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1.
Structural, morphological and chemical properties of metal/topological insulator interfaces
Katja Ferfolja, 2021, doktorska disertacija

Opis: Topological insulators (TIs) represent a new state of matter that possess a different band structure than regular insulators or conductors. They are characterized with a band gap in the bulk and conductive topological states on the surface, which are spin polarized and robust toward contamination or deformation of the surface. Since the intriguing properties of the TIs are localized at the surface, it is important to obtain knowledge of the possible phenomena happening at the interface between TIs and other materials. This is especially true in the case of metals, due to the fact that such interfaces will be present in the majority of foreseen TI applications. The presented study combines microscopy and spectroscopy techniques for characterization of morphology, stability and chemical interaction at the interface between TI and metals deposited by means of physical vapor deposition. Our research is based on the interface of Bi2Se3 topological insulator with Ag, Ti and Pt – metals that can be encountered in devices or applications predicted to utilize the special properties of topological insulators. STM and SEM imaging of Ag/Bi2Se3 interface showed that Ag atoms arrange on the surface in the form of islands, whereas significantly bigger agglomerates are found at the surface steps. The interface was found to be unstable in time and resulted in the absorption of the metal into the crystal at room temperature. Evidences of a chemical reaction at the Ag/Bi2Se3 interface are presented, showing that new phases (Ag2Se, AgBiSe2 and metallic Bi) are formed. Deposition of Ti on Bi2Se3 resulted in different morphologies depending on the film thickness. At a very low coverage (<1 Å) islands are formed. However, the islands growth is hindered before the completion of a full layer due to the occurrence of a chemical reaction. No surface features could be detected by SEM for Ti coverage up to 20 nm. In contrary, when Ti thickness reached 40 nm, compressive stress triggered buckling of the deposited film. XPS analysis revealed that a redox solid-state reaction occurs at the Ti/Bi2Se3 interface at room temperature forming titanium selenides and metallic Bi. The reaction has significant kinetics even at cryogenic temperature of 130 K. Pt forms a homogenous film over the whole substrate surface, which is stable in time at room temperature. Although the interface of Pt with Bi2Se3 was found to be i less reactive compared to Ag and Ti, an interfacial phase formed upon annealing to ∼90 °C was detected by TEM cross section experiment. A model for prediction of interfacial reactions between a metal and Bi2Se3 based on the standard reduction potential of the metals and Gibbs free energy for a model reaction is presented. Based on these two values the reaction can be expected to result in the formation of binary and/or ternary selenides and Bi. Presented work shows on the importance of metal/topological insulator interfaces characterization taking into account the possibility of a chemical reaction with all of its consequences. Results should be considered for future theoretical and applicative studies involving such interfaces as well as for the possible engineering of 2D TI heterostructures.
Najdeno v: ključnih besedah
Ključne besede: topological insulators, topological surface states, Bi2Se3, thin films, Ag, Ti, Pt, morphology, interfaces, solid-state reaction, metal selenides, reactivity, stability, electron microscopy, dissertations
Objavljeno: 09.06.2021; Ogledov: 1628; Prenosov: 111
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2.
Sn-modified TiO[sub]2 thin film photocatalysts prepared by low-temperature sol-gel processing
Ksenija Maver, 2021, doktorska disertacija

