1. Nickel-decorated ZnO nanoparticles for effective solar reduction of hexavalent chromium and removal of selected pharmaceuticalsMiha Ravbar, Ksenija Maver, Tilen Knaflič, Iztok Arčon, Nataša Novak Tušar, Urška Lavrenčič Štangar, Andraž Šuligoj, 2025, izvirni znanstveni članek Opis: The efficient visible light driven photocatalytic reduction of hexavalent chromium, Cr(VI) was demonstrated using ZnO nanoparticles (NPs) decorated with oxo-clusters of transition metals. The ZnO NPs were synthesized by a facile one-pot solvothermal synthesis followed by a fast microwave-assisted (MW) grafting of transition metals on the surface of NPs. Nickel was found to be the most active transition metal for photocatalytic activity as demonstrated by reduction of Cr(VI) to Cr(III). The optimally grafted samples contained 0.5 wt% Ni and increased photocatalytic activity by almost one-fold. The oxo-clusters did not enter the lattice of ZnO but rather resided on the surface and their efficient bonding to the ZnO surface was proved by Raman, TEM and X-Ray absorption techniques. Influence of MW power was studied and shown that excessive power load leads to formation of elongated structures of ZnO which decreases the photocatalytic activity. It was demonstrated by measuring fluorescent radical products that electrons, efficiently transferred via oxygen, were the main active species in combination with the unchanged oxidation power of holes and • OH in the grafted samples. The applicability of the materials was tested in immobilized plug flow photoreactor system degrading five pharmaceuticals simultaneously where their long-term use was shown. Ključne besede: Zinc oxide, Pharmaceuticals, Grafting, Cr(VI), Zn XANES, Zn EXAFS Objavljeno v RUNG: 24.10.2024; Ogledov: 355; Prenosov: 4 Celotno besedilo (4,49 MB) Gradivo ima več datotek! Več... |
2. Transparent vanadium doped titania-silica films : structural characterization and self-cleaning propertiesAndraž Šuligoj, Nejc Povirk, Ksenija Maver, Andraž Mavrič, Urška Lavrenčič Štangar, Angelja Kjara Surca, 2024, izvirni znanstveni članek Ključne besede: photocatalysis, TiO2-SiO2, vanadium, film, Raman spectroscopy Objavljeno v RUNG: 09.09.2024; Ogledov: 571; Prenosov: 7 Celotno besedilo (9,47 MB) Gradivo ima več datotek! Več... |
3. 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, izvirni znanstveni članek Opis: 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. Ključne besede: titanium dioxide, sol-gel processes, functionla applications, water treatment Objavljeno v RUNG: 30.09.2022; Ogledov: 2229; Prenosov: 0 Gradivo ima več datotek! Več... |
4. Characterization of Cu and Zr modified TiO[sub]2 photocatalysts by photothermal beam deflection spectrometryMahmoud Abdelhamid, Dorota Korte, Humberto Cabrera, Zeinab Ebrahimpour, Olena Pliekhova, Urška Lavrenčič Štangar, Mladen Franko, 2021, objavljeni povzetek znanstvenega prispevka na konferenci Ključne besede: photocatalysts, TiO2, Cu/Zr, photodegradation, material characterization, photothermal spectrometry Objavljeno v RUNG: 23.11.2021; Ogledov: 3352; Prenosov: 0 Gradivo ima več datotek! Več... |
5. Thermo-optical characterization of Cu- and Zr-modified TiO[sub]2 photocatalysts by beam deflection spectrometryMahmoud Abdelhamid, Dorota Korte, Humberto Cabrera, Olena Pliekhova, Zeinab Ebrahimpour, Urška Lavrenčič Štangar, Mladen Franko, 2021, izvirni znanstveni članek Ključne besede: photocatalysts, TiO2, Cu/Zr, photodegradation, material characterization, photothermal spectrometry Objavljeno v RUNG: 23.11.2021; Ogledov: 2577; Prenosov: 100 Povezava na celotno besedilo Gradivo ima več datotek! Več... |
6. Improved photocatalytic activity of SnO[sub]2-TiO[sub]2 nanocomposite thin films prepared by low-temperature sol-gel methodKsenija Maver, Iztok Arčon, Mattia Fanetti, Samar Al Jitan, Giovanni Palmisano, Matjaž Valant, Urška Lavrenčič Štangar, 2021, izvirni znanstveni članek Opis: The objective of this research was to investigate how the photocatalytic activity of pure TiO2 can be improved by
SnO2 modification. Different molar ratios of tin to titanium were prepared. The correlation between tin concentration
