11. CO[sub]2 activation over nanoshaped CeO[sub]2 decorated with nickel for low-temperature methane dry reformingKristijan 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: 1411; Downloads: 0
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12. Monitoring chemical processes on the atomic scale in catalysts by operando X-ray absorption spectrometryIztok 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 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 lecture will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ and in-situ or operando characterization of various catalyst materials before, after and during their operation. With the operando XANES and EXAFS methods it is possible to track changes in the valence states and local structures of selected elements in various (photo)catalysts, during chemical reactions under controlled reaction conditions, thus gaining insight into the dynamic functional properties and reaction mechanisms of these materials. New synchrotron light sources also opened the possibility of combining X-ray absorption or emission spectroscopy and microscopy with a resolution of up to a few tens of nanometres, allowing micro-XAS analysis with high spatial resolution.
Keywords: XAS, operando XANES, EXAFS, catalysts
Published in RUNG: 01.06.2022; Views: 1368; Downloads: 0
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13. Monitoring of chemical processes at the atomic level by X-ray absorption spectrometry using extremely bright synchrotron radiation sourcesIztok Arčon, invited lecture at foreign university 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 lecture will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ and in-situ or operando characterization of various functional porous and other nanomaterials before, after and during their operation.
Keywords: XAS, operando XANES, EXAFS, functional materials
Published in RUNG: 01.06.2022; Views: 1303; Downloads: 0
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14. Insight into the interdependence of Ni and Al in bifunctional Ni/ZSM-5 catalysts at the nanoscaleHue-Tong Vu, Iztok Arčon, Danilo Oliveira de Souza, Simone Pollastri, Goran Dražić, Janez Volavšek, Gregor Mali, Nataša Zabukovec Logar, Nataša Novak Tušar, 2022, original scientific article 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. 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
using Ni K-edge XANES and EXAFS analyses, complemented by XRD and TEM, to resolve 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. Ni species in Ni/ZSM-5 exist as NiO crystals (3–50 nm) 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 ¼ 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, zeolite, Ni XANES, EXAFS
Published in RUNG: 11.05.2022; Views: 1565; Downloads: 43
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16. Characterization of electrochemical processes in metal-organic batteries by X-ray Raman spectroscopyAva Rajh, Iztok Arčon, Klemen Bučar, Matjaž Žitnik, Marko Petric, Alen Vižintin, Jan Bitenc, Urban Košir, Robert Dominko, Hlynur Gretarsson, Martin Sundermann, Matjaž Kavčič, 2022, original scientific article Abstract: X-ray Raman spectroscopy (XRS) is an emerging
spectroscopic technique that utilizes inelastic scattering of hard Xrays
to study X-ray absorption edges of low Z elements in bulk
material. It was used to identify and quantify the amount of
carbonyl bonds in a cathode sample, in order to track the redox
reaction inside metal−organic batteries during the charge/
discharge cycle. XRS was used to record the oxygen K-edge
absorption spectra of organic polymer cathodes from different
multivalent metal−organic batteries. The amount of carbonyl bond
in each sample was determined by modeling the oxygen K-edge
XRS spectra with the linear combination of two reference compounds that mimicked the fully charged and the fully discharged
phases of the battery. To interpret experimental XRS spectra, theoretical calculations of oxygen K-edge absorption spectra based on
density functional theory were performed. Overall, a good agreement between the amount of carbonyl bond present during different
stages of battery cycle, calculated from linear combination of standards, and the amount obtained from electrochemical
characterization based on measured capacity was achieved. The electrochemical mechanism in all studied batteries was confirmed to
be a reduction of double carbonyl bond and the intermediate anion was identified with the help of theoretical calculations. X-ray
Raman spectroscopy of the oxygen K-edge was shown to be a viable characterization technique for accurate tracking of the redox
reaction inside metal−organic batteries.