Opis: Due to many advantageous physiochemical properties, titanium dioxide (TiO2) is the most widely used photocatalyst in numerous applications, such as wastewater treatment and air purification, self-cleaning surfaces and energy conversion (H2 generation). However, one of its disadvantages is the high electron-hole recombination rate, and coupling with other semiconductors is one of the strategies to improve it. The objective of this dissertation was to investigate how the photocatalytic activity of pure TiO2 can be improved by tin modification and to explain the mechanism of increased or hindered photoactivity in correlation with the structural properties of the modified TiO2 photocatalysts. A new low-temperature sol-gel synthesis route was developed to prepare Sn- or SnO2-modified TiO2 photocatalysts. In both cases, organic tin and titanium precursors were used. Tin in the form of Sn cations was used to prepare Sn-modified TiO2. In this case, the precursors went through the sol-gel reaction together to form a Sn-TiO2 sol. In the case of SnO2 modification, the SnO2 sol was prepared separately and additionally mixed with the TiO2 sol to form a TiO2/SnO2 bicomponent semiconductor system. Different molar ratios of tin to titanium were prepared to investigate the correlation between the tin concentration and the photocatalytic properties of the photocatalysts in the form of thin films. The results were used to optimize the synthesis conditions to obtain an improved activity of the modified TiO2 photocatalysts under UV-irradiation. The photocatalytic activity of the thin films was determined by measuring the degradation rate of an azo dye. An increase of up to 40 % in the photocatalytic activity of the dried samples (at 150 °C) was achieved when the TiO2 was modified with the Sn or SnO2 in a concentration range of 0.1 to 1 mol.%. At higher Sn or SnO2 loadings and after calcination of the samples at 500 °C, the photocatalytic activity of the photocatalyst was reduced compared to the unmodified TiO2. Different characterization techniques (UV-Vis, XRD, nitrogen physisorption, TEM, SEM and XAS) were employed to clarify the mechanism responsible for the enhanced and hindered photocatalytic performance of the Sn- and SnO2-modified TiO2 photocatalysts. The results showed that a nanocrystalline structure is already achieved in the samples by the low-temperature film treatment (drying at 150 °C) and that the photocatalytic efficiency is mainly influenced by the crystalline phase composition: anatase/rutile in the case of Sn-modified and TiO2/SnO2 in the case of SnO2-modified TiO2. The crystal size and specific surface area differ insignificantly between the equally thermally treated samples and partly explain the differences in photoefficiency of the calcined samples compared to the dried samples. The structural study at the atomic level, using the Sn K-edge EXAFS, revealed that Sn cations act as nucleation sites for the anatase to rutile transformation in the Sn-modified TiO2 photocatalysts, while in the SnO2-modified TiO2 samples the nanocrystalline cassiterite SnO2 is bound to the TiO2 nanocrystallites via the Sn-O-Ti bond. In both cases, the advantage of coupling the two semiconductors was achieved by separating the charge carriers and thus prolonging their lifetime for accessibility to participate in the redox reactions. The maximum activity enhancement was achieved in the low concentration range (0.1–1 mol.%), which means that an optimal ratio and contact of the two phases are obtained for the given physical parameters, such as particle size, shape and specific surface area of the catalyst.
Najdeno v: ključnih besedah
Ključne besede: Sn-modified TiO2, SnO2-modified TiO2, low-temperature sol-gel, thin films, photocatalytic activity, anatase/rutile system, Sn K-edge EXAFS, dissertations
Objavljeno: 09.06.2021; Ogledov: 1802; Prenosov: 103
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3.
Reading between the lines
Greta Mazzaggio, 2018, doktorska disertacija

Opis: This thesis' aim is to add some pieces to the complex puzzle on the mechanism behind the comprehension of conversational implicatures. To do so, in a series of experiment we manipulated both the type of implicatures (scalar vs. ad-hoc) and the population under investigation (typical vs. atypical; children vs. adults).
Najdeno v: ključnih besedah
Ključne besede: scalar implicatures, experimental pragmatics, autism developmental disorder, bilingualism, typically developing children, theory of mind, dissertations
Objavljeno: 20.09.2021; Ogledov: 945; Prenosov: 0
.pdf Polno besedilo (3,98 MB)