and structural properties was investigated to explain the mechanism of photocatalytic efficiency and
to optimize the synthesis conditions to obtain enhanced activity of the SnO2-modified TiO2 photocatalysts under
UV-irradiation. The SnO2-modified TiO2 photocatalysts were prepared by a low-temperature sol-gel method
based on organic tin and titanium precursors. The precursors underwent sol-gel reactions separately to form
SnO2-TiO2 sol. The sol-gels were deposited on a glass substrate by a dip-coating technique and dried at 150 ◦C to
obtain the photocatalysts in the form of a thin film. To test the thermal stability of the material, an additional set
of photocatalysts was prepared by calcining the dried samples in air at 500 ◦C. The photocatalytic activity of the
samples was determined by measuring the degradation rate of an azo dye. An increase of up to 30% in the
photocatalytic activity of the air-dried samples was obtained when the TiO2 was modified with the SnO2 in a
concentration range of 0.1–1 mol.%. At higher SnO2 loadings, the photocatalytic activity of the photocatalyst
was reduced compared to the unmodified TiO2. The calcined samples showed an overall reduced photocatalytic
activity compared to the air-dried samples. Various characterization techniques (UV-Vis, XRD, N2-physisorption,
TEM, EDX, SEM, XAS and photoelectrochemical characterization) were used to explain the mechanism for the
enhanced and hindered photocatalytic performances of the SnO2-modified TiO2 photocatalysts. The results
showed that the nanocrystalline cassiterite SnO2 is attached to the TiO2 nanocrystallites through the Sn-O-Ti
bonds. In this way, the coupling of two semiconductors, SnO2 and TiO2, was demonstrated. Compared to
single-phase photocatalysts, the coupling of semiconductors has a beneficial effect on the separation of charge
carriers, which prolongs their lifetime for accessibility to participate in the redox reactions. The maximum increase
in activity of the thin films was achieved in the low concentration range (0.1–1 mol.%), which means that
an optimal ratio and contact of the two phases is achieved for the given physical parameters such as particle size,
shape and specific surface area of the catalyst. Ključne besede: photocatalytic activity, Sn-modified TiO2, low-temperature, thin films, XAS analysis Objavljeno v RUNG: 05.07.2021; Ogledov: 3697; Prenosov: 0 Gradivo ima več datotek! Več... |
7. Sn-modified TiO[sub]2 thin film photocatalysts prepared by low-temperature sol-gel processing : dissertationKsenija Maver, 2021, doktorska disertacija Opis: Due to many advantageous physiochemical properties, titanium dioxide (TiO2) is the most widely used photocatalyst in numerous applications, such as wastewater treatment and air purification, self-cleaning surfaces and energy conversion (H2 generation). However, one of its disadvantages is the high electron-hole recombination rate, and coupling with other semiconductors is one of the strategies to improve it. The objective of this dissertation was to investigate how the photocatalytic activity of pure TiO2 can be improved by tin modification and to explain the mechanism of increased or hindered photoactivity in correlation with the structural properties of the modified TiO2 photocatalysts.
A new low-temperature sol-gel synthesis route was developed to prepare Sn- or SnO2-modified TiO2 photocatalysts. In both cases, organic tin and titanium precursors were used. Tin in the form of Sn cations was used to prepare Sn-modified TiO2. In this case, the precursors went through the sol-gel reaction together to form a Sn-TiO2 sol. In the case of SnO2 modification, the SnO2 sol was prepared separately and additionally mixed with the TiO2 sol to form a TiO2/SnO2 bicomponent semiconductor system. Different molar ratios of tin to titanium were prepared to investigate the correlation between the tin concentration and the photocatalytic properties of the photocatalysts in the form of thin films. The results were used to optimize the synthesis conditions to obtain an improved activity of the modified TiO2 photocatalysts under UV-irradiation.
