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dc.contributor.authorKauppinen, Minttu
dc.date.accessioned2020-05-28T13:26:23Z
dc.date.available2020-05-28T13:26:23Z
dc.date.issued2020
dc.identifier.isbn978-951-39-8182-2
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/69306
dc.description.abstractThis thesis work explores the catalytic properties of zirconia supported noble metals rhodium and platinum, using multiscale computational methods. Density functional theory (DFT) basedmethods were employed to gain atomic scale knowledge about industrially important catalytic phenomena over a wide size range of metal species. Models incorporating both the metal and the support, as well as first-principles atomistic thermodynamics and microkinetics were used in order to close the material and temperaturepressure gaps between theory and experiment. DFT results show that deposited Rh and Pt species on zirconia can enhance the reducibility of the support by accepting electrons from zirconia. A microkinetic model of the water–gas shift reaction was developed for Rh/ZrO2 and used to compare the roles the different domains of the catalyst, i.e. the metal, support, and their interface, play in the reaction mechanism. The interface of large nanoparticles, represented with a supported rod model, is shown to be a potential active site for the reaction due to its ability to bind and activate water more effectively than the pure Rh sites. A thorough screening of the water dissociation reaction on the perimeter sites of small supported clusters demonstrate that each interfacial site is unique which leads to non-scaling behaviour. A non-equilibrium nanothermodynamic framework was developed to assess the kinetics of initial stages of agglomeration of single-atoms and sub-nano clusters. Strong thermodynamic driving force is found for the process on ideal zirconia in the absence of CO. The results indicate that a CO atmosphere could stabilise Pt single-atoms and even induce cluster disintegration. Both metal single-atoms are strongly anchored by cationic and anionic defects on zirconia. These results give new atomic level insight into the behaviour of the Rh/ZrO2 and Pt/ZrO2 catalysts.en
dc.format.mimetypeapplication/pdf
dc.language.isoeng
dc.publisherJyväskylän yliopisto
dc.relation.ispartofseriesJYU dissertations
dc.relation.haspart<b>Artikkeli I:</b> Bazhenov, A., Kauppinen, M., & Honkala, K. (2018). DFT Prediction of Enhanced Reducibility of Monoclinic Zirconia upon Rhodium Deposition. <i>Journal of Physical Chemistry C, 122 (12), 6774-6778.</i> <a href="https://doi.org/10.1021/acs.jpcc.8b01046"target="_blank"> DOI: 10.1021/acs.jpcc.8b01046</a>
dc.relation.haspart<b>Artikkeli II:</b> Kauppinen, M., Melander, M., Bazhenov, A., & Honkala, K. (2018). Unraveling the role of the Rh/ZrO2-interface in the water-gas shift reaction via a first principles microkinetic study. <i>ACS Catalysis, 8 (12), 11633-11647.</i> <a href="https://doi.org/10.1021/acscatal.8b02596"target="_blank"> DOI: 10.1021/acscatal.8b02596</a>
dc.relation.haspart<b>Artikkeli III:</b> Kauppinen, Minttu M.; Korpelin, Ville; Verma, Mohan Anand; Melander, Marko M.; Honkala, Karoliina (2019). Escaping scaling relationships for water dissociation at interfacial sites of zirconia-supported Rh and Pt clusters. <i>Journal of Chemical Physics, 151 (16), 164302.</i> <a href="https://doi.org/10.1063/1.5126261"target="_blank"> DOI: 10.1063/1.5126261</a>
dc.relation.haspart<b>Artikkeli IV:</b> Kauppinen, Minttu M.; Melander, Marko M.; Honkala, Karoliina (2020). First-principles insight into CO hindered agglomeration of Rh and Pt single atoms on m-ZrO2. <i>Catalysis Science and Technology, 10 (17), 5847-5855.</i> <a href="https://doi.org/10.1039/D0CY00413H"target="_blank"> DOI: 10.1039/D0CY00413H</a>
dc.rightsIn Copyright
dc.subjectnanorakenteet
dc.subjectjalometallit
dc.subjectzirkoniumoksidi
dc.subjectkatalyysi
dc.subjectkatalyytit
dc.subjectpelkistys
dc.subjectpintakemia
dc.subjecttiheysfunktionaaliteoria
dc.subjectheterogeneous catalysis
dc.subjectdensity functional theory
dc.subjectcluster agglomeration
dc.subjectsingle-atom catalysts
dc.subjectmetal-oxide interface
dc.subjectmicrokinetic modelling
dc.subjectatomistic thermodynamics
dc.titleMultiscale computational investigation of catalytic properties of zirconia supported noble metals
dc.typeDiss.
dc.identifier.urnURN:ISBN:978-951-39-8182-2
dc.relation.issn2489-9003
dc.rights.copyright© The Author & University of Jyväskylä
dc.rights.accesslevelopenAccess
dc.type.publicationdoctoralThesis
dc.format.contentfulltext
dc.rights.urlhttp://rightsstatements.org/page/InC/1.0/?language=en
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