Mixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations
dc.contributor.author | Taddei, Marco | |
dc.contributor.author | Tiana, Davide | |
dc.contributor.author | Casati, Nicola | |
dc.contributor.author | van Bokhoven, Jeroen A. | |
dc.contributor.author | Smit, Berend | |
dc.contributor.author | Ranocchiari, Marco | |
dc.contributor.funder | Paul Scherrer Institut | en |
dc.contributor.funder | National Center of Competence in Research Materials’ Revolution: Computational Design and Discovery of Novel Materials | en |
dc.contributor.funder | Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung | en |
dc.contributor.funder | H2020 European Research Council | en |
dc.contributor.funder | Centro Svizzero di Calcolo Scientifico, CSCS | |
dc.date.accessioned | 2018-07-06T14:10:11Z | |
dc.date.available | 2018-07-06T14:10:11Z | |
dc.date.issued | 2016-12-06 | |
dc.date.updated | 2018-07-03T11:04:08Z | |
dc.description.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 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 bromofunctionalized 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. | en |
dc.description.sponsorship | Paul Scherrer Institut (Energy System Integration (ESI) platform); Centro svizzero di calcolo scientifico, CSCS (Swiss National Supercomputing Centre, Project no. s611); National Center of Competence in Research (NCCR) ‘‘Materials’ Revolution: Computational Design and Discovery of Novel Materials (MARVEL); | en |
dc.description.status | Peer reviewed | en |
dc.description.version | Published Version | en |
dc.format.mimetype | application/pdf | en |
dc.identifier.citation | Taddei, M., Tiana, D., Casati, N., van Bokhoven, J. A., Smit, B. and Ranocchiari, M. (2017) 'Mixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations', Physical Chemistry Chemical Physics, 19(2), pp. 1551-1559. doi: 10.1039/c6cp07801j | en |
dc.identifier.doi | 10.1039/c6cp07801j | |
dc.identifier.endpage | 1559 | en |
dc.identifier.issn | 1463-9076 | |
dc.identifier.journaltitle | Physical Chemistry Chemical Physics | en |
dc.identifier.startpage | 1551 | en |
dc.identifier.uri | https://hdl.handle.net/10468/6428 | |
dc.identifier.volume | 19 | en |
dc.language.iso | en | en |
dc.publisher | Royal Society of Chemistry (RSC) | en |
dc.relation.project | info:eu-repo/grantAgreement/EC/H2020::ERC::ERC-ADG/666983/EU/The Materials Genome in Action/MaGic | en |
dc.relation.uri | http://dx.doi.org/10.1039/C6CP07801J | |
dc.rights | © the Owner Societies 2017. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence | en |
dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | en |
dc.subject | Metal-organic frameworks | en |
dc.subject | Zeolitic imidazolate frameworks | en |
dc.subject | Porous coordination polymers | en |
dc.subject | Post-synthetic modification | en |
dc.subject | Band-gap | en |
dc.subject | Adsorption properties | en |
dc.subject | Postsynthetic ligand | en |
dc.subject | NMR-spectroscopy | en |
dc.subject | Solid-solutions | en |
dc.subject | Vegards law | en |
dc.title | Mixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations | en |
dc.type | Article (peer-reviewed) | en |
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