1. Photoelectrochemical conversion of biomass alcohols using in-situ Sn-doped ▫$\alpha-Fe_2O_3$▫ thin filmsManel Machreki, Artem Badasyan, Dušan Žigon, Georgi Tyuliev, Saim Emin, 2025, original scientific article Abstract: Transformation of biomass into value-added chemicals and fuels is considered an upcycling process that is beneficial to resource utilization. In this study, we used a photoelectrochemical (PEC) approach for selective oxidation of propane-1,2,3-triol to dihydroxyacetone (DHA) with high efficiency and selectivity (99%) using Sn-doped -Fe2O3 (Sn:-Fe2O3) thin films with intrinsic oxygen vacancies (OVs). DHA is an essential compound utilized in the cosmetic industry. In a similar manner, we conducted the first study of the PEC oxidation of 4-hydroxy-3-methoxybenzyl alcohol under visible light. A kinetic model has been formulated and solved to find the time-dependent generation of the products. Electrochemical impedance analyses and PEC experiments demonstrated a correlation between the concentration of molecules and the catalytic performance of Sn:-Fe2O3. Studies using scavengers indicate that the photogenerated holes (h+), singlet oxygen (1O2), hydroxyl radicals (•OH), and superoxide radicals (•O2–) play key roles in achieving high PEC activity. This work provided a new perspective on designing efficient PEC systems for biomass conversion into energy and value-added chemicals.
Keywords: Sn-doped alpha-Fe2O3, oxygen vacancies, photoelectrochemical oxidation, propane-1, 2, 3-triol, 4-hydroxy-3-methoxybenzyl alcohol
Published in RUNG: 08.01.2025; Views: 708; Downloads: 6
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3. Enhancing optical biosensing : comparing two physical treatments for GPTES chemical functionalization of cyclo-olefin copolymer foilBarbara Ressel, Jurij Urbančič, Marco Beltrami, Erik Betz-Güttner, Cinzia Cepek, Martina Conti, Ayesha Farooq, Patrizia Melpignano, 2024, original scientific article Abstract: Cyclo-olefin-copolymer (COC) transparent films are currently the best choice for micro-fluidic bio-sensors for point-of-care diagnostic applications using optical signal detection. However, while the optical and mechanical properties of this polymer are extremely good, the adhesion of the bio-probes on this surface is not optimal, due to its chemical structure, that presents only saturated carbon bonds. The deposition of organo-silane molecules on the COC surface is one of the most effective ways to overcome this problem. But, for the surface functionalization, a surface physical treatment is necessary before the chemical modification of the COC surface. In this paper a comparison of the effectiveness of two different physical treatments, oxygen plasma and UV-ozone, is reported. In particular, the exposure time of the UV-Ozone treatment has been selected to avoid the problem of auto-fluorescence of the modified COC surface, that was observed also for relatively short UV exposure (around 10 minutes). An investigation of the reactive radicals created on the surface after the physical treatments and the following chemical modification with the organo-silane molecule (GPTES) has been performed using X-ray photoemission spectroscopy. The surface energy and morphology of the films have been also measured by contact angle and optical profilometry. Finally, the bio-probes adhesion performances of the COC surfaces obtained with the two physical treatments and the chemical modification were tested in a fluorescence-based assay, using an organic light emission diode to excite the fluorescence. We observed that the UV-ozone treatment allows to obtain a siloxane network with some reactive epoxy radicals on the COC surface, however, their quantity and distribution are less important and homogeneous than in the oxygen plasma treated surfaces.