4.
Spectroscopic investigation of oxygen vacancies in CeO[sub]2
Thanveer Thajudheen, 2021, doktorska disertacija

Opis: A unique material, ceria (CeO2), which is widely applied in automobile exhaust catalysts, is functional due to presence of defects in its crystal structure. Furthermore, the structural defects dictate electrical and chemical properties of ceria. The creation of intrinsic oxygen vacancies in ceria is responsible for oxygen-ion conductivity in solid oxide fuel cells. This unfolds the keen interest in ceria defects. Using the analytical technique cathodoluminescence spectroscopy (CLS) we can characterize ceria for its band gap and the defect states within the band gap. Since CLS has a high spatial resolution, high sensitivity to low concentration of defects and ability to obtain depth resolved information it is an obvious technique of choice. The first part of the thesis is an introduction to the topic and description of the experimental techniques. Importance of ceria as a multifaceted material finding applications in areas spanning from energy production and conversion to biomedical applications is detailed. CLS as a tool to understand defect-related optical properties and advancement in the CL detection systems are discussed. To study the relationship between local structure and its impact on CL emission spectra, an X-ray absorption spectroscopy techniques were used. The X-ray absorption near edge structure (XANES) and the Extended x-ray absorption fine structure (EXAFS) techniques are summarized. The second part discusses CL emission from ceria. Initially, CL emission from reduced ceria and its dependence on oxygen vacancy concentration are presented. The origin of emission was attributed to different configurations of the oxygen vacancies and polarons. The recent F center description in ceria was adopted here. The intriguing observation of CL emission quenching as a function of oxygen vacancy concentration was explained on the basis of a relative change in population of F centers in ceria. This demonstrated the relevance of local structure for the CL emission in ceria. In order to have a better understanding of the system, La-doped ceria was proposed as a model system. A precise control over the stoichiometry helped to achieve a desired oxygen vacancy concentration. The CL emission behavior, as observed in reduced ceria, was replicated in the case of La-doped ceria and the analysis revealed that F+ centers favor CL emission whereas F0 centers are disadvantageous. The local structure investigation using EXAFS analysis of both cations Ce and La (K-Edge) showed distortion from the fluorite symmetry and corroborated the F center description of oxygen vacancies in ceria. Our results provide an experimental evidence for F center description involving oxygen vacancies and polarons.
Najdeno v: ključnih besedah
Ključne besede: ceria, cathodoluminescence spectroscopy, local structure distortion, EXAFS analysis, La doped ceria, luminescence quenching, F centers, dissertations
Objavljeno: 25.11.2021; Ogledov: 1032; Prenosov: 47
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5.
Application of machine learning techniques for cosmic ray event classification and implementation of a real-time ultra-high energy photon search with the surface detector of the Pierre Auger Observatory
Lukas Zehrer, 2021, doktorska disertacija

Opis: Despite their discovery already more than a century ago, Cosmic Rays (CRs) still did not divulge all their properties yet. Theories about the origin of ultra-high energy (UHE, > 10^18 eV) CRs predict accompanying primary photons. The existence of UHE photons can be investigated with the world’s largest ground-based experiment for detection of CR-induced extensive air showers (EAS), the Pierre Auger Observatory, which offers an unprecedented exposure to rare UHE cosmic particles. The discovery of photons in the UHE regime would open a new observational window to the Universe, improve our understanding of the origin of CRs, and potentially uncloak new physics beyond the standard model. The novelty of the presented work is the development of a "real-time" photon candidate event stream to a global network of observatories, the Astrophysical Multimessenger Observatory Network (AMON). The stream classifies CR events observed by the Auger surface detector (SD) array as regards their probability to be photon nominees, by feeding to advanced machine learning (ML) methods observational air shower parameters of individual CR events combined in a multivariate analysis (MVA). The described straightforward classification procedure further increases the Pierre Auger Observatory’s endeavour to contribute to the global effort of multi-messenger (MM) studies of the highest energy astrophysical phenomena, by supplying AMON partner observatories the possibility to follow-up detected UHE events, live or in their archival data.
Najdeno v: ključnih besedah
Ključne besede: astroparticle physics, ultra-high energy cosmic rays, ultra-high energy photons, extensive air showers, Pierre Auger Observatory, multi-messenger, AMON, machine learning, multivariate analysis, dissertations
Objavljeno: 27.10.2021; Ogledov: 1151; Prenosov: 54
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6.
Galactic dark matter distribution and its implications for experimental searches
Mihael Petač, 2019, doktorska disertacija

