Title: Study of cerium oxide-metal intraction with gases - carbon monoxide oxidation and methanol decomposition Author: Tatiana Kolářová Department: Department of Surface and Plasma Science Supervisor: Doc. RNDr. Václav Nehasil, Dr., Department of Surface and Plasma Science Abstract: Dissertation thesis is focused on the study of two catalytic systems on the basis of cerium oxide-metal. The systems were characterized by various methods of surface analysis. The first part of the work concerns influence of the preparation parameters on the character of gold nanoparticles deposited onto the sputtered cerium oxide layers from a solution. Catalytic activity of prepared Au/CeOx/(C)/Si systems, containing particles with the mean sizes of 4- 10 nm, was tested toward CO oxidation at atmospheric pressure. The results show that with increasing amount of gold present on the samples, also the productivity of CO2 during the reactions grows. The work is further focused on the preparation of an inverse model CeOx/Pt(111) system. On this system, adsorption of methanol at low temeperatures and its decomposition during a heating was studied. It is apparent from presented results that the decomposition of methanol on the inverse CeOx/Pt(111) systems behaves in a different way than on a clean platinum sample or a thick...

Acenes are a class of polycyclic aromatic hydrocarbons (PAH) with linearly fused benzene rings. They are widely considered as promising materials for organic and molecular electronics. However, larger molecules of this class possessing more than five rings are chemically extremely reactive and show a very low solubility. Hence, large acenes are difficult to handle, and the experimental data available to date is limited. The aim of this work is to show a very promising protocol of how acenes with different lengths can be stabilized and investigated on metallic surfaces. The experimental approach of on-surface synthesis is explored to generate the respective acenes directly on the metallic substrate via the reduction of suitable precursor molecules. High-resolution scanning probe microscopy (SPM) is employed at a temperature of 5 K to verify the chemical conversion at a single-molecule level. In the first part of this work, the on-surface synthesis of acenes is introduced via the example of tetracene (4-acene) formation on Cu(111). Precursors with 1,4-epoxy moieties preferably adsorb with their oxygen-rich site facing the substrate. Subsequently, they can be deoxygenated via annealing of the substrate or by single-molecule manipulation with the tip of the scanning probe microscope. In both cases, atomic force microscopy (AFM) measurements resolve the planar adsorption geometry of tetracene on the surface with atomic resolution. Based on these findings, scanning tunneling microscopy (STM) is employed to investigate the self-assembly patterns of on-surface generated anthracene (3-acene) and tetracene molecules after synthesis on Au(111). These measurements show intriguing organic nanostructures and supramolecular networks that can form at the metallic interface upon thermally-induced surface reactions. The second part of this thesis focuses on the electronic structure of acenes adsorbed on a metallic substrate. By applying the novel method of on-surface reduction, single and isolated hexacene (6-acene) molecules are investigated on Au(111). Scanning tunneling spectroscopy (STS) measurements indicate a weak interaction with the substrate and reveal five accessible molecular resonances at the organic-metal interface. The differential conductance maps with high spatial resolution at the respective resonant bias values compare well to elastic scattering quantum chemistry-based calculations. Finally, the experimental investigations of Br-substituted