11. 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: 8541; Prenosov: 144
 Celotno besedilo (3,18 MB) |
12. Photoactive nanocomposite thin films on glass and thermosensitive substratesNives Vodišek, 2019, doktorska disertacija Opis: Photocatalysis is a well-known process for the last few decades; it is predominantly used for water and air purification, but also for self-cleaning and antibacterial surfaces. The photocatalytic process is one of the advanced oxidation processes, where semiconductors are mainly used as photocatalysts. The most known and used semiconductor is nanosized titania, which can non-selectively decompose organic matters. One of the side effects of nano TiO2 under UV irradiation is photoinduced hydrophilicity, which furthermore improves the self-cleaning effect. The main drawback of TiO2 is that for its activation UV light is needed, which represents only 5 percent of the solar spectrum. Consequently, actinic irradiance power is low and the response of photocatalyst is limited. Novel approaches are being introduced to improve TiO2 response to visible light such as doping, coupling, modification of surface morphology and others.
The thesis consists of five principal chapters. The first chapter is focused on a short literature review and explanation of some basic terms and principles that are related to this thesis.
The aim of the research was to prepare transparent photocatalytically active thin films on glass and thermosensitive substrates. Four thermosensitive substrates were used: polyvinyl chloride (PVC) foil, polymethyl methacrylate (PMMA) sheet and polyester (PES) fabric coated with a polyvinyl and acrylic coating, with (D1) or without (D2) an additional polyvinylidene fluoride topcoat. The synthesis of films was modified with the introduction of zirconium aiming at improving the photocatalytic activity of the TiO2 films, and the final films had a SiO2 phase present for increased mechanical robustness.
The third chapter is dedicated to the experimental part of the thesis. The detailed process of synthesis is described. The sol-gel process was used to prepare initial Ti-Zr sols, colloidal aqueous solutions with TiO2 and ZrO2 nanoparticles derived from titanium and zirconium alkoxides. The four different Ti-Zr sols were prepared with 0, 5, 10 and 20 molar % of Zr according to Ti. The depositing solution was prepared by mixing Ti-Zr sol, SiO2 sol binder, 1-propanol and 2-propoxyethanol, and then thin films were deposited by dip-coating technique. After the deposition, samples did not require high-temperature calcination since the photocatalytic anatase phase was present already after drying the deposited layers. Coated glass slides were put into a furnace at 150 °C, while samples on thermosensitive substrates were just treated by a heat gun. Samples in powder and thin film form were characterized by UV-Vis, FTIR-ATR and laser beam deflection spectroscopy, X-ray diffraction, scanning electron microscopy and thermal analysis. One of the main aspects of the photocatalyst is its activity. Photocatalytic activity of the thin films was determined, either quantitatively by the formation of fluorescent hydroxyterephthalic acid, one of the first degradation products of terephthalic acid deposit, or qualitatively by a visual-based method where degradation of resazurin ink was observed. Two additional methods were used on glass samples, electron paramagnetic resonance, and degradation of methyl stearate by observing the change in water contact angle under UVA irradiation. Mechanical stability of films on various substrates is an essential factor, describing how successful was immobilization of the photocatalytic materials on the substrate. It was determined by the pencil hardness test, i.e., Wolff-Wilborn method.
In the fourth chapter, titled “Results and Discussion,” the most important part of the thesis is placed. Materials characterization and associated discussion of the results are divided into three major parts: i) powder samples characterization; ii) characterization of thin films on a glass substrate, and iii) characterization of films on thermosensitive substrates.
In the conclusions, the main findings of the Ph.D. research work are summarized. One of our initial hypotheses was disapproved, thin films were not more active with a higher content of zirconium. However, they were more durable. All the obtained films were transparent and photoactive, despite the low-temperature synthesis procedure. Besides commonly used glass substrate, immobilization on thermosensitive substrates was also successful.
Ključne besede: glass substrate, immobilization, nanocomposite, nanomaterials, PES, photocatalysis, PMMA, PVC, self-cleaning surfaces, silica, plastic substrates, thin films, titania, zirconia
Objavljeno v RUNG: 14.10.2019; Ogledov: 5085; Prenosov: 191
Celotno besedilo (6,23 MB) |
13. Cu and Zr surface sites in photocatalytic activity of TiO [sub] 2 nanoparticles : the effect of Zr distributionOlena Pliekhova, O. L. Pliekhov, Mattia Fanetti, Iztok Arčon, Nataša Novak Tušar, Urška Lavrenčič Štangar, 2019, izvirni znanstveni članek Opis: The present work is focused on the role of ZrO2 modification in the performance of CuO modified TiO2. Zirconia
loading leads to formation of more resistant photocatalytic layers compared to samples modified with only
copper containing species. Surface modification of mixed phase TiO2 with CuO/ZrO2 improves the degradation
of Reactive blue 19 dye under simulated solar irradiation. An in-depth investigation of the catalysts showed that
in case of CuO/ZrO2 modification, the covering of the TiO2 surface with zirconium containing species prevents
morphological and harmful energetic changes induced by copper species formed on the rutile TiO2 phase at a
higher copper loading.
