1. 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: 144; Downloads: 2
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2. In Situ Techniques for Characterization of Layered Double Hydroxide-Based Oxygen Evolution CatalystsAndraž Mavrič, Matjaž Valant, 2023, review article Abstract: Functional layered double hydroxide (LDH) usually contains different cationic substitutes to increase the activity of the oxygen evolution reaction (OER). The intrinsic OER activity of LDH materials is connected with the chemical composition and dispersion of metal cations substitutions in the matrix phase. The potential induced phase transitions, in particular hydroxide-to-oxyhydroxide transitions, are a predisposition for the high OER activity of LDH materials and can be followed by coupling the electrochemical experiments with spectroscopic techniques. The understanding of LDH catalysts under electrochemical conditions also allows an understanding of the behavior of OER catalysts based on transition metals, metal-chalcogenides, -pnictides, -carbides, and metal–organic frameworks. The surfaces of those materials are intrinsically poor OER catalysts. However, they act as precursors to catalysts, which are oxidized into a metal (oxy)hydroxide. This review summarizes the use of in situ techniques for the characterization of LDH-based OER electrocatalysts and presents the influence of these techniques on the understanding of potential induced phase transitions, identification of active sites, and reaction mechanisms. Keywords: oxygen evolution reaction, layered double hydroxide, in-situ characterization Published in RUNG: 14.07.2023; Views: 283; Downloads: 3
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3. Stable seawater oxidation with a self-healing oxygen-evolving catalystXiaojian Zhang, Chao Feng, Zeyu Fan, Beibei Zhang, Yequan Xiao, Andraž Mavrič, Nadiia Pastukhova, Matjaz Valant, Yi-Fan Han, Yanbo Li, 2023, original scientific article Abstract: Direct seawater electrolysis is key to massive hydrogen fuel production without the depletion of precious freshwater resources and the need for high-purity electrolytes. However, the presence of high-concentration chloride ions (Cl−) and alkaline-earth metal ions (Mg2+, Ca2+) poses great challenges to the stability and selectivity of the catalysts for seawater splitting. Here, we demonstrate a self-healing oxygen evolution reaction (OER) catalyst for long-term seawater electrolysis. By suppressing the competitive chlorine evolution reaction and precipitating the alkaline-earth metal ions through an alkaline treatment of the seawater, stable seawater oxidation is achieved owing to the self-healing ability of the borate-intercalated nickel–cobalt–iron oxyhydroxides (NiCoFe-Bi) OER catalyst under highly-alkaline conditions. The self-healing NiCoFe-Bi catalyst achieves stable seawater oxidation at a large current density of 500 mA cm−2 for 1000 h with near unity Faraday efficiency. Our results have demonstrated strong durability and high OER selectivity of the self-healing catalyst under harsh conditions, paving the way for industrial large-scale seawater electrolysis. Keywords: chemistry, electrocatalysis, seawater oxidation, oxygen evolution reaction Published in RUNG: 08.05.2023; Views: 384; Downloads: 0
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4. Oxygen vacancies engineering in metal oxide nanomaterials for efficient photo-electrocatalytic degradation of organic pollutants and chemical transformations : dissertationManel Machreki, 2022, doctoral dissertation Keywords: titanium dioxide nanotubes, hematite, oxygen vacancies, photoelectrochemical degradation of dye, ibuprofen, chemical transformation, glycerol, vanillyl alcohol, dissertations Published in RUNG: 01.03.2023; Views: 715; Downloads: 25
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5. 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: 1157; Downloads: 19
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8. Paramagnetic intrinsic point defects in alkali phosphate glasses : unraveling the P[sub]3 center origin and local environment effectsLuigi Giacomazzi, Nikita S. Shcheblanov, Layla Martin-Samos, Mikhail E. Povarnitsyn, Shinji Kohara, Matjaž Valant, Nicolas Richard, Nadege Ollier, 2021, original scientific article Keywords: oxygen, electron paramagnetic resonance spectroscopy, phosphates, amorphous materials, defects Published in RUNG: 04.05.2021; Views: 2096; Downloads: 0 This document has many files! More... |
9. Secondary organic aerosol formation from semi- and intermediate-volatility organic compounds and glyoxal : relevance of O/C as a tracer for aqueous multiphase chemistryEleanor M. Waxman, Katja Džepina, Barbara Ervens, Julia Lee-Taylor, Bernard Aumont, Jose L. Jimenez, Sasha Madronich, Rainer Volkamer, 2013, original scientific article Abstract: The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry. Keywords: secondary organic aerosol, glyoxal, aqueous multiphase chemistry, oxygen-to-carbon ratio, single scattering albedo Published in RUNG: 11.04.2021; Views: 1535; Downloads: 0 This document has many files! More... |
10. Effect of the Morphology of the High-Surface-Area Support on the Performance of the Oxygen-Evolution Reaction for Iridium NanoparticlesLeonard Moriau, Marjan Bele, Živa Marinko, Francisco Ruiz-Zepeda, Gorazd Koderman, Martin Šala, Angelija Kjara Šurca, Janez Kovač, Iztok Arčon, Primož Jovanovič, Nejc Hodnik, Luka Suhadolnik, 2021, original scientific article Abstract: The development of affordable, low-iridium-loading,
scalable, active, and stable catalysts for the oxygen-evolution
reaction (OER) is a requirement for the commercialization of
proton-exchange membrane water electrolyzers (PEMWEs).
However, the synthesis of high-performance OER catalysts with
minimal use of the rare and expensive element Ir is very challenging
and requires the identification of electrically conductive and stable
high-surface-area support materials. We developed a synthesis
procedure for the production of large quantities of a nanocomposite
powder containing titanium oxynitride (TiONx) and Ir.
The catalysts were synthesized with an anodic oxidation process
followed by detachment, milling, thermal treatment, and the
deposition of Ir nanoparticles. The anodization time was varied to grow three different types of nanotubular structures exhibiting different lengths and wall thicknesses and thus a variety of properties. A comparison of milled samples with different degrees of nanotubular clustering and morphology retention, but with identical
chemical compositions and Ir nanoparticle size distributions and dispersions, revealed that the nanotubular support morphology is
the determining factor governing the catalyst’s OER activity and stability. Our study is supported by various state-of-the-art
materials’ characterization techniques, like X-ray photoelectron spectroscopy, scanning and transmission electron microscopies, Xray powder diffraction and absorption spectroscopy, and electrochemical cyclic voltammetry. Anodic oxidation proved to be a very suitable way to produce high-surface-area powder-type catalysts as the produced material greatly outperformed the IrO2 benchmarks
as well as the Ir-supported samples on morphologically different TiONx from previous studies. The highest activity was achieved for the sample prepared with 3 h of anodization, which had the most appropriate morphology for the effective removal of oxygen
bubbles. Keywords: electrocatalysis, oxygen-evolution reaction, TiONx-Ir powder catalyst, iridium nanoparticles, anodic oxidation, morphology−activity correlation Published in RUNG: 04.01.2021; Views: 2035; Downloads: 0 This document has many files! More... |