precursors show the stabilization of genuine unsubstituted heptacene (7-acene), as confirmed by imaging of the molecular structure via atomic-resolution STM. Accordingly, the precise characterization of this molecule via STS allows more insight into the electronic structure of adsorbed acenes with respect to their length. / Acene sind eine Klasse von polyzyklischen aromatischen Kohlenwasserstoffen mit linear kondensierten Benzolringen. Sie gelten weithin als vielversprechende Materialien für die organische und molekulare Elektronik. Jedoch sind die größeren Moleküle dieser Klasse mit mehr als fünf Ringen chemisch extrem reaktiv und zeigen eine sehr geringe Löslichkeit, daher gibt es bisher nur wenige experimentelle Untersuchungen ihrer Eigenschaften. Das Ziel dieser Arbeit ist es, Acene mit unterschiedlichen Längen auf einer metallischen Oberfläche stabilisieren und untersuchen zu können. Dabei wird der experimentelle Ansatz der Oberflächensynthese verfolgt und die jeweiligen Acene durch Reduktion von geeigneten Präkursoren direkt an einer metallischen Grenzfläche hergestellt. Hochauflösende Rastersondenmikroskopie an einzelnen Molekülen bei einer Temperatur von 5K nimmt dabei eine Schlüsselrolle im Nachweis der chemischen Umwandlung auf der Oberfläche ein. Im ersten Teil dieser Arbeit wird die Oberflächensynthese von Acenen am Beispiel von Tetracen (4-Acen) auf Cu(111) eingeführt. Die Ausgangsmoleküle mit funktionellen Gruppen adsorbieren bevorzugt mit ihrer sauerstoffreichen Seite auf dem Substrat und können dort sowohl thermisch als auch mithilfe der Spitze des Rastersondenmikroskops umgewandelt werden. In beiden Fällen wird die planare Adsorptionsgeometrie von Tetracen auf der Oberfläche mittels Rasterkraftmikroskopie mit atomarer Auflösung abgebildet. Darauf aufbauend wird Rastertunnelmikroskopie genutzt, um die Selbstassemblierung von Anthracen (3-Acen) und Tetracen nach der jeweiligen Synthese auf Au(111) zu untersuchen. Die Messungen zeigen unerwartete organische Nanostrukturen und supramolekulare Netzwerke, welche sich an der metallischen Grenzfläche durch die induzierte Oberflächenreduktion bilden können. Der zweite Teil dieser Arbeit beschäftigt sich mit den elektronischen Eigenschaften von adsorbierten Acenen. Durch die neuartige Methode der Oberflächenreduktion können einzelne Hexacene (6-Acen) auf Au(111) untersucht werden. Messungen basierend auf Rastertunnelspektroskopie geben Hinweise auf die schwache Wechselwirkung mit dem Substrat und zeigen fünf molekulare Eigenzustände, die im Experiment zugänglich sind. Die entsprechenden Abbildungen der differentiellen Leitfähigkeiten mit hoher Ortsauflösung sind in guter Übereinstimmung mit einer quantenmechanischen Modellierung. Schließlich wird die Stabilisierung von Heptacen (7-Acen) von Br-substituierten Präkursoren mittels Rastertunnelmikroskopie mit atomarer Auflösung gezeigt. Dadurch kann die elektronische Struktur von adsorbierten Acenen anhand ihrer Länge verglichen werden.

In der Arbeit werden Fehlstellen in der Silizium (2x1)-(111)-Oberfläche mit den ab-initio-Methoden DFT-LDA und GdW betrachtet. Zunächst werden dabei die bei dieser Oberfläche auftretenden Pandeyketten innerhalb der DFT-LDA näher betrachtet und der Einfluss zwischen und innerhalb der Ketten untersucht. Um den Einfluss der Phosphorfehlstelle zu betrachten wird ein System erstellt, das groß genug ist, um einzelne Defekte in der Oberfläche untersuchen zu können. Die Ergebnisse der DFT werden durch Berechnungen der Vielteilchenstörungstheorie GdW erweitert, wodurch gleichzeitig gezeigt werden konnte, dass sich die GdW auf Systeme mit 600 Elektronen anwenden lässt. Weiterhin wird durch Betrachtung der ortsaufgelösten DOS die Wechselwirkung der Phosphordotierung mit dem Siliziumkristall untersucht.