Keywords: cyclo-olefin-copolymers, organo-silane, oxygen plasma, UV-ozone, XPS, OLED
Published in RUNG: 26.06.2024; Views: 2462; Downloads: 6
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4. Yearlong variability of oxidative potential of particulate matter in an urban Mediterranean environmentD. Paraskevopoulou, Aikaterini Bougiatioti, Iasonas Stavroulas, T. Fang, Maria Lianou, Eleni Liakakou, Evangelos Gerasopoulos, R. Weber, Athanasios Nenes, Nikolaos Mihalopoulos, 2019, original scientific article Abstract: The oxidative potential (OP) of fine and coarse fractions of ambient aerosols was studied in the urban environment of Athens, Greece. OP was quantified using a dithiothreitol (DTT) assay, applied to the water soluble fraction of aerosol that was extracted from 361 fine and 84 coarse mode of 24-h and 12-h filter samples over a one-year period. During the cold period, samples were collected on a 12-h basis, to assess the impact of night-time biomass burning emissions from domestic heating on OP. The chemical characteristics of aerosols were measured in parallel using an Aerosol Chemical Speciation Monitoring (ACSM) and a 7-wavelength Aethalometer. A source apportionment analysis on the ACSM data resulted in the identification of organic aerosol (OA) factors on a seasonal basis. A good correlation of OP with NO3−, NH4+, BC (Black Carbon), Organics and LV-OOA (low volatility oxygenated OA) was found during winter, revealing the importance of combustion and aging processes for OP. During the summertime, a good correlation between OP and SO4−2 and NH4+indicates its association with regional aerosol – thus the importance of oxidative aging that reduces its association with any characteristic source. Multiple regression analysis during winter revealed that highly oxygenated secondary aerosol (LV-OOA) and, to a lesser extent, fresh biomass burning (BBOA) and fossil fuel (HOA) organic aerosol, are the prime contributors to the OP of fine aerosol, with extrinsic toxicities of 54 ± 22 pmol min−1 μg−1, 28 ± 7 and 17 ± 4 pmol min−1μg−1, respectively. In summer, OP cannot be attributed to any of the identified components and corresponds to a background aerosol value. In winter however, the regression model can reproduce satisfactorily the water soluble DTT activity of fine aerosol, providing a unique equation for the estimation of aerosol OP in an urban Mediterranean environment.
Keywords: oxidative potential, reactive oxygen species, DTT assay, particulate matter, urban aerosol
Published in RUNG: 13.05.2024; Views: 1782; Downloads: 0
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5. Photoelectrochemical activation of peroxymonosulfate using Sn-doped ▫$α-Fe_2O_3$▫ thin film for degradation of anti-inflammatory pharmaceutical drugManel Machreki, Georgi Tyuliev, Dušan Žigon, Qian Guo, Takwa Chouki, Ana Belén Jorge Sobrido, Stoichko Dimitrov, Saim Emin, 2024, original scientific article Abstract: Introduction of oxygen vacancies (OVs) has been investigated as a promising way to improve the electrical and catalytic characteristics of a hematite (α-Fe2O3) based photoelectrode. In this work, we develop a novel method for preparing porous Sn-doped α-Fe2O3 (Sn:Fe2O3) thin films with intrinsic OVs. The procedure included spin- coating an iron precursor onto a fluorine-doped tin oxide (FTO) substrate, followed by thermal treatment at elevated temperatures. The influence of Sn dopant on the optoelectronic properties of α-Fe2O3 was demonstrated by X-ray photoelectron spectroscopy and photoelectrochemical (PEC) measurements. The combined effect of OVs and Sn doping was found to play a synergistic role in reducing the charge recombination’s. The Sn:Fe2O3 photoanodes were used as a dual catalyst to oxidise water and break down an anti-inflammatory drug called 2-(4- isobutylphenyl)propanoic acid (IBPA). The Sn:Fe2O3 thin film with a 30-minute heat treatment time displayed the highest incident photon-to-current efficiency. For the first time, Sn:Fe2O3 thin films were utilised in the effective PEC degradation of IBPA employing peroxymonosulfate (PMS) under visible light illumination. The hydroxyl radicals (•OH), singlet oxygen (1O2), photogenerated holes (h+), and sulfate radicals (SO4 • ) were discovered to be the main reactive species during PEC degradation. IBPA degradation and the formation of new compounds were verified using liquid chromatography-mass spectrometry. The Lepidium sativum L phytotoxicity test reveals that PEC-treated wastewater with IBPA exhibits decreased toxicity.
Keywords: Sn-doped Fe2O3, oxygen vacancies, photoelectrochemical degradation, 2-(4-isobutylphenyl)propanoic acid, peroxymonosulfate
Published in RUNG: 10.01.2024; Views: 2260; Downloads: 42
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6. 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: 2333; Downloads: 7
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7. 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: 3392; Downloads: 16
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8. Stable seawater oxidation with a self-healing oxygen-evolving catalystXiaojian Zhang, Chao Feng, Zeyu Fan, Beibei Zhang, Yequan Xiao, Andraž Mavrič, Nadiia Pastukhova, Matjaž 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: 2790; Downloads: 7
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9. 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: 3658; Downloads: 58
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10. 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: 3023; Downloads: 22
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