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3. Green synthesis of Zeolitic Imidazolate Frameworks and their evaluation for ▫$CO_2$▫ capture in humid conditions : dissertationAljaž Škrjanc, 2024, doktorska disertacija Opis: Emissions of green-house gasses have been in the forefront of scientific research in recent decades. One of the approaches towards reducing the amount of green gas CO2 in the atmosphere is its capture and storage with subsequent conversion where pure enough CO2 can be regenerated. While CO2 capture widely utilizes two mature technologies, amine absorption and cryogenic distillation, they both have significant downsides, in either cost or potential new danger to the environment. To that end an adsorption-based CO2 capture has seen quite a lot of interest in recently. Nanoporous materials have been extensively studied for this application, starting with zeolites, followed by aluminophosphates and also the new members of the porous materials group, the so called reticular porous materials. Metal-Organic Frameworks (MOFs), the first discovered reticular porous materials have shown very promising results for post combustion CO2 capture and recently also for in-door and direct air capture. MOFs are in general enough thermally stable for CO2 capture, their main weakness for wide applicability is sometimes lower selectivity for CO2 in real gas mixtures and lower stability in humid conditions.
Zeolitic imidazolate frameworks (ZIFs), a subgroup of MOFs, have in recent years been extensively studied for sorption applications, also CO2, due to their superior stability and kinetics for vapour/gas adsorption if compared to carboxylate-based MOFs. While extensively studied, an overview of articles shows that most research is limited to a limited set group of frameworks, with ZIF-8 being used in more than half of ZIF papers. While ZIF-8 has successfully been prepared in water and even in solvent-free conditions, the rest of the ZIFs synthesis still heavily rely on solvothermal synthesis with formamide based solvent systems and synthesis times upwards of 5 days. Even in the case of ZIF-8, while greener synthesis approaches are available, dimethylformamide (DMF) synthesis still prevails in the cases tested for CO2 capture, mainly due to the increased CO2 uptake resulting from the synergistic contribution of the remaining DMF solvent in the pores.
The goal of this thesis was to develop green synthesis approaches, both solvothermal and mechanochemical, for known ZIFs and then to extend the scope towards preparation of new ZIF materials. The goal for latter was to experimentally determine the optimal topology and functionality of ZIFs for CO2 adsorption in humid conditions. Model humid gas isotherms were developed and measured for a series of ZIFs with mostly SOD (sodalite) and RHO framework topologies and Zn and Ni as metal nodes. Finally, some novel bio-based binder materials were tested for the use with ZIFs.
The sorption tests revealed than the SOD topology ZIFs have high potential for CO2 sorption applications, as the adsorption is rapid and further combination of terminally functionalised imidazoles in those frameworks drastically increases the frameworks affinity for CO2 at lower pressures. With most common 4,5- functionalised imidazole having hydrophilic functional groups, the challenge of competitive water sorption still remains. On the other hand some hydrophobic 4,5-substituted sodalite ZIFs, both with 4,5-dichloroimidazole, show excellent CO2 sorption and even complete hydrophobicity. The results led us to hypothesize that further research on ZIFs- for CO2 capture has to shift form 2 substituted sodalite frameworks to 4,5 substituted frameworks with strongly dipolar hydrophobic groups. The hydrophilic polar groups currently in use lead to issues with competitive water adsorption, due to their potential to form hydrogen bonds with water. Furthermore, some new agar and alginate based shaping methods were tested, as both potential binders are not environmentally toxic and are already used on the industrial scale world-wide for other applications. Ključne besede: carbon capture, synthesis, metal-organic frameworks, zeolitic imidazolate frameworks, nanoporous materials, dissertations Objavljeno v RUNG: 10.09.2024; Ogledov: 730; Prenosov: 21 Celotno besedilo (15,56 MB) |
4. Single crystal synthesis and surface electronic structure of Bi_{1.993}Cr_{0.007}Se_{3}Sandra Gardonio, Zipporah Rini Benher, Mattia Fanetti, Paolo Moras, Polina M. Sheverdyaeva, Matjaž Valant, 2024, izvirni znanstveni članek Ključne besede: topological insulators, magnetic atoms, crystal synthesis, formation of clusters, surface electronic structure Objavljeno v RUNG: 21.08.2024; Ogledov: 773; Prenosov: 8 Celotno besedilo (2,05 MB) Gradivo ima več datotek! Več... |
