Bi2O3-BASED PYROCHLORE NANOSTRUCTURES AND THEIR CRYSTALLOGRAPHIC, OPTOELECTRONIC AND PHOTOCATALYTIC PROPERTIESMetka Benčina
, 2015, doctoral dissertation
Abstract: Bi2O3-based pyrochlore nanomaterials and their photocatalytic, optoelectronic and crystallographic properties are the research topics of this doctoral dissertation. We synthesized these materials at nanoscale, since they are expected to possess photoactivity in the visible-light spectrum, which is an important target for the high-performance photocatalysts. To prepare nanoparticles that are not agglomerated, different synthesis methods (coprecipitation, coprecipitation followed by the digestion, reverse micelle) and post-treatments (furnace or hydrothermal reactor) were examined. Micrometer size materials were prepared with the solid-state reaction and annealing at high temperature.
Bi2Ti2O7 nanoparticles were synthesized with the coprecipitation reaction, followed by annealing at 570 °C in the furnace or in the hydrothermal reactor at 230 °C for 18h in NH4OH medium. UV-Vis diffuse reflectance spectra of the Bi2Ti2O7 samples showed that they exhibit the maximum absorption edge at ~420-440 nm. The UV-Vis diffuse reflectance measurements of Bi2Ti2O7 loaded with 10 wt. % of Ag as a co-catalyst showed an enhanced absorbance in the visible region, presumably due to a contribution of Local Surface Plasmon Resonance. The Bi2Ti2O7 nanoparticles are not photocatalytically active under the visible light irradiation without assistance of a sacrificial reagent. The photocatalytic activity does not increase even with Ag as a co-catalyst under visible light irradiation. All samples are active under UV light irradiation, especially the sample with Ag that is able to decolourize 7 mg/L of metyl orange in just 3 min of exposure to UV light. However, H2O2 as a sacrificial reagent increases the photocatalytic activity of Bi2Ti2O7 under visible light irradiation.
Phase pure pyrochlore Bi1.647Nb1.118Fe1.157O7 (BNF) nanoparticles were synthesized with coprecipitation reaction and further annealing in the furnace at 570 °C for 7h or 15h and in the hydrothermal reactor at 160 °C for 18h in 3 M or 6 M NaOH medium. The BNF materials exhibit shift toward longer wavelengths in absorbance of visible light (up to ~550-650 nm). This result confirmed that incorporation of Fe in the pyrochlore structure decreases the band gap. The BNF nanoparticles annealed for 7h showed intense photoactivity under visible light irradiation in the presence of a sacrificial reagent. The improved photoactivity, much better than with BNF, was shown for the composite nanoparticles BiOCl/BNF. They decolourize 100 % of the 7 mg/L methyl orange within only 2h of the visible light irradiation in the presence of H2O2.
Phase pure pyrochlore Bi1.9Te0.58Fe1.52O6.87 (BTF) nanoparticles were synthesised by coprecipitation reaction and further annealing in the furnace at 570 °C for 7h. Although the BTF nanoparticles include higher amount of Fe than BNF nanoparticles and exhibit narrower band gap, the photoactivity of these nanoparticles is a bit lower than that of BNF nanoparticles. We assume that Fe at some critical concentration causes formation of mid-band states, which act as recombination centers. The same as BiOCl/BNF, the BiOCl/BTF composite is able to decolourize 100 % of the 7 mg/L MO within 2h of the visible light irradiation in the presence of H2O2.
Based on the band gap determination and estimation of valence and conduction band levels, the proposed photodecolourization mechanisms are discussed. The conduction band levels of all synthesized materials lie more positively than O2/O2● redox potential (vs. negative hydrogen electrode potential), but are more close to H2O2/●OH redox potential. Thus, we assume that the photogenerated electrons form ●OH radicals, the species that induce dye decolourization under visible light irradiation. We believe that better performance of composite materials (BiOCl/BNF, BiOCl/BTF) is due to the formation of heterojunction, which facilitates the electron transfer between semiconductors, and O2 vacancy states formation in the BiOCl material.
Keywords: nanoparticles, pyrochlore structure, photocatalysis, visible light
Published: 26.06.2015; Views: 5489; Downloads: 138
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Novel applications of oxygenic photosynthetic organismsDanijel Stojković
, 2015, doctoral dissertation
Abstract: Inspired by natural microorganisms that possess a rigid cell wall to protect them in harsh conditions, individual cells of Chlamydomonas reinhardtii were artificially encapsulated with different materials and hydrogen production was enhanced.
The first attempt was to cover the cells with hydrated silicon dioxide, which is naturally formed by diatoms. The cells covered with silica were not able to produce hydrogen, but the improved TiO2-encapsualtion of Chlamydomonas reinhardtii was found to positively affect their hydrogen production under sulfur-deprived conditions. It was shown that incubation of the cells in the dark before exposure to light was necessary in order to overcome the toxic effects of the (RKK)4D8 catalytic peptide that is essential for TiO2 formation. The TiO2-encapsulated cells were able to produce H2 with about double efficiency during 5-day period compared to non-encapsulated cells. The light-to-H2 conversion efficiency of TiO2-encapsulated Chlamydomonas reinhardtii system was estimated to be more than 4 % under optimized conditions.
The encapsulation with platinum led us to discover the bioreductive properties of Chlamydomonas reinhardtii. Beside the homogeneous Pt reduction carried out by the algae, the most surprising discovery was the possibility to use algae culture for targeted heterogeneous nucleation. An important discovery was that is possible to control the nucleation mechanism and redirect predominantly homogeneous into fully heterogeneous nucleation.
Keywords: photosynthesis, H2 production, TiO2, encapsulation, Chlamydomonas reinhardtii, platinum reduction
Published: 01.04.2015; Views: 5585; Downloads: 197
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The impact of gravel extraction on hyporheic ecology: a case study of the Bača river (W Slovenia)Nataša Mori
, 2008, doctoral dissertation
Keywords: hyporheic invertebrate, Soča river, Bača river, hyporheic biota, benthic organisms, particulate organic matter, POM, fine sediment, ETS activity, electron transport system, sediments, Nematoda, Harpacticoida, Chironomidae, gravel extraction, environmental impact assessment
Published: 19.02.2015; Views: 3378; Downloads: 279
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