Najdeno v: ključnih besedah
Povzetek najdenega: ...dwarf spheroidal galaxies, spiral galaxies, Milky Way, dissertations, direct detection, indirect detection...
Ključne besede: dark matter, phase-space distribution function, dwarf spheroidal galaxies, spiral galaxies, Milky Way, dissertations, direct detection, indirect detection
Objavljeno: 01.10.2021; Ogledov: 890; Prenosov: 0
.pdf Polno besedilo (72,39 MB)

7.
Features of narrative language in fluent aphasia
Sara Andreetta, 2014, doktorska disertacija

Najdeno v: ključnih besedah
Ključne besede: aphasia, discourse analysis, language evaluation, dissertations
Objavljeno: 18.11.2021; Ogledov: 869; Prenosov: 0
.pdf Polno besedilo (2,76 MB)

8.
Novel analytical approaches in quality and safety control in production of fermented beverages
Jelena Topić, 2022, doktorska disertacija

Opis: The exploitation of microorganisms for fermentation goes back centuries. Two types of fermentation are usually used in the winemaking process – alcoholic fermentation and malolactic fermentation. Nowadays, inoculated fermentations with the use of starter cultures are commonly used in order to produce wine with more consistent quality. However, wines can lack in flavour complexity, so scientists and the industry are constantly looking for new and improved starters that can be adapted to different types of wine. In this work we focused on the development and implementation of novel analytical methods for wine quality control. In the course of method development native yeasts and lactic acid bacteria isolates were characterized for wine starter properties. We focused on the determination of biologically active compounds that determine wine quality and safety. Yeasts can influence wine colour through their adsorption capacity and synthesis of stable colour pigments pyranoanthocyanins and lactic acid bacteria can produce biogenic amines which can have adverse detrimental health effects on sensitive consumers when they are present in wines.
Najdeno v: ključnih besedah
Ključne besede: Saccharomyces yeasts, non-Saccharomyces yeasts, pyranoanthocyanins, thermal-lens spectrometry, lactic acid bacteria, biogenic amines, thin layer chromatography, dissertations
Objavljeno: 18.02.2022; Ogledov: 802; Prenosov: 26
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9.
Exploration of yeast biodiversity potential for development of alternative biofungicides in viticulture
Rowland Adesida, 2022, doktorska disertacija