The photocatalytic activity of the thin films was determined by measuring the degradation rate of an azo dye. An increase of up to 40 % in the photocatalytic activity of the dried samples (at 150 °C) was achieved when the TiO2 was modified with the Sn or SnO2 in a concentration range of 0.1 to 1 mol.%. At higher Sn or SnO2 loadings and after calcination of the samples at 500 °C, the photocatalytic activity of the photocatalyst was reduced compared to the unmodified TiO2.
Different characterization techniques (UV-Vis, XRD, nitrogen physisorption, TEM, SEM and XAS) were employed to clarify the mechanism responsible for the enhanced and hindered photocatalytic performance of the Sn- and SnO2-modified TiO2 photocatalysts. The results showed that a nanocrystalline structure is already achieved in the samples by the low-temperature film treatment (drying at 150 °C) and that the photocatalytic efficiency is mainly influenced by the crystalline phase composition: anatase/rutile in the case of Sn-modified and TiO2/SnO2 in the case of SnO2-modified TiO2. The crystal size and specific surface area differ insignificantly between the equally thermally treated samples and partly explain the differences in photoefficiency of the calcined samples compared to the dried samples. The structural study at the atomic level, using the Sn K-edge EXAFS, revealed that Sn cations act as nucleation sites for the anatase to rutile transformation in the Sn-modified TiO2 photocatalysts, while in the SnO2-modified TiO2 samples the nanocrystalline cassiterite SnO2 is bound to the TiO2 nanocrystallites via the Sn-O-Ti bond. In both cases, the advantage of coupling the two semiconductors was achieved by separating the charge carriers and thus prolonging their lifetime for accessibility to participate in the redox reactions. The maximum activity enhancement was achieved in the low concentration range (0.1–1 mol.%), which means that an optimal ratio and contact of the two phases are obtained for the given physical parameters, such as particle size, shape and specific surface area of the catalyst. Ključne besede: Sn-modified TiO2, SnO2-modified TiO2, low-temperature sol-gel, thin films, photocatalytic activity, anatase/rutile system, Sn K-edge EXAFS, dissertations Objavljeno v RUNG: 09.06.2021; Ogledov: 6161; Prenosov: 173 Povezava na celotno besedilo Gradivo ima več datotek! Več... |
8. Photodegradation mechanisms of reactive blue 19 dye under UV and simulated solar light irradiationZeinab Ebrahimpour, Olena Pliekhova, Humberto Cabrera, Mahmoud Abdelhamid, Dorota Korte, Komlan Segbéya Gadedjisso-Tossou, Joseph J. Niemela, Urška Lavrenčič Štangar, Mladen Franko, 2021, izvirni znanstveni članek Ključne besede: reactive blue 19, photocatalytic, photosensitization, thermal lens, UV-Vis Objavljeno v RUNG: 02.02.2021; Ogledov: 3435; Prenosov: 0 Gradivo ima več datotek! Več... |
9. Improved photocatalytic activity of anatase-rutile nanocomposites induced by low-temperature sol-gel Sn-modification of TiO2Ksenija Maver, Iztok Arčon, Urška Lavrenčič Štangar, Mattia Fanetti, Saim Emin, Matjaž Valant, 2020, izvirni znanstveni članek Opis: The Sn-modified TiO2 photocatalysts are prepared by low-temperature sol-gel processing based on organic titanium
and tin precursors with varied Sn concentrations (from 0.1–20 mol .%). The role of Sn dopant as the
promotor of the formation of TiO2 rutile crystalline phase is explained and the optimal Sn concentration for
preparation of efficient Sn-modified titania photocatalyst is determined. Up to 40 % increase in photocatalytic
activity is achieved in Sn-modified TiO2 photocatalytic thin films dried at 150 °C with low Sn concentrations in
the range from 0.1 to 1 mol .%. At low Sn concentrations optimal ratio between anatase and rutile (nano)crystals
is obtained, which facilitates charge separation at the TiO2 photocatalyst’s surface. When the concentration of Sn
increases above 5 mol.% or when the films are calcined at 500 °C, the relative amount of rutile phase with
inferior photocatalytic activity, increases and the nanocrystals of titania grow, leading to fewer active sites per
unit mass and the reduction of activity in comparison to unmodified TiO2. Ključne besede: Anatase-rutile
Sn-modified TiO2
XAS analysis
Photocatalytic activity Objavljeno v RUNG: 10.02.2020; Ogledov: 3811; Prenosov: 0 Gradivo ima več datotek! Več... |
10. Zr/Cu-TiO2 CATALYSTS FOR PHOTOCATALYTIC WATER TREATMENTOlena Pliekhova, 2019, doktorska disertacija Opis: This work entitled «Zr/Cu-TiO2 catalysts for photocatalytic water treatment» tackles a problem of tons of dyes discharged everyday mainly from textile industries. This is a huge concern because of dyes persistence, toxicity and potential to the bioaccumulation in living organisms. Here, a small contribution to overall problem is presented.
