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High pressure CO and methanol oxidation study over nanopowders Rare Earth Oxides and platinum thin film catalysts
Rednyk, Andrii ; Matolín, Vladimír (advisor) ; Lykhach, Yaroslava (referee) ; Šmíd, Břetislav (referee)
Title: High pressure CO and methanol oxidation study over nanopowder Rare Earth Oxides and platinum thin film catalysts Author: Mgr. Andrii Rednyk Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. matolin@mbox.troja.mff.cuni.cz Abstract: This doctoral thesis focuses on reactivity study of nanopowder rare earth oxides (REOs) and platinum based thin film catalysts using microreactor with high pressure reaction cell. REOs nanoparticles were prepared by new approach based on sol-gel chemistry. Magnetron sputtering technique was used for preparation of thin film samples. In the first part of the thesis CO oxidation on REOs and on Pt, PtOx thin films were performed. Among prepared REOs catalyst better activity exhibited alumina stabilized ceria, due to higher surface area. Both Pt and PtOx deposited on silicon substrate exhibited similar activity. When carbon (G-foil or C interlayer) is used as support, activity of Pt thin film decreases while PtOx preserves high activity. In the second part of the thesis steam reforming of methanol (SRM) and partial oxidation of methanol (POM) were performed on Pt thin films. It was shown that PtOx thin film exhibited superior activity compared to other samples with the same thickness. It is due to the reduction of platinum...
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Reactivity of transition metals - influence of the degree of oxidation of active substrate
Kettner, Miroslav ; Nehasil, Václav (advisor) ; Jiříček, Petr (referee) ; Lykhach, Yaroslava (referee)
The impacts of fluorine doping of ceria are studied by means of surface science experimental methods. Fluorine-doped and fluorine-free ceria layers are epitaxially grown on rhodium single crystals and their properties are compared in regular and inverse catalyst configurations. A procedure for epitaxial growth of CeO2(110) and CeOxFy(110) layers on Rh(110) single crystal is developed and described in detail. Shape alterations of Ce 3d spectrum brought about by fluorine doping are explained and a suitable deconvolution method is proposed. Special attention is focused towards stability of fluorine in ceria. Presented data show that fluorine incorporation in ceria lattice causes stable reduction of ceria, which withstands up to 200řC in near-ambient pressure conditions. Morphological changes are observed due to elongation of surface lattice constant of reduced ceria. Oxygen storage capacities and hydrogen oxidation reaction rates of four different studied systems are compared and discussed. The twofold nature of oxygen exposure of fluorinated ceria is discovered and explained. Oxygen repels fluorine from the surface, while the remaining part of fluorine is expelled to adsorbate positions, where its electronic state is altered. Moreover, such fluorine is prone to interact with atomic hydrogen. This reaction is...
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Model systems with the use of CeO2 for bioapplication
Bercha, Sofiia ; Tsud, Nataliya (advisor) ; Lykhach, Yaroslava (referee) ; Švec, Martin (referee)
Title: Model systems with the use of CeO2 for bioapplication Author: Sofiia Bercha Department: Department of Surface and Plasma Science Supervisor: Ing. Nataliya Tsud Ph.D., Department of Surface and Plasma Science Abstract: This thesis is focused on the investigation of model systems for bioapplications. Interfaces between biomolecules and inorganic materials were studied by means of advanced surface science techniques with emphasis on the molecular electronic structure and bonding geometry as a function of material morphology and/or molecular deposition method. For the histidine/cerium oxide system it is demonstrated that the morphology of the oxide determines the mechanism of the molecular adsorption. The presence of an aqueous medium does not alter the histidine interaction with the nanostructured cerium oxide. For the adenine/cerium oxide system we have shown that the adenine molecule chemisorbs on CeO2 intact via nitrogen atoms, independent of the oxide morphology and deposition technique. The adenine molecule was found to decompose on a reduced surface of the cerium oxide. Combining experimental and theoretical methods two distinct phases of adenine on CeO2 were found. For adenine/Cu(111) system it was shown that the strong interaction with the surface keeps the molecule intact on the surface till...
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Reactivity of transition metals - influence of the degree of oxidation of active substrate
Kettner, Miroslav ; Nehasil, Václav (advisor) ; Jiříček, Petr (referee) ; Lykhach, Yaroslava (referee)
The impacts of fluorine doping of ceria are studied by means of surface science experimental methods. Fluorine-doped and fluorine-free ceria layers are epitaxially grown on rhodium single crystals and their properties are compared in regular and inverse catalyst configurations. A procedure for epitaxial growth of CeO2(110) and CeOxFy(110) layers on Rh(110) single crystal is developed and described in detail. Shape alterations of Ce 3d spectrum brought about by fluorine doping are explained and a suitable deconvolution method is proposed. Special attention is focused towards stability of fluorine in ceria. Presented data show that fluorine incorporation in ceria lattice causes stable reduction of ceria, which withstands up to 200řC in near-ambient pressure conditions. Morphological changes are observed due to elongation of surface lattice constant of reduced ceria. Oxygen storage capacities and hydrogen oxidation reaction rates of four different studied systems are compared and discussed. The twofold nature of oxygen exposure of fluorinated ceria is discovered and explained. Oxygen repels fluorine from the surface, while the remaining part of fluorine is expelled to adsorbate positions, where its electronic state is altered. Moreover, such fluorine is prone to interact with atomic hydrogen. This reaction is...
