1. Light-Assisted Catalysis and the Dynamic Nature of Surface Species in the Reverse Water Gas Shift Reaction over Cu/γ-Al2O3Kristijan Lorber, Iztok Arčon, Matej Huš, Janez Zavašnik, Jordi Sancho-Parramon, Anže Prašnikar, Blaž Likozar, Nataša Novak Tušar, Petar Djinović, original scientific article Abstract: The reverse water gas shift (RWGS) reaction converts CO2 and H2 into CO and water. We investigated Cu/γ-Al2O3 catalysts in both thermally driven and light-assisted RWGS reactions using visible light. When driven by combined visible light and thermal energy, the CO2 conversion rates were lower than in the dark. Light-assisted reactions showed an increase in the apparent activation energy from 68 to 87 kJ/mol, indicating that light disrupts the energetically favorable pathway active in the dark. A linear correlation between irradiance and decreasing reaction rate suggests a photon-driven phenomenon. In situ diffuse reflectance infrared Fourier transform spectroscopy and TD-DFT analyses revealed that catalyst illumination causes significant, partly irreversible surface dehydroxylation, highlighting the importance of OH groups in the most favorable RWGS pathway. This study offers a novel approach to manipulate surface species and control activity in the RWGS reaction.
Keywords: light-assisted catalysis, reaction mechanism, in situ spectroscopy, hydroxyl, copper, RWGS
Published in RUNG: 07.01.2025; Views: 500; Downloads: 6
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2. Hell thunders : how sound influences the film narrativeMilan Bajčetić, 2024, master's thesis Abstract: This master thesis deals with the theoretical and practical part of my short film “Hell Thunders”. In the theoretical part, the topic is about the usage of sound and how it influences the understanding of the film narrative, where my film was used as an example.
In the practical part, I will describe the process behind the pre-production phase, where I will also explain how and why I made specific sound choices that helped create the film.
Keywords: film, sound, music, narrative, information, metaphor
Published in RUNG: 09.10.2024; Views: 901; Downloads: 9
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4. Molecular screening for cyanobacteria and their cyanotoxin potential in diverse habitatsMaša Jablonska, Tina Eleršek, Polona Kogovšek, Sara Skok, Andreea Oarga-Mulec, Janez Mulec, 2024, original scientific article Keywords: extreme environments, cylindrospermopsin, sulphidic springs, caves, qPCR, PC-IGS
Published in RUNG: 05.08.2024; Views: 1530; Downloads: 7
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5. XAS analysis of bifunctional Ni/ZSM-5 catalystsIztok Arčon, Hue-Tong Vu, Goran Dražić, Janez Volavšek, Gregor Mali, Nataša Zabukovec Logar, Nataša Novak Tušar, 2024, published scientific conference contribution abstract Abstract: In a bifunctional Ni/ZSM-5 zeolite type catalyst, catalytic properties are usually tuned via varying Al
and Ni contents [1]. Here we present a systematic structural study of the Ni/ZSM-5 materials by Ni
K-edge XANES and EXAFS analyses, to monitor the changes of local structure and chemical state
of Ni species in the catalysts as a function of Al and Ni content. A series of Ni/ZSM-5 type zeolites
with different Al to Si and Ni to Si molar ratios were synthesized by a “green”, template free technique
[2]. With a combination of XAS, XRD and TEM we resolved the changes in the local environment
of Ni species induced by the different Al contents in the
Ni/ZSM-5 catalysts.
Ni species in Ni/ZSM-5 exist as NiO nanocrystals and as
charge compensating Ni2+ cations. The Ni K-edge
XANES and EXAFS results enabled the quantification
of Ni-containing species. At a low Al to Si ratio (nAl/nSi
< 0.04), the NiO nanoparticles predominate in the
samples and account for over 65% of Ni phases.
However, NiO is outnumbered by Ni2+ cations attached
to the zeolite framework in ZSM-5 with a high Al to Si
ratio (nAl/nSi = 0.05) due to a higher number of
framework negative charges imparted by Al. The
obtained results show that the number of highly reducible
and active NiO nanocrystals is strongly correlated with
the framework Al sites present in Ni/ZSM-5 zeolites.
