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Kristijan Lorber, 2023, doktorska disertacija

Opis: Dry reforming of methane (DRM) is an attractive reaction for converting the two major greenhouse gases CH4 and CO2 into the product syngas. H2 and CO as synthesis gas are important chemical feedstocks for the further production of valuable products as well as for the production of long-chain hydrocarbons by the Fisher-Tropsch process. High operating temperatures due to the endothermic nature of the DRM process and the occurrence of several side reactions such as Reverse Water Gas Shift, Methane Cracking and Boudoard reaction make the DRM process unattractive for industrial application. For the catalytic application of DRM in thermal mode (thermal energy drives the reaction), different CeO2 morphologies, namely nanorods, nanocubes, and nanospheres, were synthesized by a hydrothermal method. The best catalyst for DRM was found to be 2 wt. % Ni loaded in CeO2 rods morphology (2Ni-R). Characterization techniques (XRD, N2-physisorption, TEM, in-situ XANES/EXAFS TPR and CO2 TPD) were used to investigate the structural and redox properties of the catalysts. The mechanism of CO2 activation on reduced Ni/CeO2-x during DRM was proposed using DFT calculations and in-situ DRIFTS measurements combined with mass spectrometry. The 2Ni-R catalyst, which performed best in thermal DRM reaction, was studied under photo-thermal conditions where it was stimulated by both visible light and thermal energy. The catalytic activity was observed even at low (140 °C) temperatures, and the obtained CH4 and CO2 conversion, as well as H2/CO ratio exceeded thermodynamic limitations. XRD, TEM, and H2-physisorption techniques were used for structural characterization, while in-situ UV-Vis measurements were performed to study the optical properties of the catalyst. By using suitable long-pass filters and with the help of theoretical calculations, we were able to distinguish two photo mechanisms which contribute to photocatalytic activity under photo-thermal mode of the DRM reaction. Shorter wavelengths (< 450 nm) supported the charge transfer and generation mechanism in reduced CeO2-x, while longer wavelengths (> 450 nm) promoted near-field enhancement. However, under full spectrum of visible light (400 - 800 nm), the charge transfer and generation mechanism was dominant and led to 2-3 times higher CH4 activation rates compared to near-field enhancement.
Ključne besede: DRM, CeO2 nanoshapes, reaction mechanism, photocatalysis
Objavljeno v RUNG: 22.09.2023; Ogledov: 685; Prenosov: 29
.pdf Celotno besedilo (6,64 MB)

Effect of Na, Cs and Ca on propylene epoxidation selectivity over CuOx/SiO2 catalysts studied by catalytic tests, in-situ XAS and DFT
Janvit Teržan, Matej Huš, Iztok Arčon, Blaž Likozar, Petar Djinović, 2020, izvirni znanstveni članek

Opis: This research focuses on epoxidation of propylene over pristine, Na, Ca and Cs modified CuOx/SiO2 catalysts using O2. The selectivity of the reaction is analyzed using a combination of catalytic tests, in-situ XAS and DFT calculations. The initially present subnanometer CuO clusters are present in all catalysts which re-disperse/flatten during reaction. During catalytic reaction, the Cu1+ becomes the predominant oxidation state. There is no correlation between propylene oxide (PO) selectivity and copper oxidation state. DFT analysis of the propylene reaction pathway revealed that Na, Cs, and Ca addition decreases the bonding strength of propylene to CuO and decreases the O2 activation barrier, while simultaneously increase the exothermicity of O2 dissociation. The Na induced Cu-O bond modification decreases the activation barrier from 0.87 to 0.71 eV for the oxametallacycle (OMC) ring closure (first step in the reaction pathway favoring selectivity towards PO) compared to pristine 5Cu catalyst. At the same time, we observed an increase (from 0.45 to 0.72 eV) of the barrier for the abstraction of allylic hydrogen. The opposite effect is achieved by Ca addition: the activation barrier for OMC ring closure increases to 1.08 eV and that for allylic hydrogen stripping decreases to 0.16 eV.
Ključne besede: Alkali modification, propylene epoxidation, reaction mechanism, copper oxide, activation barrier.
Objavljeno v RUNG: 05.06.2020; Ogledov: 2740; Prenosov: 0
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