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51.
52.
Surface modified titanium dioxide using transition metals
Andraž Šuligoj, Iztok Arčon, Matjaž Mazaj, Goran Dražić, Denis Arčon, Pegie Cool, Urška Lavrenčič Štangar, Nataša Novak Tušar, 2018, izvirni znanstveni članek

Opis: Titanium dioxide has been widely used as an antimicrobial agent, UV-filter and catalyst for pollution abatement. Herein, surface modifications with selected transition metals (Me) over colloidal TiO2 nanoparticles and immobilization with a colloidal SiO2 binder as composite films (MeTiO2/SiO2) on a glass carrier were used to enhance solar-light photoactivity. Colloidal TiO2 nanoparticles were modified by loading selected transition metals (Me ¼ Mn, Fe, Co, Ni, Cu, and Zn) in the form of chlorides on their surface. They were present primarily as oxo-nanoclusters and a portion as metal oxides. The structural characteristics of bare TiO2 were preserved up to an optimal metal loading of 0.5 wt%. We have shown in situ that metal-oxo-nanoclusters with a redox potential close to that of O2/O2 were able to function as co-catalysts on the TiO2 surface which was excited by solar-light irradiation. The materials were tested for photocatalytic activity by two opposite methods; one detecting O2 (reduction, Rz ink test) while the other detecting OH (oxidation, terephthalic acid test). It was shown that the enhancement of the solar-light activity of TiO2 by the deposition of transition metal oxo-nanoclusters on the surface depends strongly on the combination of the reduction potential of such species and appropriate band positions of their oxides. The latter prevented excessive self-recombination of the photogenerated charge carriers by the nanoclusters in Ni and Zn modification, which was probably the case in other metal modifications. Overall, only Ni modification had a positive effect on solar photoactivity in both oxidation and reduction reactions.
Najdeno v: osebi
Ključne besede: surface modified TiO2, XANES, EXAFS, Nickel, solar light photocatalyst
Objavljeno: 01.06.2018; Ogledov: 496; Prenosov: 0
.pdf Polno besedilo (1,24 MB)

53.
Polysulfides formation in different electrolytes from the perspective of X-ray absorption spectroscopy
Robert Dominko, Alen Vižintin, Giuliana Aquilanti, Lorenzo Stievano, Maria Joseph Helen, Anji Reddy Munnangi, Maximilian Fichtner, Iztok Arčon, 2018, izvirni znanstveni članek

Opis: Li-S batteries are promising energy storage technology for the future, however there two major problems remained which need to be solved before successful commercialization. Capacity fading due to polysulfide shuttle and corrosion of lithium metal are directly connected with the type and quantity of electrolyte used in the cells. Several recent works show dependence of the electrochemical behavior of Li-S batteries on type of the electrolyte. In this work we compare and discuss a discharge mechanism of sulfur conversion in three different electrolytes based on measurements with sulfur K-edge XAS. The sulfur conversion mechanism in the ether based electrolytes, the most studied type of solvents in the Li-S batteries, which are enabling high solubility of polysulfides are compared with the fluorinated ether based electrolytes with a reduced polysulfide solubility and in carbonate based electrolytes with the sulfur confined into a ultramicroporous carbon. In all three cases the sulfur reduction proceeds through polysulfide intermediate phases with a difference on the type polysulfides detected at different steps of discharge.
Najdeno v: osebi
Ključne besede: Li-S batteries, operando sulphur K-edge XANES, EXAFS, Li-polysulphides
Objavljeno: 01.06.2018; Ogledov: 566; Prenosov: 0
.pdf Polno besedilo (579,89 KB)

54.
Effects of Different Copper Loadings on the Photocatalytic Activity of TiO2-SiO2 Prepared at a Low Temperature for the Oxidation of Organic Pollutants in Water
T. Čižmar, Iztok Arčon, Mattia Fanetti, Urška Lavrenčič Štangar, 2018, izvirni znanstveni članek

