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

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

doi:10.1038/s41557-019-0263-4

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

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

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397 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	622-628
Number of pages	7
Journal	Nature Chemistry
Volume	11
Issue number	7
DOIs	https://doi.org/10.1038/s41557-019-0263-4
State	Published - May 13 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): FCC/1/1972-19
Acknowledgements: This research was supported by Competitive Center Funds (FCC/1/1972-19) to Y.H. and M.E. from King Abdullah University of Science and Technology. This research used resources of the Core Labs of King Abdullah University of Science and Technology. Yi.Z. acknowledges financial support from the National Natural Science Foundation of China (21771161) and the Thousand Talents Program for Distinguished Young Scholars. S.L. and B.S. are thankful to the Materials Chemistry Consortium (EPSRC: EP/L000202) for provision of computer time on ARCHER UK National Supercomputing Service. B.S. acknowledges the Royal Society for financial support through an industry fellowship
(F160062). The authors acknowledge helpful discussions with A. Goodwin, M. Cliffe and G. Shearer.

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https://repository.kaust.edu.sa/bitstream/10754/655981/1/s41557-019-0263-4.pdf

Cite this

@article{dccb1a2b85794ce8b8668b0caf221756,

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

abstract = "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 {\textquoteleft}missing linker{\textquoteright} and {\textquoteleft}missing cluster{\textquoteright} 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.",

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

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): FCC/1/1972-19 Acknowledgements: This research was supported by Competitive Center Funds (FCC/1/1972-19) to Y.H. and M.E. from King Abdullah University of Science and Technology. This research used resources of the Core Labs of King Abdullah University of Science and Technology. Yi.Z. acknowledges financial support from the National Natural Science Foundation of China (21771161) and the Thousand Talents Program for Distinguished Young Scholars. S.L. and B.S. are thankful to the Materials Chemistry Consortium (EPSRC: EP/L000202) for provision of computer time on ARCHER UK National Supercomputing Service. B.S. acknowledges the Royal Society for financial support through an industry fellowship (F160062). The authors acknowledge helpful discussions with A. Goodwin, M. Cliffe and G. Shearer.",

year = "2019",

month = may,

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doi = "10.1038/s41557-019-0263-4",

language = "English (US)",

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pages = "622--628",

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T1 - Imaging defects and their evolution in a metal–organic framework at sub-unit-cell resolution

AU - Liu, Lingmei

AU - Chen, Zhijie

AU - Wang, Jianjian

AU - Zhang, Daliang

AU - Zhu, Yihan

AU - Ling, Sanliang

AU - Huang, Kuo-Wei

AU - Belmabkhout, Youssef

AU - Adil, Karim

AU - Zhang, Yuxin

AU - Slater, Ben

AU - Eddaoudi, Mohamed

AU - Han, Yu

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): FCC/1/1972-19 Acknowledgements: This research was supported by Competitive Center Funds (FCC/1/1972-19) to Y.H. and M.E. from King Abdullah University of Science and Technology. This research used resources of the Core Labs of King Abdullah University of Science and Technology. Yi.Z. acknowledges financial support from the National Natural Science Foundation of China (21771161) and the Thousand Talents Program for Distinguished Young Scholars. S.L. and B.S. are thankful to the Materials Chemistry Consortium (EPSRC: EP/L000202) for provision of computer time on ARCHER UK National Supercomputing Service. B.S. acknowledges the Royal Society for financial support through an industry fellowship (F160062). The authors acknowledge helpful discussions with A. Goodwin, M. Cliffe and G. Shearer.

PY - 2019/5/13

Y1 - 2019/5/13

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/655981

UR - http://www.nature.com/articles/s41557-019-0263-4

UR - http://www.scopus.com/inward/record.url?scp=85065795379&partnerID=8YFLogxK

U2 - 10.1038/s41557-019-0263-4

DO - 10.1038/s41557-019-0263-4

M3 - Article

C2 - 31086300

SN - 1755-4330

VL - 11

SP - 622

EP - 628

JO - Nature Chemistry

JF - Nature Chemistry

IS - 7

ER -

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

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