Keywords: Ni EXAFS, XANES Ni/ZSM-5 catalyst
Published in RUNG: 05.07.2024; Views: 1333; Downloads: 4
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6. Non-oxidative calcination enhances the methane dry reforming performance of ▫$Ni/CeO_{2−x}$▫ catalysts under thermal and photo-thermal conditionsKristijan Lorber, Vasyl Shvalya, Janez Zavašnik, Damjan Vengust, Iztok Arčon, Matej Huš, Andraž Pavlišič, Janvit Teržan, Uroš Cvelbar, Blaž Likozar, Petar Djinović, 2024, original scientific article Abstract: We analyzed the effect of the calcination atmosphere and visible-light contribution to an accelerated
reaction rate and improved H2 selectivity over 2 wt% Ni/CeO2−x nanorod catalysts. Spectroscopic and
structural characterization was performed by operando DRIFTS, in situ Raman, UV-vis and XAS
techniques, which were complemented by DFT calculations. Calcination in an argon or H2 atmosphere
yields 15% more active catalysts in the thermally driven reaction, which are also more susceptible to
light-induced rate acceleration compared to the catalyst calcined in air. The most active 2Ni/CeO2
catalyst calcined in hydrogen converts methane with a rate of 7.5 mmol (gcat min)−1 and produces a H2/
CO ratio of 0.6 at 460 °C when stimulated by a combination of visible light and thermal energy. In the
absence of visible light illumination and at an identical catalyst temperature, the achieved methane rate
was 4.2 mmol (gcat min)−1 and the H2/CO ratio was 0.49. The non-oxidative calcination improves nickel
dispersion and the formation of subnanometer sized Ni clusters, together with a higher abundance of
surface and bulk oxygen vacancies in ceria nanorods. The Ni–Ov–Ce3+components constitute the
catalytically active sites under visible light illumination, which enable the DRM reaction to proceed with
an Ea value of 20 kJ mol−1. Visible light also induces the following changes in the 2Ni/CeO2−x catalyst
during the DRM reaction: (1) decomposition and desorption of carbonates from the nickel–ceria
interface sites, (2) reduced population of nickel surface with carbonyl species and (3) promoted
adsorption and dissociation of methane.
Keywords: methane dry reforming performance, calcination
Published in RUNG: 05.07.2024; Views: 1706; Downloads: 18
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7. Pošta Slovenije kot prodajni kanal za trgovsko blago : diplomsko deloJanez Maček, 2024, undergraduate thesis Abstract: V časih, ko je konkurenca na trgu vse večja in pogoji poslovanja vse bolj zahtevni, je treba spremljati in prilagajati poslovanje z namenom doseganja čim boljših poslovnih rezultatov. Podjetja iščejo najboljše poslovne partnerje, ki jim na tej poti lahko najbolj pomagajo. Če razumemo lastno poslovanje in navade kupcev, lahko s tem znanjem lažje zadovoljujemo potrebe in želje tako poslovnih uporabnikov kot klasičnih kupcev. Pri izbiri poslovnih parterjev moramo biti zato pazljivi, da izbiramo parterje, ki imajo produkt ali storitev, ki jo lahko trgovec trži in prodaja, ker si jo kupci na trgu želijo in so jo pripravljeni po postavljeni ceni tudi plačati. Podjetje si prizadeva zagotoviti najboljšo uporabniško izkušnjo, ukvarja se s pridobivanjem novih strank in stremi k temu, da čim bolj zadovolji potrebe obstoječih strank, pa tudi poslovnih partnerjev.
V diplomskem delu smo z namenom natančnega prikaza prodaje storitev in blaga naredili analizo na področju prodaje, s poudarkom na stanju prodaje glede na pretekla leta. Na osnovi prodajnih rezultatov preteklih let smo opredelili vzroke za trenutno stanje in ukrepe za izboljšavo. Podali smo tudi ugotovitve, če je podjetje primeren partner za sodelovanje pri prodaji blaga in storitev z drugimi podjetji oz. poslovnimi partnerji, ter to tudi obrazložili.
Keywords: diplomske naloge, prodaja, poslovanje, dobavitelji, prodajni kanali, asortiment
Published in RUNG: 28.02.2024; Views: 2671; Downloads: 26
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8. Resolving a structural issue in cerium-nickel-based oxide : single compound or a two-phase system?Jelena Kojčinović, Dalibor Tatar, Stjepan Šarić, Cora Pravda Bartus, Andraž Mavrič, Iztok Arčon, Zvonko Jagličić, Maximilian Mellin, Marcus Einert, Angela Altomare, Rocco Caliandro, 2023, original scientific article Abstract: CeNiO3 has been reported in the literature in the last few years as a novel LnNiO3 compound with promising applications in different catalytic fields, but its structure has not been correctly reported so far. In this research, CeNiO3 (RB1), CeO2 and NiO have been synthesized in a nanocrystalline form using a modified citrate aqueous sol-gel route. A direct comparison between the equimolar physical mixture (n(CeO2) : n(NiO) = 1:1) and a compound RB1 was made. Their structural differences were investigated by laboratory powder X-ray diffraction (PXRD), selected area electron diffraction (SAED), transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy detector (EDS), and Raman spectroscopy. The surface of the compounds was analyzed by X-ray photoelectron spectroscopy (XPS), while the thermal behaviour was explored by thermogravimetric analysis (TGA). Their magnetic properties were also investigated with the aim of exploring the differences between these two compounds. There were clear differences between the physical mixture of CeO2 + NiO and RB1 presented by all of these employed methods. Synchrotron methods, such as atomic pair distribution function analysis (PDF), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to explore the structure of RB1 in more detail. Three different models for the structural solution of RB1 were proposed. One structural solution proposes that RB1 is a single-phase pyrochlore compound (Ce2Ni2O7) while the other two solutions suggest that RB1 is a two-phase system of either CeO2 + NiO or Ce1–xNixO2 and NiO.
