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Insight into the interdependence of Ni and Al in bifunctional Ni/ZSM-5 catalysts by Ni K-edge XAS analysis
Iztok Arčon, Vu Hue-Tong, 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: 122; Downloads: 1
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Saturation magnetisation as an indicator of the disintegration of barium hexaferrite nanoplatelets during the surface functionalisation
Klemen Lisjak, Iztok Arčon, Matic Poberžnik, Gabriela Herrero‑Saboya, Ali Tufani, Andraž Mavrič, Matjaž Valant, Patricija Hribar, Alenka Mertelj, Darko Makovec, Layla Martin‑Samos, 2023, original scientific article

Abstract: Barium hexaferrite nanoplatelets (BHF NPLs) are permanent nanomagnets with the magnetic easy axis aligned perpendicular to their basal plane. By combining this specific property with optimised surface chemistry, novel functional materials were developed, e.g., ferromagnetic ferrofluids and porous nanomagnets. We compared the interaction of chemically different phosphonic acids, hydrophobic and hydrophilic with 1–4 phosphonic groups, with BHF NPLs. A decrease in the saturation magnetisation after functionalising the BHF NPLs was correlated with the mass fraction of the nonmagnetic coating, whereas the saturation magnetisation of the NPLs coated with a tetraphosphonic acid at 80 °C was significantly lower than expected. We showed that such a substantial decrease in the saturation magnetisation originates from the disintegration of BHF NPLs, which was observed with atomic-resolution scanning transmission electron microscopy and confirmed by a computational study based on state-of-the-art first-principles calculations. Fe K-edge XANES (X-ray absorption near-edge structure) and EXAFS (Extended X-ray absorption fine structure) combined with Fourier-transformed infrared (FTIR) spectroscopy confirmed the formation of an Fe–phosphonate complex on the partly decomposed NPLs. Comparing our results with other functionalised magnetic nanoparticles confirmed that saturation magnetisation can be exploited to identify the disintegration of magnetic nanoparticles when insoluble disintegration products are formed.
Keywords: barium hexaferrite, Fe XANES, EXAFS, magnetic nanoparticles
Published in RUNG: 06.07.2023; Views: 312; Downloads: 1
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Winning combination of Cu and Fe oxide clusters with an alumina support for low-temperature catalytic oxidation of volatile organic compounds
Tadej Žumbar, Iztok Arčon, Petar Djinović, Giuliana Aquilanti, Gregor Žerjav, Albin Pintar, Alenka Ristić, Goran Dražić, Janez Volavšek, Gregor Mali, Margarita Popova, Nataša Zabukovec Logar, Nataša Novak Tušar, 2023, original scientific article

Abstract: A γ-alumina support functionalized with transition metals is one of the most widely used industrial catalysts for the total oxidation of volatile organic compounds (VOCs) as air pollutants at higher temperatures (280−450 °C). By rational design of a bimetal CuFe-γ-alumina catalyst, synthesized from a dawsonite alumina precursor, the activity in total oxidation of toluene as a model VOC at a lower temperature (200−380 °C) is achieved. A fundamental understanding of the catalyst and the reaction mechanism is elucidated by advanced microscopic and spectroscopic characterizations as well as by temperature-programmed surface techniques. The nature of the metal−support bonding and the optimal abundance between Cu−O−Al and Fe−O−Al species in the catalysts leads to synergistic catalytic activity promoted by small amounts of iron (Fe/Al = 0.005). The change in the metal oxide−cluster alumina interface is related to the nature of the surfaces to which the Cu atoms attach. In the most active catalyst, the CuO6 octahedra are attached to 4 Al atoms, while in the less active catalyst, they are attached to only 3 Al atoms. The oxidation of toluene occurs via the Langmuir−Hinshelwood mechanism. The presented material introduces a prospective family of low-cost and scalable oxidation catalysts with superior efficiency at lower temperatures.
Keywords: Iron oxide clusters, copper oxide clusters, alumina support, synergistic effect, low-temperature total catalytic oxidation, toluene, Cu, Fe XANES, EXAFS
Published in RUNG: 06.07.2023; Views: 375; Downloads: 4
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Selenium affects mercury ligand environment in terrestrial food chain – a XAS study
Katarina Vogel Mikuš, Alojz Kodre, Iztok Arčon, Anja Kavčič, 2022, published scientific conference contribution abstract