Fuel cells are more efficient and cleaner than combustion engines. Ethanol as a fuel has a high energy density and is safer and easier to handle than hydrogen which is normally used in fuel cells. If efficient fuel cells on alcohol were available, they could be used for engines and power sources for electronics. Platinum-tin surfaces have proven to be good catalysts for ethanol and an improvement over pure platinum. The mechanism and the structure during catalysis are not well known. An experiment was performed at the Hippie beam line at Max IV to improve the knowledge in this area. The (111) surface of Pt and Pt3Sn alloy and the (223) surface of Pt, was exposed to ethanol and oxygen. Pt and Pt3Sn both have face-centered-cubic (FCC) crystal structures. The (111) surface is the most close-packed in an FCC crystal. A (223) surface is a (111) surface cut at a low angle. So it has the appearance of a stepped (111) surface. The edges on the (223) surface should increase the activity compared to the (111) surface. The surfaces and the gas phases were measured in situ with ambient pressure x-ray photoelectron spectroscopy and a quadrupole mass spectrometer was used to analyze the gas composition. The hypothesis that increasing the number of edges as with the Pt(223) surface should increase the activity is accurate. Pt(223) was more active than Pt(111). Pt(223) and Pt3Sn(111) have similar ethanol conversion rate. Increasing the oxygen-to-ethanol ratio increased the activity both with Pt(111) and Pt(223), Pt3Sn(111) was not tested with increased oxygen-to-ethanol ratio. The gas phases were analyzed, and the existing compounds were identified. Acetaldehyde shows up in the C1s gas spectrum in all of the sequences. When ethanol decreases acetaldehyde increase. The difference between these two compounds is only two hydrogen atoms. This reaction is the start of the catalytic process and it is the same for all tested crystals. Ethylene (CH2CH2) shows up as a vague peak in the gas phase. It is only present at higher temperatures and with a low oxygen rate. Compared to the other crystals the Pt3Sn(111) sample doesn't produce CO2, at least not to a detectable degree. In the gas phases of the other crystals, the CO2 peak was visible. Pt(223) creates CO2 but to a lesser degree than Pt(111). The goal of the experiment was to investigate which Sn phases are present during ethanol oxidation. This turned out to be difficult. The Pt3Sn crystal was carbon poisoned during the first test sequence and the graphite layer was not possible to remove during the beam time. Curve fitting of the Sn3d peak resulted in two components. The components were Pt3Sn alloy and Sn with adsorbed molecules. The expected SnO2 and SnO peaks notably absent. The oxygen probably bonds with carbon instead of tin. Carbon was present on the surface due to insufficient cleaning. In the oxygen spectrum, chemically bonded oxygen seems to be present from 100 °C, as SnO2 or SnO. This peak is most likely from some other component containing oxygen. If oxygen is bonded to Sn, it should be visible in the Sn3d peak, unless it is hiding underneath one of the present peaks. According to Batzill et al. a quasimetalic state consisting of oxidized Sn alloyed with Pt has a similar binding energy as Pt3Sn alloy. So it could be that the oxygen is hiding underneath the Pt3Sn alloy component. The experiment has improved the knowledge of ethanol oxidation on platinum and platinum-tin surfaces. The knowledge gained here is a good start for further experiments and simulations.

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The hyperfine interaction between carrier spins and nuclear spins is an important component in exploring spin-dependent properties in materials with strong spin orbit interaction.However hyperfine interaction has been less studied in bismuth (Bi), a heavy element exhibiting a strong Rashba-like spin-orbit interaction in its two-dimensional surface states due to the broken spatial inversion symmetry. In this dissertation we experimentally explore the carrier spin polarization due to transport under strong spin-orbit interaction and the nuclear polarization resulting from the relatively unexplored hyperfine interaction on Bi(111) films.The carrier and nuclear spin polarizations are expected to dynamically interact, a topic with ramifications to other materials where surface states with noteworthy properties play a role.To achieve this goal, an optimized van der Waals epitaxy growth technique for Bi(111) on mica substrates was developed and used, resulting in flat Bi surfaces with large grain sizes and a layered step height of 0.39±0.015 nm, corresponding to one Bi(111) bilayer height. A comparison between Bi(111) films grown on three different substrates (mica, InSb(111)B, and Si(111)) is discussed, for which scanning electron microscopy and atomic force microscopy are applied to obtain the structural and morphological characteristics on the film surface. Magnetotransport measurements are carried out to extract the transport properties of theBi(111) films. Using the high quality Bi(111) film deposited on mica, we develop quantum magnetotransport techniques as delicate tools to study hyperfine interaction. The approach is based on measuring quantum corrections to the conductivity due to weak antilocalization, which depend on the coherence of the spin state of the carriers. The carrier spin polarization is generated by a strong DC current in the Bi(111) surface states (here called the Edelstein effect), which then induces dynamic nuclear polarization by hyperfine interaction. Quantum transport antilocalization measurements in the Bi(111) thin-films grown on mica indicate a suppression of antilocalization by the