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Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!

Marco Taddei Orcid Logo, Russell J. Wakeham, Athanasios Koutsianos, Enrico Andreoli Orcid Logo, Andrew Barron Orcid Logo

Angewandte Chemie International Edition, Volume: 57, Issue: 36, Pages: 11706 - 11710

Swansea University Authors: Marco Taddei Orcid Logo, Enrico Andreoli Orcid Logo, Andrew Barron Orcid Logo

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DOI (Published version): 10.1002/anie.201806910

Abstract

Post‐synthetic ligand exchange in the prototypical zirconium‐based metal‐organic framework UiO‐66 was investigated by in situ solution 1H nuclear magnetic resonance. Samples of UiO‐66 having different degrees of defectivity were exchanged using solutions of several terephthalic acid analogues in a r...

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Published in: Angewandte Chemie International Edition
ISSN: 1433-7851
Published: 2018
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URI: https://cronfa.swan.ac.uk/Record/cronfa40989
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spelling 2020-12-17T11:18:49.7485800 v2 40989 2018-07-13 Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects! 5cffd1038508554d8596dee8b4e51052 0000-0003-2805-6375 Marco Taddei Marco Taddei true false cbd843daab780bb55698a3daccd74df8 0000-0002-1207-2314 Enrico Andreoli Enrico Andreoli true false 92e452f20936d688d36f91c78574241d 0000-0002-2018-8288 Andrew Barron Andrew Barron true false 2018-07-13 EEN Post‐synthetic ligand exchange in the prototypical zirconium‐based metal‐organic framework UiO‐66 was investigated by in situ solution 1H nuclear magnetic resonance. Samples of UiO‐66 having different degrees of defectivity were exchanged using solutions of several terephthalic acid analogues in a range of conditions. Linker exchange only occurred in defect‐free UiO‐66, whereas monocarboxylates grafted at defective sites were found to be preferentially exchanged with respect to terephthalic acid over the whole range of conditions investigated. A 1:1 exchange ratio between the terephthalic acid analogue and modulator was observed, providing evidence that the defects had missing‐cluster nature. Ex situ characterisation of the MOF powders after exchange corroborated these findings and evidenced that the physical‐chemical properties of the MOF depend on whether the functionalisation occurs at defective sites or on the framework. N2 sorption analysis showed that, upon exchange, defective samples underwent significant decrease of surface area and disappearance of large pores, associated with the presence of missing‐cluster defects in the starting material. CO2 sorption studies displayed the different impact of pure defect functionalisation and pure framework functionalisation on isosteric heat of adsorption and CO2/N2 selectivity. Journal Article Angewandte Chemie International Edition 57 36 11706 11710 1433-7851 31 12 2018 2018-12-31 10.1002/anie.201806910 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2020-12-17T11:18:49.7485800 2018-07-13T08:59:25.3456005 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Marco Taddei 0000-0003-2805-6375 1 Russell J. Wakeham 2 Athanasios Koutsianos 3 Enrico Andreoli 0000-0002-1207-2314 4 Andrew Barron 0000-0002-2018-8288 5 0040989-13072018090641.pdf taddei2018.pdf 2018-07-13T09:06:41.5900000 Output 1464242 application/pdf Accepted Manuscript true 2019-07-10T00:00:00.0000000 true eng
title Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
spellingShingle Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
Marco Taddei
Enrico Andreoli
Andrew Barron
title_short Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
title_full Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
title_fullStr Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
title_full_unstemmed Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
title_sort Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
author_id_str_mv 5cffd1038508554d8596dee8b4e51052
cbd843daab780bb55698a3daccd74df8
92e452f20936d688d36f91c78574241d
author_id_fullname_str_mv 5cffd1038508554d8596dee8b4e51052_***_Marco Taddei
cbd843daab780bb55698a3daccd74df8_***_Enrico Andreoli
92e452f20936d688d36f91c78574241d_***_Andrew Barron
author Marco Taddei
Enrico Andreoli
Andrew Barron
author2 Marco Taddei
Russell J. Wakeham
Athanasios Koutsianos
Enrico Andreoli
Andrew Barron
format Journal article
container_title Angewandte Chemie International Edition
container_volume 57
container_issue 36
container_start_page 11706
publishDate 2018
institution Swansea University
issn 1433-7851
doi_str_mv 10.1002/anie.201806910
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
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description Post‐synthetic ligand exchange in the prototypical zirconium‐based metal‐organic framework UiO‐66 was investigated by in situ solution 1H nuclear magnetic resonance. Samples of UiO‐66 having different degrees of defectivity were exchanged using solutions of several terephthalic acid analogues in a range of conditions. Linker exchange only occurred in defect‐free UiO‐66, whereas monocarboxylates grafted at defective sites were found to be preferentially exchanged with respect to terephthalic acid over the whole range of conditions investigated. A 1:1 exchange ratio between the terephthalic acid analogue and modulator was observed, providing evidence that the defects had missing‐cluster nature. Ex situ characterisation of the MOF powders after exchange corroborated these findings and evidenced that the physical‐chemical properties of the MOF depend on whether the functionalisation occurs at defective sites or on the framework. N2 sorption analysis showed that, upon exchange, defective samples underwent significant decrease of surface area and disappearance of large pores, associated with the presence of missing‐cluster defects in the starting material. CO2 sorption studies displayed the different impact of pure defect functionalisation and pure framework functionalisation on isosteric heat of adsorption and CO2/N2 selectivity.
published_date 2018-12-31T03:52:13Z
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