Abstract: Selenium (Se) supplied in inorganic form (as selenate or selenite) was shown to decrease mercury (Hg) toxicity by forming HgSe in soils as well as in animal and human tissues, while for plants there is no evidence of Hg-Se complexation. Although Se in not an essential element for plants it was shown to counteract various abiotic stresses when applied at trace amounts. The aim of this work was therefore to study physiological responses and Hg speciation in plant/ fungi-animal food chain. Lettuce (Lactuca sativa) and porcini mushrooms (Boletus edulis) were taken as model plant/ fungal species and Spanish slug (Arion vulgaris) as a model animal species. The plants, fed to the slugs, were grown in HgCl2 contaminated soil or soil from the vicinity of Hg mine in Idrija with traces of HgS and methyl Hg). Physiological parameters of plants and slugs were monitored during the experiment. At the end the biological material was frozen in LN2 and freeze dried. Hg L3-edge (12284 eV) XANES and EXAFS spectra of the biological samples and standards were measured at liquid helium temperature in fluorescence detection mode at the BM30B beamline of the ESRF synchrotron in Grenoble, using the 30-segment germanium solid state detector [1]. The results showed that addition of Se alleviated Hg toxic effects in the food chain started at HgCl2-contaminated soil, while for the soil from Idrija, containing low amounts of highly toxic methyl-Hg, the beneficial effect was less prominent [2]. No Hg-Se complexes were detected in plants, while in mushrooms and slugs the complexation was confirmed. Addition of Se to the plants, however, changed Hg ligand environment in plant tissues from sulphur to nitrogen ligands. Hg and Se both target the -SH functional groups in the plant tissues, so toxic effects of Hg are rather enhanced than alleviated by addition of Se. Nevertheless, the addition of Se to the plants is beneficial for higher trophic levels and lowers Hg toxicity for the primary consumers, the slugs.
Keywords: mercury, toxicity, ligand environment, XANES, EXAFS, food chain, plant, slug, fungi
Published in RUNG: 05.12.2022; Views: 811; Downloads: 0
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Monitoring chemical processes in (photo)catalysts and energy storage materials by operando X-ray absorption spectroscopy
Iztok Arčon, 2022, published scientific conference contribution abstract (invited lecture)

Abstract: X-ray absorption spectroscopy (XAS) is a powerful tool for characterisation of local structure and chemical state of selected elements in different new functional materials and biological or environmental samples. The XAS spectroscopy is based on extremely bright synchrotron radiation X-rays sources, which allow precise characterisation of bulk, nanostructured or highly diluted samples. The rapid development of extremely bright synchrotron sources of X-ray and ultraviolet light in recent years has opened new possibilities for research of matter at the atomic or molecular level, indispensable in the development of new functional nanostructured materials with desired properties. The talk will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ or operando characterization of various functional porous and other nanomaterials, before, after and during their operation [1,2,3,4]. New generation of synchrotron light sources also opened the possibility of combining X-ray absorption with high-resolution emission [5] and inelastic scattering spectroscopy [6], and microscopy with sub-micron resolution [7]. Examples of operando XANES and EXAFS analysis to track changes in the valence states and local structures of selected elements in different energy storage materials and in various (photo)catalysts, during chemical reactions under controlled reaction conditions, will be presented, which provided insight into the dynamic functional properties and reaction mechanisms of these materials. Access to SR facilities of Petra III (beamlines P65, P64 and P01), ESRF (beamlines BM23, ID21, ID26) and Elettra (beamlines XAFS, XRF), for the presented research is kindly acknowledged.
Keywords: X-ray absorption spectroscopy, operando XANES, EXAFS, catalysts, batteries
Published in RUNG: 07.10.2022; Views: 582; Downloads: 0
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Photocatalytic sol-gel/P25 TiO [sub] 2 coatings for water treatment : degradation of 7 selected pharmaceuticals (CO3:IL02)
Lev Matoh, Boštjan Žener, Marin Kovačić, Hrvoje Kušić, Iztok Arčon, Meta Levstek, Urška Lavrenčič Štangar, 2022, original scientific article

