://doi.org/10.1073/pnas.0910146107	journal	August 2010
Imaging of intact MOF-5 nanocrystals by advanced TEM at liquid nitrogen temperature Wiktor, Christian; Turner, Stuart; Zacher, Denise Microporous and Mesoporous Materials, Vol. 162 https://doi.org/10.1016/j.micromeso.2012.06.014	journal	November 2012
Electron CrystallographyElectron Microscopy and Electron Diffraction Zou, Xiaodong; Hovmöller, Sven; Oleynikov, Peter https://doi.org/10.1093/acprof:oso/9780199580200.001.0001	book	January 2011
Low-dose high-resolution electron microscopy of zeolite materials with a slow-scan CCD camera Pan, M.; Crozier, P. A. Ultramicroscopy, Vol. 48, Issue 3 https://doi.org/10.1016/0304-3991(93)90108-A	journal	March 1993
Dirac–Fock calculations of X-ray scattering factors and contributions to the mean inner potential for electron scattering Rez, D.; Rez, P.; Grant, I. Acta Crystallographica Section A Foundations of Crystallography, Vol. 50, Issue 4 https://doi.org/10.1107/S0108767393013200	journal	July 1994
Generation and applications of structure envelopes for porous metal–organic frameworks Yakovenko, Andrey A.; Reibenspies, Joseph H.; Bhuvanesh, Nattamai Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889812050935	journal	February 2013
Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework Cravillon, Janosch; Münzer, Simon; Lohmeier, Sven-Jare Chemistry of Materials, Vol. 21, Issue 8 https://doi.org/10.1021/cm900166h	journal	April 2009
CRISP: crystallographic image processing on a personal computer Hovmöller, Sven Ultramicroscopy, Vol. 41, Issue 1-3 https://doi.org/10.1016/0304-3991(92)90102-P	journal	April 1992
Direct observations of the MOF (UiO-66) structure by transmission electron microscopy Zhu, Liangkui; Zhang, Daliang; Xue, Ming CrystEngComm, Vol. 15, Issue 45 https://doi.org/10.1039/c3ce41122b	journal	January 2013
First Direct Imaging of Giant Pores of the Metal−Organic Framework MIL-101 Lebedev, O. I.; Millange, F.; Serre, C. Chemistry of Materials, Vol. 17, Issue 26 https://doi.org/10.1021/cm051870o	journal	December 2005
2.2 A resolution cryo-EM structure of -galactosidase in complex with a cell-permeant inhibitor Bartesaghi, A.; Merk, A.; Banerjee, S. Science, Vol. 348, Issue 6239 https://doi.org/10.1126/science.aab1576	journal	May 2015
Recent developments and future directions in the growth of nanostructures by van der Waals epitaxy Bakti Utama, Muhammad Iqbal; Zhang, Qing; Zhang, Jun Nanoscale, Vol. 5, Issue 9 https://doi.org/10.1039/c3nr34011b	journal	January 2013
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Surface nano-architecture of a metal–organic framework Makiura, Rie; Motoyama, Soichiro; Umemura, Yasushi Nature Materials, Vol. 9, Issue 7 https://doi.org/10.1038/nmat2769	journal	May 2010
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
Electric Field-Induced Assembly of Monodisperse Polyhedral Metal–Organic Framework Crystals Yanai, Nobuhiro; Sindoro, Melinda; Yan, Jing Journal of the American Chemical Society, Vol. 135, Issue 1 https://doi.org/10.1021/ja309361d	journal	December 2012
Zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes for gas separation Song, Qilei; Nataraj, S. K.; Roussenova, Mina V. Energy & Environmental Science, Vol. 5, Issue 8 https://doi.org/10.1039/c2ee21996d	journal	January 2012
Atomic Observations of Microporous Materials Highly Unstable under the Electron Beam: The Cases of Ti-Doped AlPO ₄ -5 and Zn-MOF-74 Mayoral, Alvaro; Sanchez-Sanchez, Manuel; Alfayate, Almudena ChemCatChem, Vol. 7, Issue 22 https://doi.org/10.1002/cctc.201500617	journal	September 2015
Electron counting and beam-induced motion correction enable near-atomic-resolution single-particle cryo-EM Li, Xueming; Mooney, Paul; Zheng, Shawn Nature Methods, Vol. 10, Issue 6 https://doi.org/10.1038/nmeth.2472	journal	May 2013
Correlated defect nanoregions in a metal–organic framework Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5176	journal	June 2014
Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
Defect-Engineered Metal-Organic Frameworks Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E. Angewandte Chemie International Edition, Vol. 54, Issue 25 https://doi.org/10.1002/anie.201411540	journal	June 2015

Similar Records

Insights into the Structure and Dynamics of Metal–Organic Frameworks via Transmission Electron Microscopy

Journal Article · Thu Sep 17 20:00:00 EDT 2020 · Journal of the American Chemical Society · OSTI ID:1779735

Unraveling the Interfacial Structure–Performance Correlation of Flexible Metal–Organic Framework Membranes on Polymeric Substrates

Journal Article · Wed Jan 09 19:00:00 EST 2019 · ACS Applied Materials and Interfaces · OSTI ID:1499805

Bio-Templated Chiral Zeolitic Imidazolate Framework for Enantioselective Chemoresistive Sensing

Journal Article · Thu May 25 20:00:00 EDT 2023 · Angewandte Chemie (International Edition) · OSTI ID:1991682

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
imaging techniques
metal-organic frameworks
solid-state chemistry
transmission electron microscopy

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

Citation Formats

References (28)

Similar Records

Related Subjects