5. Air-water interface-assisted synthesis and charge transport characterization of quasi-2d polyacetylene films with enhanced electron mobility via ring-opening polymerization of pyrroleKejun Liu, Nadiia Pastukhova, Egon Pavlica, Gvido Bratina, Xinliang Feng, 2024, drugi sestavni deli Opis: Water surfaces catalyze some organic reactions more effectively, making them unique for 2D organic material synthesis. This report introduces a new synthesis method via surfactant-monolayer-assisted interfacial synthesis on water surfaces for ring-opening polymerization of pyrrole, producing distinct polypyrrole derivatives with polyacetylene backbones and ionic substitutions. The synthesis result in quasi 2D polyacetylene (q2DPA) film with enhanced charge transport behavior. We employed time-of-flight photoconductivity (TOFP) measurements using pulsed laser light of tunable wavelength for photoexcitation of the charge carriers within the q2DPA film. The charge transport was measured in the lateral direction as a function of external bias voltage ranging from 0 V to 200 V. We observed high electron mobility ({\mu}) of q2DPA reaching values of 375 cm2 V-1 s-1 at bias voltage Vb = -20V and photon energy of 3.8 eV. Ključne besede: air-water interface-assisted synthesis, time-of-flight photoconductivity, 2D polymers, quasi 2D polyacetylene, q2DPA Objavljeno v RUNG: 09.04.2024; Ogledov: 1529; Prenosov: 7 Celotno besedilo (3,89 MB) Gradivo ima več datotek! Več... |
6. An in situ proton filter covalent organic framework catalyst for highly efficient aqueous electrochemical ammonia productionKayaramkodath C. Ranjeesh, Sukhjot Kaur, Abdul K. Mohammed, Safa Gaber, Divyani Gupta, Khaled Badawy, Mohamed Aslam, Nirpendra Singh, Tina Škorjanc, Matjaž Finšgar, 2024, izvirni znanstveni članek Opis: The electrocatalytic nitrogen reduction reaction (NRR) driven by renewable electricity provides a green synthesis route for ammonia (NH3) production under ambient conditions but suffers from a low conversion yield and poor Faradaic efficiency (F.E.) because of strong competition from hydrogen evolution reaction (HER) and the poor solubility of N2 in aqueous systems. Herein, an in situ proton filter covalent organic framework catalyst (Ru-Tta-Dfp) is reported with inherent Ruthenium (Ru) sites where the framework controls reactant diffusion by suppressing proton supply and enhancing N2 flux, causing highly selective and efficient catalysis. The smart catalyst design results in a remarkable ammonia production yield rate of 2.03 mg h−1 mgcat−1 with an excellent F.E. of ≈52.9%. The findings are further endorsed with the help of molecular dynamics simulations and control COF systems without in situ proton filter feasibility. The results point to a paradigm shift in engineering high-performance NRR electrocatalysts for more feasible green NH3 production. Ključne besede: covalent organic frameworks, ammonia, electrochemical synthesis, electrochemistry, nitrogen reduction reaction, ruthenium Objavljeno v RUNG: 11.12.2023; Ogledov: 1528; Prenosov: 8 Celotno besedilo (2,77 MB) Gradivo ima več datotek! Več... |
7. The Cherenkov Telescope ArrayDaniel Mazin, Christopher Eckner, Gašper Kukec Mezek, Samo Stanič, Serguei Vorobiov, Lili Yang, Gabrijela Zaharijas, Danilo Zavrtanik, Marko Zavrtanik, Lukas Zehrer, 2019, objavljeni znanstveni prispevek na konferenci Opis: The Cherenkov Telescope Array (CTA) is the next generation ground-based observatory
for gamma-ray astronomy at very-high energies. It will be capable of detecting gamma rays in the energy range from 20 GeV to more than 300 TeV with unprecedented precision in energy and directional reconstruction. With more than 100 telescopes of three different types it will be located in the northern hemisphere at La Palma, Spain, and in the southern
at Paranal, Chile. CTA will be one of the largest astronomical infrastructures in the world with open data access and it will address questions in astronomy, astrophysics and fundamental physics in the next decades. In this presentation we will focus on the status
of the CTA construction, the status of the telescope prototypes and highlight some of the physics perspectives. Ključne besede: very-high-energy gamma-ray astronomy, Cherenkov Telescope Array, CTA sensitivity, gamma-ray bursts, POpulation Synthesis Theory Integrated project for very high-energy emission Objavljeno v RUNG: 04.12.2023; Ogledov: 1841; Prenosov: 6 Celotno besedilo (27,92 MB) Gradivo ima več datotek! Več... |
8. POSyTIVE : a GRB population study for the Cherenkov Telescope ArrayMaria Grazia Bernardini, Christopher Eckner, Gašper Kukec Mezek, Samo Stanič, Serguei Vorobiov, Lili Yang, Gabrijela Zaharijas, Danilo Zavrtanik, Marko Zavrtanik, Lukas Zehrer, 2019, objavljeni znanstveni prispevek na konferenci Opis: One of the central scientific goals of the next-generation Cherenkov Telescope Array
(CTA) is the detection and characterization of gamma-ray bursts (GRBs). CTA will be sensitive to gamma rays with energies from about 20 GeV, up to a few hundred TeV.