Opis: The objective of this research is to examine how Cu modification can improve the photocatalytic activity of TiO2-SiO2, to explainthe correlation between the Cu concentration and the chemical state of Cu cations in the TiO2-SiO2 matrix, and the photocatalytic activity under UV/solar irradiation. The Cu-modified TiO2-SiO2 photocatalysts were prepared by a low-temperature sol–gel method from organic Cu, Si and Ti precursors with various Cu concentrations (0.05–3 mol %). The sol–gels were dried at 150 8C to obtain the photocatalysts in a powder form. The photocatalytic activity was determined by using a fluorescence- based method of terephthalic acid decomposition. An up to three times increase in photocatalytic activity is obtained if the TiO2-SiO2 matrix is modified with Cu in a narrow concentration range from 0.05 to 0.1 mol%. At higher Cu loadings, the photocatalytic activity of the Cu-modified photocatalysts is lower than that of the un-modified reference TiO2-SiO2 photocatalyst. XRD was used to show that all Cu-modified TiO2-SiO2 composites with different Cu concentrations have the same crystalline structure as un-modified TiO2-SiO2 composites. The addition of Cu does not change the relative ratio between the anatase and brookite phases or unit cell parameters of the two TiO2 crystalline structures. We used Cu K-edge X-ray absorption near edge structure and extended X-ray absorption fine structure analyses to determine the valence state and local structure of Cu cations in the Cu-modified TiO2-SiO2 photocatalysts. The results elucidate the mechanism responsible for the improved photocatalytic activity. In samples with a low Cu content, which exhibit the highest activity, Cu@O@Ti connections are formed, which suggests that the activity enhancement is caused by the attachment of CuII cations on the surface of the photocatalytically active TiO2 nanoparticles, so CuII cations may act as free-electron traps, which reduce the intensity of recombination between electrons and holes at the TiO2 photocatalyst surface. At higher Cu loadings no additional Cu@O@Ti connections are formed, instead only Cu@O@Cu connections are established. This indicates the formation of amorphous or nanocrystalline copper oxide, which hinders the photocatalytic activity of TiO2.
Najdeno v: osebi
Ključne besede: Cu modified TiO2-SiO2 photocatalyst Cu EXAFS, XANES, Organic pollutants
Objavljeno: 30.08.2018; Ogledov: 530; Prenosov: 0
.pdf Polno besedilo (1,53 MB)

55.
Cadmium associates with oxalate in calcium oxalate crystals and competes with calcium for translocation to stems in the cadmium bioindicator Gomphrena claussenii
Paula Pongrac, Tania Serra, Hiram Castillo Michel, Katarina Vogel-Mikuš, Iztok Arčon, Mitja Klemen, Boštjan Jencic, Anja Kavčič, Mina T. Villafort Carvalho, Mark G. M. Aarts, 2018, izvirni znanstveni članek

Opis: Cadmium (Cd) was shown to co-localise with calcium (Ca) in oxalate crystals in the stems and leaves of Cd tolerant Gomphrena claussenii, but Cd binding remained unresolved. Using synchrotron radiation X-ray absorption near edge spectroscopy we demonstrate that in oxalate crystals of hydroponically grown G. claussenii the vast majority of Cd is bound to oxygen ligands in oxalate crystals (488%; Cd–O–C coordination) and the remaining Cd is bound to sulphur ligands (Cd–S–C coordination). Cadmium binding to oxalate does not depend on the amount of Ca supplied or from which organs the crystals originate (stems and mature leaves). By contrast, roots contain no oxalate crystals and therein Cd is bound predominantly by S ligands. The potential to remove Cd by extraction of Cd-rich oxalate crystals from plant material should be tested in phytoextraction or phytomining strategies.
Najdeno v: osebi
Ključne besede: Cd XANES, Cd oxalate, Gomphrena claussenii
Objavljeno: 06.09.2018; Ogledov: 416; Prenosov: 0
.pdf Polno besedilo (3,68 MB)

56.
57.
XAS studies of Sn modified TiO2 coatings
Urška Lavrenčič Štangar, Iztok Arčon, Ksenija Maver, 2018, objavljeni povzetek znanstvenega prispevka na konferenci

Opis: Coatings based on TiO2 are extensively investigated material for the preparation of surfaces which are referred as self-cleaning. Under solar illumination these coatings catalyze pollutants degradation and enhance their removal from the surface due to photoinduced superhydrophilicity [1]. There are two main drawbacks of using pure TiO2 (anatase) as a photocatalyst; i) its band gap lies in the UVA region so it can exploit only a part of the sunlight spectrum, and ii) it has a high degree of recombination between photo generated electrons and holes on the surface. There are various strategies to improve the photocatalytic efficiency of TiO2, one of them is the modification with transition metals. Based on our previous experiences with sol-gel synthesis of low-temperature TiO2 thin films [2], we prepared a series of Sn modified TiO2 photocatalysts. As a starting material only organic (Ti and Sn alkoxide) precursors were used. The loadings of Sn cations were varied in the range of 0.05 to 20 mol.%. The coatings, deposited on glass substrates by dip-coating technique, were dried at 150 oC. In addition, another set of photocatalyst coatings was prepared by further calcination at 500 °C in air. The comparison of photocatalytic activities of Sn modified TiO2 to unmodified TiO2 showed that Sn loadings in the range of 1-10 mol.% improved photocatalytic activity up to 8 times. At lower loadings of Sn, the photocatalytic activity was improved only by 30 %. After the coatings are calcined, their photocatalytic activity was significantly reduced. The objective of the research was to examine the mechanism responsible for photocatalytic properties of Sn modified TiO2 and to to clarify the role of Sn cations in the TiO2 photocatalytic process. For this purpose, Sn and Ti K-edge XANES and EXAFS analysis was used to precisely determine the local structure and the site of incorporation of Sn cations on titania nanoparticles in the coatings. We examined the hypothesis that the solid-solid interface was a crucial structural feature that facilitates charge separation and enhances photocatalytic efficiency of titania.
Najdeno v: osebi
Ključne besede: Sn, EXAFS, TiO2 fotokatalizator
Objavljeno: 12.09.2018; Ogledov: 484; Prenosov: 0
.pdf Polno besedilo (97,78 KB)

