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Opis: Widespread application of organic-inorganic halide perovskites (OIHP) still faces a major obstacle in mitigating moisture-induced degradation. Integrating organic spacers, as defect passivation facilitators along with low-dimensional phase (LDP) formation is an effective approach to enhance the efficiency and robustness of 3D methyl ammonium lead iodide (MAPI) in photovoltaics (PV). Here, the formamidinium cation (FA+) employing 3,5-difluorobenzene-1-carboximidamidium iodide (2F), 4-(trifluoromethyl)benzene-1-carboximidamidium iodide (3F), and 2,3,4,5,6-pentafluorobenzene-1-carboximidamidium iodide (5F) organic spacers as passivation layer in 3D/LDP OIHP solar cells is utilized. Fluorine atom position and quantity in organic spacers change the optoelectronic characteristics of the perovskites, enhancing hydrophobicity, facilitating LDP formation, and augmenting dipole moments, thereby facilitating charge separation processes. PV performance analysis reveals that 3F-treated 3D/LDP devices achieve the highest efficiency of 19.22%. Experimental results and density functional theory (DFT) studies attribute the higher performance of 3F-modified devices to effective LDP formation, enhanced passivation of defect states at perovskite surfaces and grain boundaries, the highest dipole moment and lowest band gap among the evaluated spacers. The stability tests show that, after 1000 h, 3F- and 5F-modified 3D/LDP OIHP devices retain over 85% of their initial efficiency. This research opens novel avenues for designing appropriate organic spacers to attenuate defects in 3D/LDP PV devices.
Ključne besede: fluorine-functionalized molecules, MAPI perovskite solar cells, deffect passivation
Objavljeno v RUNG: 20.02.2025; Ogledov: 334; Prenosov: 2
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Opis: This study explores Slovenian bio-art through the lens of new materialism and feminist posthumanism, focusing on six prominent artists: Saša Spačal, Robertina Šebjanič, Špela Petrič, Doroteja Dolinšek, Zoran Srdič Janežič, and Maja Smrekar. Their work interrogates interspecies relationships, ecological entanglements, and technological mediation, offering critical insights into contemporary bio-media practices. Positioned within a robust institutional framework of long-standing associations and a national funding scheme, these artists have achieved international recognition while contributing significantly to the development of intermedia art globally. Exemplified by a selected artwork each, their artistic practices are situated within new materialist, media ecological and posthuman feminist theoretical discourses. The paper highlights how contemporary bio-artistic practices challenge anthropocentric narratives, foster multispecies ethics, and redefine both uman and non-human agency. The particular ecosystem of the globally entangled yet in some ways also specifically Slovenian bio-art may demonstrate how artistic practices can facilitate ecological awareness and technological critique while fostering alternative modes of knowing, and eventually contribute to positioning art as a transformative force in contemporary cultural discourse.
Ključne besede: Slovenian bio-art, feminist posthumanism, new materialism, political ecology, media anthropology, Saša Spačal, Robertina Šebjanič, Špela Petrič, Doroteja Dolinšek, Zoran Srdič Janežič, Maja Smrekar
Objavljeno v RUNG: 19.02.2025; Ogledov: 436; Prenosov: 0
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Opis: Hemicellulose, one of the key components of lignocellulosic biomass, and its sugar monomers offer significant potential as a substrate for producing value-added platform chemicals. With both pentoses (xylose and arabinose) and hexoses (glucose, galactose, and mannose), the conversion of hemicellulose can yield various products including furfural, hydroxymethylfurfural (HMF), and levulinic acid. This doctoral thesis investigates the dehydration of various hemicellulose-derived monosaccharides, utilizing catalyst-free systems, as well as homogeneous and heterogeneous catalysts, in both aqueous and organic solvents. Monosaccharide conversion was evaluated in a catalyst-free aqueous solution at temperatures ranging between 130 – 190 °C. Conducting dehydration reactions under simple, hydrothermal conditions highlighted the differences in the reactivity of individual monosaccharides. Experimental data from extensive activity testing enabled the development of accurate kinetic models. Aiming at the optimization of reaction parameters relevant to the post-Organosolv production of furanics and levulinic acid, sulfuric and formic acid were introduced into the reaction system as homogeneous acid catalysts. Reaction kinetics of acid catalysed conversion using sulfuric and formic acid indicated a significant reduction in the activation energy of ketose dehydration. In addition, the addition of both acids enhanced the dehydration rates and promoted the conversion of HMF towards levulinic acid due to its low activation energies 86 – 91 kJ mol−1 and high reaction rate constants. The established kinetic model for individual saccharides was proven to be robust and able to accurately predict optimal reaction conditions for two distinct industrially relevant hemicellulose streams. In pursuit of a more sustainable and recyclable catalyst, various zeolites, specifically H-BEA, were tested. Although H-BEA exhibited excellent catalytic activity, its selectivity towards furanics remained limited in aqueous media. The low activation energy for HMF rehydration facilitated the formation of levulinic acid even at a moderate reaction temperature of 165 °C. Notably, the addition of THF as an organic solvent in combination with H-BEA, drastically improved the product selectivity towards furanics, particularly furfural. In addition to H-BEA zeolite, various types of zeolites with different Si/Al ratios were studied. Catalyst characterization revealed a strong correlation between catalytic activity and acidity. The addition of THF resulted in 90 mol % of furfural after only 30 min, demonstrating an exponential increase in dehydration rates and a decrease in activation energies. This zeolite-THF system was therefore applied for tandem reactions involving both xylose dehydration and furfural hydrogenation. The addition of metallic active sites via a Ni/H-BEA catalyst, and a hydrogen atmosphere, resulted in the catalytic hydrogenation of xylose to tetrahydrofurfuryl alcohol. Adjusting reaction temperatures allowed the production of secondary hydrogenated (2-methylfuran and 2-methyltetrahydrofuran) and dehydration products (tetrahydropyran), while the addition of water as a co-solvent with THF resulted in the complete inhibition of dehydration reactions and the selective formation of xylitol. Through a systematic study of reaction conditions and the development of comprehensive kinetic models, this work provides an in-depth investigation of monosaccharide dehydration. This doctoral thesis represents a comprehensive study to systematically investigate both catalytic and non-catalytic dehydration of five relevant monosaccharides, providing a methodical kinetic modelling approach that addresses the challenges associated with the complexity related to hemicellulose conversion.
Ključne besede: hemicellulose, monosaccharides, kinetic modelling, furanics, catalysis, dissertations
Objavljeno v RUNG: 19.02.2025; Ogledov: 383; Prenosov: 6
Celotno besedilo (11,80 MB)

Objavljeno v RUNG: 19.02.2025; Ogledov: 347; Prenosov: 1
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Ključne besede: visoko šolstvo, študij v tujini, študijski programi, mobilnost
Objavljeno v RUNG: 18.02.2025; Ogledov: 229; Prenosov: 0
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