Ključne besede: titanium dioxide, surface modification, XAS analysis, surface acidity, Hammett indicators
Objavljeno v RUNG: 26.03.2019; Ogledov: 4140; Prenosov: 0
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14. Self-cleaning and photoactive TiO2 – ZrO2 – SiO2 films on thermosensitive and glass substratesNives Vodišek, Urška Lavrenčič Štangar, 2017, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Nanosized TiO2 is well-known for its photocatalytic property. From the combination of photocatalysis and photoinduced hydrophilicity properties, thin films of this material have also anti-fogging, self-cleaning and antimicrobial properties. There are numerous deposition techniques e.g. spin-coating, dip-coating, spraying, the most suitable one is chosen based on substrate or solution characteristics. Thin films are often required to be transparent for visible light, especially if we use them on transparent substrates, or they should not affect the color of the substrate. Radicals that are produced during photosensitizing process are able to destroy structure of a substrate and substrate can lose mechanical stability [1,2]. Some studies show that adding a SiO2 protective layer can prevent the damage of the substrate [3–5]. Ti-Zr containing sols were prepared with sol-gel process, where titanium(IV) isopropoxide, zirconium(IV) butoxide and ethanol were hydrolyzed with aqueous solution of perchloric acid. Solution was then refluxed for 48 hours. During that time crystallization and deaggregation took place and that resulted in a stable final solution [6]. To prepare suitable solution for production of durable films silica binder was added. On glass and plastic substrates, thin films were deposited with the dip-coating method and dried with a heat-gun. Thin films were characterized by measurements of photocatalytic activity with terephthalic acid as model organic pollutant subjected to oxidation via fluorescent degradation product, photoinduced superhydrophilicity phenomena, UV-Vis and ATR-FTIR spectroscopy, SEM images, as well as mechanical properties measurements.
References
[1] H. Schmidt, M. Naumann, T.S. Müller, M. Akarsu, Thin Solid Films (2006) 502, 132– 137.
[2] W. A. Daoud, J.H. Xin, Y.H. Zhang, Surf. Sci. (2005) 599, 69–75.
[3] Ž. Senić, S. Bauk, M. Vitorović-Todorović, N. Pajić, A. Samolov, D. Rajić, Sci. Tech. Rev. (2011) 61, 63–72.
[4] T. Yuranova, R. Mosteo, J. Bandara, D. Laub, J. Kiwi, J. Mol. Catal. A: Chem. (2006) 244, 160–167.
[5] T. Yuranova, D. Laub, J. Kiwi, Catal. Today (2007) 122, 109–117.
[6] N. Vodišek, K. Ramanujachary, V. Brezová, U. Lavrenčič Štangar, Catal. Today (2017) 287, 142–147.
Ključne besede: Self-cleaning surface, photocatalysis, TiO2, ZrO2, SiO2, PVC, PMMA, thermosensitive substrates, glass
Objavljeno v RUNG: 05.03.2019; Ogledov: 4676; Prenosov: 0
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15. Photocatalytic properties of metal modified TiO2 by photothermal techniquesZeinab Ebrahimpour, Olena Pliekhova, Humberto Cabrera, Dorota Korte, Urška Lavrenčič Štangar, Mladen Franko, 2018, objavljeni povzetek znanstvenega prispevka na konferenci Ključne besede: Thermal lens spectrometry, Photothermal beam deflection spectroscopy, Dye remediation, Photothermal technique, Photocatalytic degradation, Reactive Blue 19, TiO2 modification
Objavljeno v RUNG: 09.11.2018; Ogledov: 4702; Prenosov: 0
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16. Transparent Photocatalytic Thin Films on Flexible Polymer SubstratesNives Vodišek, Andraž Šuligoj, Dorota Korte, Urška Lavrenčič Štangar, 2018, izvirni znanstveni članek Ključne besede: photocatalysis, self-cleaning surface, TiO2, ZrO2, SiO2, transparent films, thermosensitive
substrates, PMMA, PVC, PES, PVDF
Objavljeno v RUNG: 19.10.2018; Ogledov: 4459; Prenosov: 152
Celotno besedilo (4,37 MB) |
17. XAS studies of Sn modified TiO2 coatingsKsenija Maver, Iztok Arčon, Urška Lavrenčič Štangar, 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.
Ključne besede: Sn, EXAFS, TiO2 fotokatalizator
Objavljeno v RUNG: 12.09.2018; Ogledov: 4384; Prenosov: 0
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19. The effect of Zr loading on photocatalytic activity of Cu modified TiO2Olena Pliekhova, O. L. Pliekhov, Mattia Fanetti, Iztok Arčon, Nataša Novak Tušar, Urška Lavrenčič Štangar, 2018, objavljeni znanstveni prispevek na konferenci Ključne besede: Titanium diokside, acidic sites, surface titration, copper, zirconium
Objavljeno v RUNG: 10.09.2018; Ogledov: 4877; Prenosov: 0
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