The research work consists of three main parts: Theoretical background, Experimental and Results and discussion. In the Theoretical background chapter the overall problem is identified and discussed. The main water treatment techniques are presented briefly with their advantages and drawbacks. Photocatalysis assisted with TiO2 is shown as an alternative additional technique with its own pros and cons. Further, a cursory overview of TiO2 modification techniques is made and advantages in using copper and zirconium oxides for TiO2 modification are presented. The reason and possible positive effect of using of two oxides simultaneously for TiO2 modification is indicated. Additionally, a positive impact of solar light for overall rate of dyes degradation assisted with TiO2 is discussed. Within the framework of photosensitization effect, the problem of using dyes for assessment of photocatalytic properties of materials under the visible light is touched on. Photothermal methods as possible beneficial techniques for this purpose are proposed.
In the Experimental chapter, all experimental techniques used in current research work with the technical details specific for the research work are presented. There are methods of materials preparation, photocatalytic tests under different conditions and varying model pollutants, and physico-chemical characterization techniques.
The Results and discussion chapter is divided by three subchapters. Each chapter is dedicated to one hypothesis, which was checked and confirmed or disproved. The first hypothesis is about beneficial loading of copper and zirconium oxides to TiO2. After numerous experiments held, it was concluded that the pair of copper and zirconium oxides is beneficial for simultaneous application on TiO2 surface to promote its performance.
The second subchapter is about zirconium distribution and its impact on the activity of studied materials towards the antraquinone dye Reactive Blue 19. Different techniques such as XRD, TEM, EXAFS and many others were used in order to characterize the materials and to understand the details of the processes taking place. The existence of upper limit of copper oxide loading for its beneficial effect on TiO2 performance was demonstrated. It was observed that zirconium species loading leads to improvement in performance of materials with higher copper loading, which otherwise lowers activity of TiO2 – this is in case when copper only above its optimal level is present. It was concluded that zirconium oxide containing species occupy rutile surface sites in mixed phase TiO2 and this way beneficially influence the material performance towards the dye removal.
The third subchapter is about the visible light TiO2 assisted dye degradation. It is well known that photosensitization mechanism of dye degradation appears under the visible and as a consequence under the solar light irradiation. This leads to the overall enhancement of dyes degradation, which is positive and may be used as a benefit for faster pollutant destruction. However, this fact leads to mishmash in the determination of real photocatalytic activity of materials towards the dye. It was hypothesized that the impact of photosensitization mechanism on the overall material performance against Reactive blue 19 dye (RB19) descends with the dye concentration lowering. Thermal lens spectrometry (TLS) which is sensitive to chemicals at low concentrations was used for hypothesis evaluation.
To summarize the research work achievements, the conclusions of the thesis are given at the end. Ključne besede: titanium dioxide, photocatalysis, zirconium/copper, surface modification, water treatment, dyes Objavljeno v RUNG: 03.12.2019; Ogledov: 8213; Prenosov: 144 Celotno besedilo (3,18 MB) |