The energy range below 1 TeV is particularly important for GRBs. CTA will allow exploration of this regime with a ground-based gamma-ray facility with unprecedented sensitivity.
As such, it will be able to probe radiation and particle acceleration mechanisms at work in GRBs. In this contribution, we describe POSyTIVE, the POpulation Synthesis Theory Integrated project for very high-energy emission. The purpose of the project is to make realistic predictions for the detection rates of GRBs with CTA, to enable studies
of individual simulated GRBs, and to perform preparatory studies for time-resolved
spectral analyses. The mock GRB population used by POSyTIVE is calibrated using the entire 40-year dataset of multi-wavelength GRB observations. As part of this project we explore theoretical models for prompt and afterglow emission of long and short GRBs,
and predict the expected radiative output. Subsequent analyses are performed
in order to simulate the observations with CTA, using the publicly available ctools and Gammapy frameworks. We present preliminary results of the design and implementation
of this project. Ključne besede: very-high-energy gamma-ray astronomy, Cherenkov Telescope Array, CTA sensitivity, gamma-ray bursts, population Synthesis Theory, very high-energy emission Objavljeno v RUNG: 04.12.2023; Ogledov: 2619; Prenosov: 3 Celotno besedilo (1,50 MB) Gradivo ima več datotek! Več... |
9. Self-adaptive amorphous ▫$CoO_xCl_y$▫ electrocatalyst for sustainable chlorine evolution in acidic brineMengjun Xiao, Qianbao Wu, Ruiqi Ku, Liujiang Zhou, Chang Long, Junwu Liang, Andraž Mavrič, Lei Li, Jing Zhu, Matjaž Valant, 2023, izvirni znanstveni članek Opis: Electrochemical chlorine evolution reaction is of central importance in the chlor-alkali industry, but the chlorine evolution anode is largely limited by water oxidation side reaction and corrosion-induced performance decay in strong acids. Here we present an amorphous CoOxCly catalyst that has been deposited in situ in an acidic saline electrolyte containing Co2+ and Cl- ions to adapt to the given electrochemical condition and exhibits ~100% chlorine evolution selectivity with an overpotential of ~0.1 V at 10 mA cm−2 and high stability over 500 h. In situ spectroscopic studies and theoretical calculations reveal that the electrochemical introduction of Cl- prevents the Co sites from charging to a higher oxidation state thus suppressing the O-O bond formation for oxygen evolution. Consequently, the chlorine evolution selectivity has been enhanced on the Cl-constrained Co-O* sites via the Volmer-Heyrovsky pathway. This study provides fundamental insights into how the reactant Cl-itself can work as a promoter toward enhancing chlorine evolution in acidic brine. Ključne besede: catalyst synthesis, electrocatalysis, chlorine evolution Objavljeno v RUNG: 04.09.2023; Ogledov: 2422; Prenosov: 8 Celotno besedilo (3,05 MB) Gradivo ima več datotek! Več... |
10. Iron phosphide as an efficient electrocatalysts for hydrogen evolution : abstractTakwa Chouki, Manel Machreki, Saim Emin, 2020, objavljeni povzetek znanstvenega prispevka na konferenci Opis: We report the solvothermal synthesis of iron phosphide electrocatalysts using a low-cost phosphorus precursor. The synthetic protocol allows for the preparation of a Fe2P phase at 300°C and FeP phase at 350°C. To enhance the catalytic activities of obtained iron phosphide particles, heat-treatments were carried out at elevated temperatures. Annealing at 500°C induced structural changes in the samples: (i) Fe2P provided a pure Fe3P phase (Fe3P−500°C) and (ii) FeP transformed into a mixture of iron phosphide phases (Fe2P/FeP−500°C). The electrocatalytic activities of heat-treated Fe2P−450°C, Fe3P−500°C, and Fe2P/FeP−500°C catalysts were studied for hydrogen evolution reaction (HER) in 0.5 M sulfuric acid (H2SO4). The lowest recorded overpotential of 110 mV at 10 mA cm−2 vs. a reversible hydrogen electrode was achieved with Fe2P/FeP−500°C catalyst. The present approach allows preparation of immobilized iron phsphide catalyst onto carbon support which is essential for application purpose. The procedure developed by us is an elegant approach to tune the composition of iron phosphide catalyst and control the morphology of particles Ključne besede: solvothermal synthesis
iron phosphide
electrocatalysis
HER Objavljeno v RUNG: 06.02.2023; Ogledov: 2058; Prenosov: 0 Gradivo ima več datotek! Več... |