Keywords: X-ray Raman spectroscopy, meta-organic batteries, oxygen K-edge XANES, electrochemical processes
Published in RUNG: 24.03.2022; Views: 1673; Downloads: 20
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17. Nutritional quality and safety of the spirulina dietary supplements sold on the Slovenian marketJasmina Masten, Marta Jagodic Hudobivnik, Marijan Nečemer, Katarina Vogel-Mikuš, Iztok Arčon, Nives Ogrinc, 2022, original scientific article Abstract: The microalgae Spirulina may be a popular dietary supplement rich in essential nutrients
and vitamins, but oversight of the supplement industry, in general, remains limited, and increasing
incidents of adulteration, misbranding, and undeclared ingredients together with misleading claims
create potential risks. In response, this study characterized the elemental, amino acid and fatty acid
content of commercially available Spirulina supplements in Slovenia using EDXRF, ICP-MS and
GC-MS and compared the results with their nutritional declaration. The gathered data confirm that
Spirulina supplements are a good source of calcium (0.15 to 29.5% of RDA), phosphorous (3.36–26.7%
of RDA), potassium (0.5 to 7.69% of RDA) and selenium (0.01 to 38.6% of RDA) when consumed
within recommended amounts. However, although iron contents were relatively high (7.64 to 316%
of RDA), the actual bioavailability of iron was much lower since it was mainly present as the ferric
cation. This study also confirms that pure Spirulina supplements are a good source of essential
and non-essential amino acids, and !-6 but not !-3 polyunsaturated fatty acids. The presence of
additives resulted in significant variation in nutrient content and, in some instances, lower product
quality. Moreover, a high proportion (86.7%) of inappropriate declarations regarding the elemental
content was observed. Overall, the study conclusions underline the need for a stricter control system
for Spirulina-based supplements.
Keywords: Spirulina, microalgae, cyanobacteria, elements, toxic elements, amino acids, fatty acids, authenticity, safety, quality
Published in RUNG: 24.03.2022; Views: 1534; Downloads: 0
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18. Structure and population of complex ionic species in FeCl[sub]2 aqueous solution by X-ray absorption spectroscopyUroš Luin, Iztok Arčon, Matjaž Valant, 2022, original scientific article Abstract: Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl2). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl2 solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl2 aqueous solution 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. 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 observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. 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.
Keywords: structure, population, ionic species, aqueous ferrous chloride, in situ X-ray absorption spectroscopy
Published in RUNG: 24.01.2022; Views: 1720; Downloads: 42 (1 vote)
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19. Photoexcitation processes in atomsAlojz Kodre, Iztok Arčon, Jana Padežnik Gomilšek, 2021, independent scientific component part or a chapter in a monograph Abstract: Photoelectric absorption is characterized by a smooth power-law decrease of the
cross section with photon energy. Absorption edges reveal rich structure, which
continues into the high-energy side. The quasiperiodic signal, superposed onto
the smooth basis, due to scattering of the photoelectron on the neighbours of the
target atom provides the basis for the structural (XAFS) analysis of the material.
Irregular tiny resonances and edges that appear over the same general range as
XAFS are recognized as intra-atomic effects: multielectron excitations (MEE)
owing to correlated motion in the electronic cloud. The systematic study of MEE
began on noble gases and metallic vapours, both of which are gases of free
atoms. With some extremely strong MEE, mostly coexcitations of the subvalence
d and f electrons, the structural XAFS analysis may be compromised;
hence, there is a need to independently determine the MEE signal, the atomic
absorption background (AAB) for the analyzed element, and remove it prior to
analysis. In view of the scarcity of elements which can practically be prepared in
a free-atom gas state, several approaches to approximate the AAB have been
developed: analysis of disordered compounds, where the weak and simple
XAFS signal can be modelled and removed, and correlation analysis of the
absorption spectra of several independent samples, where the AAB is extracted
in an iterative procedure.
Keywords: photoexcitation, XAFS, multielectron excitations, atomic
absorption background
Published in RUNG: 15.12.2021; Views: 1653; Downloads: 0
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20. Monitoring of chemical processes at the atomic level by X-ray absorption spectrometry using extremely bright synchrotron radiation sourcesIztok Arčon, unpublished invited conference 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 lecture will present the possibilities offered by X-ray absorption spectroscopy with synchrotron light for ex-situ and in-situ or operando characterization of various functional porous and other nanomaterials before, after and during their operation. With the operando micro-XANES and EXAFS methods it is possible to track changes in the valence states and local structures of selected elements in different energy storage materials or in various (photo)catalysts, during chemical reactions under controlled reaction conditions, thus gaining insight into the dynamic functional properties and reaction mechanisms of these materials. New synchrotron light sources also opened the possibility of combining X-ray absorption or emission spectroscopy and microscopy with a resolution of up to a few tens of nanometres, crucial for analysis of environmental and biological samples on sub-cellular level, to understand the mechanisms of uptake, transport, accumulation, and complexation of metal cations on subcellular level in various plant tissues or accumulation in environment, to develop effective remediation approaches.
Keywords: X-ray absorption spectroscopy, EXAFS, XANES, synchrotron radiation sources, operando
Published in RUNG: 15.12.2021; Views: 1779; Downloads: 0
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