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

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dc.contributor.authorTaddei, Marco
dc.contributor.authorTiana, Davide
dc.contributor.authorCasati, Nicola
dc.contributor.authorvan Bokhoven, Jeroen A.
dc.contributor.authorSmit, Berend
dc.contributor.authorRanocchiari, Marco
dc.contributor.funderPaul Scherrer Instituten
dc.contributor.funderNational Center of Competence in Research Materials’ Revolution: Computational Design and Discovery of Novel Materialsen
dc.contributor.funderSchweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschungen
dc.contributor.funderH2020 European Research Councilen
dc.contributor.funderCentro Svizzero di Calcolo Scientifico, CSCS
dc.date.accessioned2018-07-06T14:10:11Z
dc.date.available2018-07-06T14:10:11Z
dc.date.issued2016-12-06
dc.date.updated2018-07-03T11:04:08Z
dc.description.abstractThe 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.sponsorshipPaul 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.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationTaddei, 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/c6cp07801jen
dc.identifier.doi10.1039/c6cp07801j
dc.identifier.endpage1559en
dc.identifier.issn1463-9076
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen
dc.identifier.startpage1551en
dc.identifier.urihttps://hdl.handle.net/10468/6428
dc.identifier.volume19en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::ERC::ERC-ADG/666983/EU/The Materials Genome in Action/MaGicen
dc.relation.urihttp://dx.doi.org/10.1039/C6CP07801J
dc.rights© the Owner Societies 2017. This article is licensed under a Creative Commons Attribution 3.0 Unported Licenceen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subjectMetal-organic frameworksen
dc.subjectZeolitic imidazolate frameworksen
dc.subjectPorous coordination polymersen
dc.subjectPost-synthetic modificationen
dc.subjectBand-gapen
dc.subjectAdsorption propertiesen
dc.subjectPostsynthetic liganden
dc.subjectNMR-spectroscopyen
dc.subjectSolid-solutionsen
dc.subjectVegards lawen
dc.titleMixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculationsen
dc.typeArticle (peer-reviewed)en
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