Keywords: cerium oxide, nickel oxide, crystallography
Published in RUNG: 22.12.2023; Views: 2824; Downloads: 10
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9. Insight into the interdependence of Ni and Al in bifunctional Ni/ZSM-5 catalysts by Ni K-edge XAS analysisIztok Arčon, Hue-Tong Vu, Goran Dražić, Janez Volavšek, Gregor Mali, Nataša Zabukovec Logar, Nataša Novak Tušar, 2023, published scientific conference contribution abstract Abstract: Catalyst design is crucial for improving catalytic activity and product selectivity. In a bifunctional Ni/ZSM-5
zeolite type catalyst, catalytic properties are usually tuned via varying Al and Ni contents [1]. While changes in
acid properties associated with Al sites are usually closely investigated, Ni phases, however, receive inadequate
attention. Herein, we present a systematic structural study of Ni in the Ni/ZSM-5 materials by Ni K-edge
XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) analyses,
to monitor the local structure and chemical state of Ni species in the catalysts. In combination with XRD and
TEM we resolved the changes in the local environment of Ni species induced by the different Al contents of
the parent ZSM-5 prepared by a “green”, template free technique [2].
Ni species in Ni/ZSM-5 exist as NiO crystals (3–50 nm) and as charge compensating Ni2+ cations. The Ni Kedge
XANES and EXAFS results enabled the quantification of Ni-containing species. At a low Al to Si ratio
(nAl/nSi < 0.04), the NiO nanoparticles predominate in the samples and account for over 65% of Ni phases.
However, NiO is outnumbered by Ni2+ cations attached to the zeolite framework in ZSM-5 with a high Al to Si
ratio (nAl/nSi = 0.05) due to a higher number of framework negative charges imparted by Al. The obtained
results show that the number of highly reducible and active NiO crystals is strongly correlated with the
framework Al sites present in ZSM-5 zeolites, which depend greatly on the synthesis conditions. Therefore,
this kind of study is beneficial for any further investigation of the catalytic activities of Ni/ZSM-5 and other
metal-modified bifunctional catalysts.
Keywords: Ni/ZSM-5 catalysts, Ni EXAFS, XANES
Published in RUNG: 19.09.2023; Views: 2212; Downloads: 7
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10. Time-series analysis of oxygen as an important environmental parameter for monitoring diversity hotspot ecosystems : an example of a river sinking into the karst undergroundSaptashwa Bhattacharyya, Janez Mulec, Andreea Oarga-Mulec, 2023, original scientific article Abstract: Predicting variations in dissolved oxygen concentration (DO) is important for management and environmental monitoring of aquatic ecosystems. Regression analyses and univariate and multivariate time-series analyses based on autoregressive methods were performed to investigate oxygen conditions in the Pivka River, Slovenia. The monitoring site was established upstream where the river sinks into the karst cave Postojnska jama, which hosts one of the richest subterranean faunas yet studied worldwide. It was found that abnormal variations of DO started to be noticeable at values of DO < 3 mg/L and became more pronounced until the ecosystem reached fully anoxic conditions. The abnormal fluctuations during the critical summer period were due to environmental conditions, organic load and resident biota. Predictions for future detection of anomalies in DO values were made from stable residuals of the measured data, and it was demonstrated that the model could be used to obtain a reliable estimate for a short period, such as one day. The example presented an analysis pipeline based on specific and established threshold DO values, and it is particularly important for ecosystems with diversity hotspots where prolonged low DO values can pose a threat to their biota.
Keywords: karst (geology), aquatic ecosystems, dissolved oxygen, modelling, prediction
Published in RUNG: 05.09.2023; Views: 2095; Downloads: 7
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