Urška Lavrenčič Štangar

Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment

One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO2-SnS2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO2-SnS2/H2O2, for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO2-SnS2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO2-SnS2/H2O2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO2-SnS2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO2-SnS2 morphology due to the partial transformation of visible-active SnS2 into non-active SnO2. Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO2-SnS2 composite in applied solar-driven water treatment.

Design and evaluation of a compact photocatalytic reactor for water treatment

A compact reactor for photocatalytic oxidation and photocatalytic ozonation water treatment was developed and evaluated by using four model pollutants. Additionally, combinations of pollutants were evaluated. Specially produced Al2O3 porous reticulated monolith foams served as TiO2 carriers, offering a high surface area support. UV lamps were placed in the interior to achieve reduced dimensions of the reactor (12xa0cm in diameter × 20xa0cm in height). Despite its small size, the overall photocatalytic cleaning capacity was substantial. It was evaluated by measuring the degradation of LASxa0+xa0PBIS and RB19 as representatives of surfactants and textile dyes, respectively. These contaminants are commonly found in household grey wastewater with phenol as a trace contaminant. Three different commercial photocatalysts and one mixture of photocatalysts (P25, P90, PC500 and P25xa0+xa0PC500) were introduced in the sol-gel processing and immobilized on foamed Al2O3 monoliths. RB19 and phenol were easily degradable, while LAS and PBIS were more resistant. The experiments were conducted at neutral-acidic pH because alkaline pH negatively influences both photocatalyic ozonation (PCOZ) and photocatalysis. The synergistic effect of PCOZ was generally much more expressed in mineralization reactions. Total organic carbon TOC half lives were in the range of between 13 and 43xa0min in the case of individual pollutants in double-deionized water. However, for the mixed pollutants in tap water, the TOC half-life only increased to 53xa0min with the most efficient catalyst (P90). In comparison to photocatalysis, the PCOZ process is more suitable for treating wastewater with a high loading of organic pollutants due to its higher cleaning capacity. Therefore, PCOZ may prove more effective in industrial applications.

TiO2-SnS2 nanocomposites: solar-active photocatalytic materials for water treatment

The study is aimed at evaluating TiO2-SnS2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO2-SnS2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO2 and SnS2) within the immobilization step. The as-prepared TiO2-SnS2 composites and their sole components (TiO2 or SnS2) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO2-SnS2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO2-SnS2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO2-SnS2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO2-SnS2 composites showed higher activity at neutral pH.

Surface modified titanium dioxide using transition metals: nickel as a winning transition metal for solar light photocatalysis

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 = 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.

WO3-decorated ZnO nanostructures for light-activated applications

In the present work, a two-step vapor-phase route was implemented for the tailored design of ZnO–WO3 nanoheterostructures supported on fluorine-doped tin oxide (FTO) substrates. Under optimized conditions, the sequential use of chemical vapor deposition (CVD) and radio frequency (RF)-sputtering for the deposition of zinc and tungsten oxides respectively, resulted in the growth of calyx-like ZnO nanostructures uniformly decorated by a conformal dispersion of low-sized WO3 nanoparticles. The target materials were characterized by means of a multi-technique approach, with particular regard to their structural, compositional, morphological and optical properties. Finally, their photocatalytic performances were preliminarily tested in the abatement of NOX gases (NO and NO2). Due to the unique porous morphology of the ZnO nanodeposit and the high density of ZnO–WO3 heterojunctions, WO3-decorated ZnO revealed appealing De-NOX characteristics in terms of both degradation efficiency and selectivity. Such features, along with the photoinduced superhydrophilicity and self-cleaning properties of the present nanomaterials, candidate them as promising functional platforms for applications in smart windows and building materials for environmental remediation.

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

The objective of this research is to examine how Cu modification can improve the photocatalytic activity of TiO2‐SiO2, to explain the 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 (0.05–3u2005molu2009%). The sol–gels were dried at 150u2009°C 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 0.1u2005molu2009%. 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.