Opis: Botrytis cinerea Pers., the fungal plant pathogen and the causal agent of gray mould diseases in grapevine, is vastly responsible for substantial economic losses in table and wine grapes production worldwide by negatively affecting plant growth and causing the reduction of grape and wine quality. The conventional approach for pathogen control has been up to date based on synthetic fungicides with good effectiveness against pathogens but a negative impact on the environment. The growing level of harmful residues in the environment and some also detected in wines have led the European Union and many winemakers to limit the application of synthetic fungicides to earlier season. However, with a high risk of disease also late in the season, the need for other solutions is clear. Consequently, more and more research is focused on finding potential alternatives in the form of effective biological control agents. Although there are several reports of yeast’s biocontrol activity, they are up to date still poorly commercialized for such purposes. As the yeasts represent an important part of the grape microflora, competing with other microorganisms (including pathogens) for nutrients and space, we decided to examine the potential of autochthonous yeasts as "green" alternatives in fighting against phytopathogens such as B. cinerea in viticulture. With this aim, we tested the biocontrol activity of 119 different indigenous yeasts belonging to 30 different species of 17 genera against filamentous fungus B. cinerea, the causal agent of grey mould or botrytis bunch rot in grape. The yeasts were screened for putative multidimensional modes of action such as antifungal volatiles (VOC), in vitro inhibition of fungal mycelial growth, competition for nutrients, hydrolytic enzyme activities, and yeast tolerance to fungicides like copper, iprodione and cyprodinil/fludioxonil combination. With a qualitative detection of the hydrolysis activity by using screening methods based on solid medium with chitin or βD-glucosides as substrates, we found that many tested yeasts were capable of producing lytic enzymes with the ability to degrade the cell wall of phytopathogenic fungi and are potentially also able to produce VOCs via hydrolysis of grape glycosides as a result of β-glucosidase presence. Furthermore, we observed the capability of tested yeast to inhibit fungal mycelia growth on plate and assimilation of a wide variety of carbon sources; however, no siderophore producers were detected. In general, the yeasts under observation were tolerant to the tested fungicides. Their fungicide resistance can indeed be regarded as a beneficial trait for potential biofungicide agent (PBA) candidates due to open possibilities of applications and combinations within low input pest management strategies in the vineyard. Finally, a field experiment in Pinot noir and Pinot gris vineyards was designed to study different combinations of optimized canopy microclimate manipulation (CMM) techniques and potential biocontrol agent (PBA) application. In experimental conditions, the ability of PBA’s to maintain appropriate population density for disease prevention was observed. In addition, the grape and wine quality parameters were analysed to observe the possible impact of implemented biocontrol yeast on final products. The biocontrol yeast Pichia guilliermondii ZIM 624 was selected and applied in experimental vineyards based on yeast testing results. We were able to detect and confirm PBA yeast’s suitable density on grapes until harvest. In the case of early defoliation for both varieties lower grape compactness was observed together with lower yield/ plant, regardless of PBA yeast/ no yeast application. Among grape basic quality parameters, the optimized techniques showed a positive effect on sugar content. Still, unexpectedly, in the treatments with biocontrol yeasts some trends toward higher acidity were noticed in Pinot gris.
Najdeno v: ključnih besedah
Ključne besede: sustainable viticulture, Botrytis cinerea, gray mould, yeasts, biocontrol, canopy microclimate manipulation, grapevine metabolite, dissertations
Objavljeno: 07.07.2022; Ogledov: 254; Prenosov: 24
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10.
Synthesis and application of transition metal phosphide nanomaterials as electrocatalysts for water splitting and chemical transformations
Takwa Chouki, 2022, doktorska disertacija

Opis: In this thesis, we will focus on the solvothermal synthesis of iron phosphides (FeP, Fe2P) using triphenylphosphine (TPP) as an inexpensive and stable phosphorus source. The obtained iron phosphides were applied as electrocatalysts in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), Rhodamine B (RhB) degradation, Escherichia coli (E. coli) inactivation, nitrates reduction reaction (NO3RR) to ammonia (NH3), and as counter electrodes in dye-sensitized solar cells (DSSCs). Detailed characterizations of catalysts were carried out to investigate the correlations between the material structure and catalytic activity. The first part of the thesis gives an introduction to the topic which cover overview of literature about the use of transition metal phosphide as efficient electrocatalysts in water splitting studies, NO3RR to NH3 and DSSCs. The second part is a description of the experimental methods. The third part discusses the solvothermal synthesis of FeP and Fe2P catalysts using TPP precursor. The phase conversion of iron phosphides at elevated temperatures under reductive atmosphere was reported. Structural characterizations of the obtained materials were achieved using multiple techniques. The electrocatalytic activities of heat-treated iron phosphide films for HER were studied in acidic environment. The fourth part discusses the use of Fe2P nanoparticles (NPs) for OER. The fifth part outlines the use of Fe2P precatalyst in water treatment studies. Using a thin film of Fe2P precatalyst, RhB degradation and E. coli inactivation in the presence of in-situ generated reactive chlorine species were reported. Characterization of Fe2P electrocatalysts before and after the test was carried out using different techniques. The sixth part shows for the first time the use of FeP and Fe2P as a noble metal-free electrocatalysts for NO3RR to NH3. In this chapter we will emphasize the nitrate reaction pathways, which are highly complex and poorly understood. The seventh part demonstrates the use of FeP and Fe2P catalysts as robust and efficient counter electrodes in DSSCs.
Najdeno v: ključnih besedah
Ključne besede: solvothermal synthesis, iron phosphides, electrocatalysis, HER, OER, RhB degradation, E. coli inactivation, NO3RR to NH3, DSSCs, dissertations
Objavljeno: 29.08.2022; Ogledov: 137; Prenosov: 9
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