Abstract: The effect of different water matrices on the photocatalytic degradation of dissolved pharmaceuticals was explored. The focus was on the degradation efficiencies in wastewater effluent from a bioreactor and water effluent from a central wastewater treatment plant and comparing the results with degradation in deionized H2O. The compounds tested included: oxytetracycline, marbofloxacin, ibuprofen, diclofenac, phenytoin, ciprofloxacin, sulfamethoxazole. For the experiments performed in this study, a compact packed-bed photocatalytic reactor was used in which the hybrid TiO2 photocatalyst (sol-gel/P25) was deposited on ~3 mm glass beads. As expected, the reactions proceed more slowly in wastewater than in deionized water, yet it is shown that removal of the compounds from the water is still possible even when other organic molecules are present. Total organic carbon measurements have shown that complete mineralization takes place albeit at slower rates than the initial degradation of parent compounds. The results show that an acidic pH can increase the reaction rates and the adsorption on the photocatalyst surface. Analyses of the degradation intermediates were performed using tandem liquid chromatography triple-quadrupole mass spectrometry system. Additionally, X-ray absorption spectroscopy was applied to get insight into the local structure of the photocatalyst before and after use. Understanding the effects that different wastewater compositions have on photocatalytic reactions will help to refine the potential applications of the technology.
Keywords: titanium dioxide, sol-gel processes, functionla applications, water treatment
Published in RUNG: 30.09.2022; Views: 672; Downloads: 0
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Correlation between FeCl2 electrolyte conductivity and electrolysis efficiency
Luin Uroš, Valant Matjaz, Arčon Iztok, 2022, published scientific conference contribution abstract

Abstract: The electrolysis efficiency is an important aspect of the Power-to-Solid energy storage technology (EST) based on the iron chloride electrochemical cycle [1]. This cycle employs an aqueous FeCl2 catholyte solution for the electro-reduction of iron. The metal iron deposits on the cathode. The energy is stored as a difference in the redox potential of iron species. Hydrogen, as an energy carrier, is released on demand over a fully controlled hydrogen evolution reaction between metallic Fe0 and HCl (aq) [1]. Due to these characteristics, the cycle is suitable for long-term high-capacity and high-power energy storage. In a previous work [2] we revealed that the electrolyte conductivity linearly increases with temperature. Contrary, the correlation between the electrolyte concentration and efficiency is not so straightforward. Unexpectedly small efficiency variations were found between 1 and 2.5 mol dm-3 FeCl2 (aq) followed by an abrupt efficiency drop at higher concentrations. To explain the behavior of the observed trends and elucidate the role of FeCl2 (aq) complex ionic species we performed in situ X-ray absorption studies. We made a dedicated experimental setup, consisting of a tubular oven and PMMA liquid absorption cell, and performed the measurements at the DESY synchrotron P65 beamline. The XAS investigation covered XANES and EXAFS analyses of FeCl2 (aq) at different concentrations (1 - 4 molL-1) and temperatures (25 - 80 °C). We found that at low temperature and low FeCl2 concentration the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å [3]. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The transition from the single charged Fe[Cl(H2O)5]+ to the neutral Fe[Cl2(H2O)4]0 causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models [3]. [1] M. Valant, “Procedure for electric energy storage in solid matter. United States Patent and Trademark Office. Patent No. US20200308715,” Patent No. US20200308715, 2021. [2] U. Luin and M. Valant, “Electrolysis energy efficiency of highly concentrated FeCl2 solutions for power-to-solid energy storage technology,” J. Solid State Electrochem., vol. 26, no. 4, pp. 929–938, Apr. 2022, doi: 10.1007/S10008-022-05132-Y. [3] U. Luin, I. Arčon, and M. Valant, “Structure and Population of Complex Ionic Species in FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy,” Molecules, vol. 27, no. 3, 2022, doi: 10.3390/molecules27030642.
Keywords: Iron chloride electrochemical cycle, Power-to-Solid energy storage, XANES, EXAFS, electrical conductivity, electrolyte complex ionic species structure and population
Published in RUNG: 26.09.2022; Views: 784; Downloads: (1 vote)
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CO[sub]2 activation over nanoshaped CeO[sub]2 decorated with nickel for low-temperature methane dry reforming
Kristijan Lorber, Janez Zavašnik, Iztok Arčon, Matej Huš, Janvit Teržan, Blaž Likozar, Petar Djinović, original scientific article

Abstract: Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H2 and CO (syngas). CeO2 nanorods, nanocubes, and nanospheres were decorated with 1−4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO2 activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO2 morphologies expose {111} and {100} terminating facets, varying the strength of the CO2 interaction and redox properties, which influence the CO2 activation. Temperature-programmed CO2 DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H2O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO2 cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria’s surface, resulting in less-abundant surface sites for CO2 dissociation
Keywords: surface carbonates, in situ characterization, Ni XANES, Ni EXAFS, spectator species, CeO2 nanoshapes, CO2 activation
Published in RUNG: 13.07.2022; Views: 897; Downloads: 0
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