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Experimental control of Ce3+ concentration in ceria based model catalysts
Stetsovych, Vitalii ; Mysliveček, Josef (advisor) ; Lykhach, Yaroslava (referee) ; Rezek, Bohuslav (referee)
Concentration of Ce3+ is one of the most important parameters that influence the reactivity of ceria based catalyst. In this work we examine different experimental approaches for controlling Ce3+ concentration in cerium oxide model catalyst systems such as: i) influencing the stoichiometry of ceria, ii) introducing high valence doping agent, and iii) growing ultra thin ceria films with a strong metal substrate interaction. Structure, morphology and chemical state of prepared reduced ceria based systems were examined by means of surface science techniques: scanning tunneling microscopy, low-energy electron diffraction and X-ray photoelectron spectroscopy. In the present work an original method of ceria film reduction was introduced that allows stepwise control on stoichiometry and degree of film reduction (i). Further we introduce preparation procedures for well-ordered tungsten doped ceria model system (ii) and for the high quality 2D ultrathin ceria system on Cu (1 1 1) (iii). Preparation methods and model systems introduced in this work incorporate different physicochemical principles of Ce3+ induction and provide a variety of model systems useful for examining different effects that diversely prepared Ce3+ ions have on the activity of the catalyst.
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High pressure CO and methanol oxidation study over nanopowders Rare Earth Oxides and platinum thin film catalysts
Rednyk, Andrii ; Matolín, Vladimír (advisor) ; Lykhach, Yaroslava (referee) ; Šmíd, Břetislav (referee)
Title: High pressure CO and methanol oxidation study over nanopowder Rare Earth Oxides and platinum thin film catalysts Author: Mgr. Andrii Rednyk Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. matolin@mbox.troja.mff.cuni.cz Abstract: This doctoral thesis focuses on reactivity study of nanopowder rare earth oxides (REOs) and platinum based thin film catalysts using microreactor with high pressure reaction cell. REOs nanoparticles were prepared by new approach based on sol-gel chemistry. Magnetron sputtering technique was used for preparation of thin film samples. In the first part of the thesis CO oxidation on REOs and on Pt, PtOx thin films were performed. Among prepared REOs catalyst better activity exhibited alumina stabilized ceria, due to higher surface area. Both Pt and PtOx deposited on silicon substrate exhibited similar activity. When carbon (G-foil or C interlayer) is used as support, activity of Pt thin film decreases while PtOx preserves high activity. In the second part of the thesis steam reforming of methanol (SRM) and partial oxidation of methanol (POM) were performed on Pt thin films. It was shown that PtOx thin film exhibited superior activity compared to other samples with the same thickness. It is due to the reduction of platinum...
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Study of the structural properties of model ceria based catalysts
Beran, Jan ; Mašek, Karel (advisor) ; Olejník, Kamil (referee) ; Lykhach, Yaroslava (referee)
This work is concerning the study of model ceria based calalysts structure by methods of electron diffraction RHEED and photoelectron spectroscopy XPS. The influence of deposition conditions and substrate on the growth of epitaxial cerium oxide films on copper single crystals is described in detail. The work then describes the interaction of cerium and tin in model systems and the creation of SnCeOx mixed oxide and its structure. In the last chapter, the interaction of palladium with cerium and tin oxide layers is examined, and the creation of paladium bimetallic alloys is described. Powered by TCPDF (www.tcpdf.org)
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Investigation of magnetron sputtered Pt-CeO2 thin film catalyst for fuel cell applications
Vorokhta, Mykhailo ; Matolín, Vladimír (advisor) ; Lykhach, Yaroslava (referee) ; Jiříček, Petr (referee)
Title: Investigation of magnetron sputtered Pt-CeO2 thin film catalyst for fuel cell applications. Author: Mgr. Mykhailo Vorokhta Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. matolin@mbox.troja.mff.cuni.cz Abstract: This doctoral thesis focuses on magnetron sputtered Pt-doped CeO2 thin films that were found to be very active catalysts in proton exchange membrane fuel cells (PEMFC). The films were prepared on different substrates (silicon wafers, carbon nanotubes and flat carbon substrates) and investigated mainly by means of Hard x-ray photoelectron spectroscopy (HAXPES). The HAXPES method showed that deposition of the Pt doped cerium oxide catalyst layers on carbon nanotubes and flat carbon substrates by magnetron sputtering leads to growth of a highly porous "Pt-Ce-O" solid solution film, where platinum is mostly in ionic states, Pt2+ , Pt4+ . The results obtained showed that the mechanism of film growth is strongly influenced by interaction of the Ce atoms with the substrate and their oxidation by oxygen containing RF plasma. The formation of Ptn+ states together with the porous character of the catalyst films are used to explain the high activity of Pt-CeO2 catalyst in PEMFCs. Keywords: magnetron sputtering, cerium oxide, Pt, XPS, SRPES.
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