Computational studies on metal-organic frameworks as catalysts

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dc.availability.bitstreamopenaccess
dc.contributor.advisorTiana, Davideen
dc.contributor.authorPareras, Gerard
dc.contributor.funderIrish Research Councilen
dc.date.accessioned2022-05-16T11:58:11Z
dc.date.available2022-05-16T11:58:11Z
dc.date.issued2021-12-16
dc.date.submitted2021-12-16
dc.description.abstractMetal-Organic Frameworks (MOFs) are nanoporous materials containing three-dimensional (3D) periodic networks of metal clusters held together by bridging organic linkers. They are thermally stable, crystalline, and characterized by high porosities and record-breaking surface. Moreover, their stability and perfect crystalline net offer the possibility to perform catalytic processes within its framework as well as intervening as catalysts themselves. The applicability of MOFs within the branch of catalysis is immense and makes an impossible task to experimentally explore and test all the possible applications. However, computational chemistry can help in to predict such catalytic behaviour reducing the number of test-and-error experiments by preliminary discarding those that theoretically show no catalytic performance. This manuscript gathers four works (two published, two to be submitted) where computational methodologies have been applied to predict and unveil catalytic applications in different reaction processes. In the first chapter is reported CO2 activation over defective UiO-66 functionalized with amino acids. DFT calculations confirms not only the activation of CO2 but also the formation of carbamic acid due to a cooperative effect between the amino acid chains. Following to the second chapter, it has been described that MOF UiO-67 can be functionalized with a TMEDA like homogenous catalyst, to enhance CO2-ethylene direct coupling reaction. The third chapter is a multidisciplinary work that shows how micropores in metal-organic frameworks (MOFs) push homogeneous catalytic reactions into kinetic regimes inaccessible under standard conditions. Such property allows branched selectivity up to 90% in the Co-catalysed hydroformylation of olefins without directing groups. Finally, chapter 4 describes the encapsulation of Ru olefin catalysts within MOF MIL-101, such encapsulation is a strategy not only for avoiding catalyst decomposition but also to enhance reactivity. All this works apart from studying catalytic performance, selected MOFs have been studied under different computational approaches (molecular cluster and periodic boundary conditions simulations) and using different computational tools (NCI plots, steric maps, frontier molecular orbital, etc.).en
dc.description.statusNot peer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationPareras, G. 2021. Computational studies on metal-organic frameworks as catalysts. PhD Thesis, University College Cork.en
dc.identifier.endpage308en
dc.identifier.urihttps://hdl.handle.net/10468/13186
dc.language.isoenen
dc.publisherUniversity College Corken
dc.rights© 2021, Gerard Pareras.en
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectCatalysisen
dc.subjectComputational chemistryen
dc.subjectMetal-organic frameworksen
dc.titleComputational studies on metal-organic frameworks as catalystsen
dc.typeDoctoral thesisen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD - Doctor of Philosophyen
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