58.
X-ray spectrometry in plant biology
Primož Pelicon, Peter Kump, Anja Kavčič, Alojz Kodre, Iztok Arčon, Katarina Vogel-Mikuš, 2018, objavljeni povzetek znanstvenega prispevka na konferenci (vabljeno predavanje)

Opis: Trace elements are essential components of living systems, but at the same time they can be toxic at concentrations beyond those necessary for their biological functions. In addition, the toxicity can be extended to other non-essential elements of very similar atomic characteristics that can mimic the properties of a trace element. Trace element malnutrition affects more than half of the world’s population, while on the other hand industrialization, traffic and extensive use of fertilizers have resulted in exceedingly high concentrations of non-essential elements in food crops, posing risks to human health. In order to be able to develop and improve phyto-technologies that enable production of safe and quality food, knowledge on the basic mechanisms involved in trace and non-essential element uptake, transport, accumulation and ligand environment in plants is needed. Such studies are nowadays supported by highly sophisticated X-ray based techniques, such as synchrotron based X-ray fluorescence spectrometry, proton induced X-ray emission and X-ray absorption spectroscopy, enabling imaging of element distribution and determination of speciation and ligand environment of trace elements in biological tissues and cells with high spatial resolution and sensitivity. Selected case studies of metal distribution and speciation in selected model and crop plants, achieved by interdisciplinary work, will be presented.
Najdeno v: osebi
Ključne besede: X-ray spectrometry, plants, XANES, EXAFS
Objavljeno: 12.09.2018; Ogledov: 482; Prenosov: 0
.pdf Polno besedilo (62,44 KB)

59.
Operando XAS analysis of CuO/SiO2 and CuO/CeO2 catalysts
Albin Pintar, Maxim Zabilsky, Petar Djinović, Janvit Teržan, Iztok Arčon, 2018, objavljeni povzetek znanstvenega prispevka na konferenci

Opis: The possibilities of the operando XAS analysis of catalysts will be presented on two case studies of promising new catalytic materials: alkali doped nano-dispersed copper oxide clusters on ordered mesoporous SiO2, which is highly active and selective towards propylene epoxidation [1], and nanoshaped CuO/CeO2 catalysts used in N2O decomposition reaction [2]. Operando Cu K-edge and Ce L3-edge XANES and EXAFS analysis was performed during catalytic reactions under controlled reaction conditions in a tubular reactor filled with protective He atmosphere at 1 bar. The spectra were measured before the reaction at RT, then during heating, and during catalytic reaction at 400 °C under controlled atmosphere. Operando XANES analysis is used to monitor the changes in valence states and local symmetries of Cu and Ce cations in the catalysts. A partial reduction of Cu2+ to Cu+ and Cu0 and Ce4+ to Ce3+ species was detected during catalyst activation, and re-oxidation during catalytic reaction. Different dynamics of reaching a quasi-steady oxidation state were revealed as the tested catalysts approached the quasi-steady state after 300 min of reaction. Operando EXAFS spectra are used to precisely determine local structure of Cu and Ce cations, to identify structural characteristics and changes of Cu and Ce species during the catalytic reactions. In this way, the active site in the catalytic reactions can be identified and the mechanism of the reaction clarified. The results of operando XAS analyses are crucial to guide further material modification, to obtain more effective catalyst, and material which is more resistant to inhibiting effects that cause catalyst deactivation during catalytic reaction.
Najdeno v: osebi
Ključne besede: katalizatorji, Cu XANES, EXAFS
Objavljeno: 12.09.2018; Ogledov: 503; Prenosov: 0
.pdf Polno besedilo (62,04 KB)

60.
The effect of Zr loading on photocatalytic activity of Cu modified TiO [sub] 2
Urška Lavrenčič Štangar, Nataša Novak Tušar, Iztok Arčon, Mattia Fanetti, O. L. Pliekhov, Olena Pliekhova, 2018, objavljeni povzetek znanstvenega prispevka na konferenci

Najdeno v: osebi
Ključne besede: Cu Zr modified TiO2, EXAFS, XANES
Objavljeno: 12.09.2018; Ogledov: 430; Prenosov: 0
.pdf Polno besedilo (990,75 KB)

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