in-plane Overhauser field from the nuclear polarization, and allow for the quantification of the Overhauser field, which is shown to depend on both polarization duration and the DC current magnitude. Various delay times between the polarization and the measurement result in an exponential decay of the Overhauser field, driven by relaxation time T1. We observe that in the Bi surface states, the appreciable electron density and strong spin-orbit interaction allow for dynamic nuclear polarization in the absence of an external magnetic field. / Doctor of Philosophy / This dissertation focuses on the heavy element bismuth (Bi), a semimetal with strong spin-orbit interaction at its two-dimensional surface. Given the challenge to grow high qualityBi(111) films, we present an optimized van der Waals epitaxy technique to grow Bi(111)films on mica substrates, which show a flat surface with large grain sizes and a layered step height of 0.391±0.015 nm, corresponding to one Bi(111) bilayer height. To demonstrate the high quality of the Bi(111) surface, a comparison of surface morphology was conducted among Bi(111) films deposited on three different substrates (mica, Si(111), and InSb(111)B),along with a comparison between their electronic transport properties. By applying a DC current on the high quality Bi(111) film on mica, a carrier spin polarization is established via mainly what we here call the Edelstein effect, which then induces dynamic nuclear polarization by hyperfine interaction and generates a non-equilibrium nuclear spin polarization without externally applied magnetic field. We quantified the Overhauser field from the nuclear polarization all-electrically by conducting quantum transport antilocalization experiments, which showed a suppression of antilocalization by the in-plane Overhauser field.Comparative measurements indicated that the magnitude of the Overhauser field depends onthe spin-polarizing DC current magnitude and the polarization duration. The experiments also show that antilocalization forms a sensitive probe for hyperfine interaction and nuclear polarization.

Beethoven’s musical descendants, such as Carl Czerny, Franz Liszt, Hans von Bülow (Bülow), and Artur Schnabel, realizing that Beethoven’s music needed more directions, published their own Beethoven sonata editions. Czerny and Liszt tried to retain as much of Beethoven’s manuscript as possible in their editions, but later pianist editors such as Bülow and Schnabel boldly added many indications. Bülow’s Beethoven Sonata edition, which was admired by Liszt and was used by Liszt to teach his pupils in his later years, acquired some notoriety among serious pianists and piano students. The reasons for this notoriety were two-fold. First, Bülow’s additions and alterations were believed to be his own interpretations. Second, Bülow’s Beethoven Sonata edition, which is still in print today contains many misprints. The distinction between these two issues is the focus of this dissertation. In this study, I examine the issue of Bülow’s alterations by extensively researching the following accounts: seven historical sources including Beethoven’s manuscripts and early editions; nine editions edited by Beethoven’s musical descendants, Beethoven scholars and musicologists; and three historical recordings created by Beethoven’s musical descendants. This dissertation compares these accounts with Bülow’s edition, particularly the Allegro movement of Beethoven Sonata Op. 111. The comparative study in this dissertation sheds light on Beethoven’s intent for his composition and clarifies whether Bülow’s alterations in his edition were based on his own interpretation, reflect what he learned from Liszt—a close musical descendant of Beethoven, or are simply misprints.

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The ability of RNA bases to self-assemble into larger structures is an important research area relevant to the origins of life. In the RNA helix the bases are arranged on a sugar-phosphate carcass but it has been suggested that the initial ordering could form on a flat surface. This thesis is an attempt to establish experimentally whether the complementary RNA bases, adenine and uracil, have the ability to self-assemble into large ordered structures when adsorbed on metal and mineral surfaces. The Au (111) surface was chosen as a preferred substrate as it is flat, relatively free of defects, chemically inert and reconstructs in a characteristic pattern of corrugation lines, which provide a reference for crystallographic directions. Six of the molecular phases shown were observed for the first time with molecular resolution and the possible two-dimensional arrangements of adenine and uracil molecules for these phases are proposed. The pure adenine and pure uracil structures have chiral unit cells and in the case of pure uracil alternating monochiral domains within the polychiral islands are created. Well-ordered intricate uracil-adenine bimolecular networks were also observed. The self-assembly of both uracil and adenine appears to be weakly influenced by the surface crystallography. The (100) surface of the mineral pyrite (FeS₂) was chosen as the alternative substrate as it is the most common face that occurs naturally in pyrite crystals. The experiments show the formation of small adenine and uracil crystals at the terrace edges. Neither uracil nor adenine were observed to form a monolayer on the surface of the terraces. The results of the experiments described in this thesis are very interesting in terms of establishing the possible mechanisms for creating regular chiral molecular networks and provide a useful insight into the role of surfaces in the processes of self-assembly of RNA bases.