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Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations

Marco Taddei Orcid Logo, Davide Tiana, Nicola Casati, Jeroen A. van Bokhoven, Berend Smit, Marco Ranocchiari

Physical Chemistry Chemical Physics, Volume: 19, Issue: 2, Pages: 1551 - 1559

Swansea University Author: Marco Taddei Orcid Logo

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DOI (Published version): 10.1039/c6cp07801j

Abstract

The use of mixed-linker metal–organic frameworks (MIXMOFs) is one of the most effective strategies to modulate the physical–chemical properties of MOFs without affecting the overall crystal structure. In many instances, MIXMOFs have been recognized as solid solutions, with random distribution of lig...

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Published in: Physical Chemistry Chemical Physics
ISSN: 1463-9076 1463-9084
Published: Royal Society of Chemistry (RSC) 2017
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URI: https://cronfa.swan.ac.uk/Record/cronfa32738
first_indexed 2017-03-29T13:47:14Z
last_indexed 2018-02-09T05:20:59Z
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spelling 2017-10-06T11:52:47.0993969 v2 32738 2017-03-29 Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations 5cffd1038508554d8596dee8b4e51052 0000-0003-2805-6375 Marco Taddei Marco Taddei true false 2017-03-29 The use of mixed-linker metal–organic frameworks (MIXMOFs) is one of the most effective strategies to modulate the physical–chemical properties of MOFs without affecting the overall crystal structure. In many instances, MIXMOFs have been recognized as solid solutions, with random distribution of ligands, in agreement with the empirical rule known as Vegard's law. In this work, we have undertaken a study combining high-resolution powder X-ray diffraction (HR-PXRD) and density functional theory (DFT) calculations with the aim of understanding the reasons why UiO-66-based amino- and bromo-functionalized MIXMOFs (MIXUiO-66) undergo cell expansion obeying Vegard's law and how this behaviour is related to their physical–chemical properties. DFT calculations predict that the unit cell in amino-functionalized UiO-66 experiences only minor expansion as a result of steric effects, whereas major modification to the electronic features of the framework leads to weaker metal–linker interaction and consequently to the loss of stability at higher degrees of functionalization. For bromo-functionalized UiO-66, steric repulsion due to the size of bromine yields a large cell expansion, but the electronic features remain very similar to pristine UiO-66, preserving the stability of the framework upon functionalization. MIXUiO-66 obtained by either direct synthesis or by post-synthetic exchange shows Vegard-like behaviour, suggesting that both preparation methods yield solid solutions, but the thermal stability and the textural properties of the post-synthetic exchanged materials do not display a clear dependence on the chemical composition, as observed for the MOFs obtained by direct synthesis. Journal Article Physical Chemistry Chemical Physics 19 2 1551 1559 Royal Society of Chemistry (RSC) 1463-9076 1463-9084 31 12 2017 2017-12-31 10.1039/c6cp07801j COLLEGE NANME COLLEGE CODE Swansea University 2017-10-06T11:52:47.0993969 2017-03-29T09:52:31.8688615 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Marco Taddei 0000-0003-2805-6375 1 Davide Tiana 2 Nicola Casati 3 Jeroen A. van Bokhoven 4 Berend Smit 5 Marco Ranocchiari 6 32738__16375__9dd574ae83af4863bffcca618a4c7115.pdf 32738.pdf 2020-01-21T12:59:49.9206293 Output 2799828 application/pdf Version of Record true Released under the terms of a Creative Commons Attribution 3.0 Unported Licence (CC-BY). true eng http://creativecommons.org/licenses/by/3.0/
title Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
spellingShingle Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
Marco Taddei
title_short Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
title_full Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
title_fullStr Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
title_full_unstemmed Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
title_sort Mixed-linker UiO-66: structure–property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
author_id_str_mv 5cffd1038508554d8596dee8b4e51052
author_id_fullname_str_mv 5cffd1038508554d8596dee8b4e51052_***_Marco Taddei
author Marco Taddei
author2 Marco Taddei
Davide Tiana
Nicola Casati
Jeroen A. van Bokhoven
Berend Smit
Marco Ranocchiari
format Journal article
container_title Physical Chemistry Chemical Physics
container_volume 19
container_issue 2
container_start_page 1551
publishDate 2017
institution Swansea University
issn 1463-9076
1463-9084
doi_str_mv 10.1039/c6cp07801j
publisher Royal Society of Chemistry (RSC)
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 - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
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description The use of mixed-linker metal–organic frameworks (MIXMOFs) is one of the most effective strategies to modulate the physical–chemical properties of MOFs without affecting the overall crystal structure. In many instances, MIXMOFs have been recognized as solid solutions, with random distribution of ligands, in agreement with the empirical rule known as Vegard's law. In this work, we have undertaken a study combining high-resolution powder X-ray diffraction (HR-PXRD) and density functional theory (DFT) calculations with the aim of understanding the reasons why UiO-66-based amino- and bromo-functionalized MIXMOFs (MIXUiO-66) undergo cell expansion obeying Vegard's law and how this behaviour is related to their physical–chemical properties. DFT calculations predict that the unit cell in amino-functionalized UiO-66 experiences only minor expansion as a result of steric effects, whereas major modification to the electronic features of the framework leads to weaker metal–linker interaction and consequently to the loss of stability at higher degrees of functionalization. For bromo-functionalized UiO-66, steric repulsion due to the size of bromine yields a large cell expansion, but the electronic features remain very similar to pristine UiO-66, preserving the stability of the framework upon functionalization. MIXUiO-66 obtained by either direct synthesis or by post-synthetic exchange shows Vegard-like behaviour, suggesting that both preparation methods yield solid solutions, but the thermal stability and the textural properties of the post-synthetic exchanged materials do not display a clear dependence on the chemical composition, as observed for the MOFs obtained by direct synthesis.
published_date 2017-12-31T07:07:08Z
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