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1.
Preparation of porous [alpha]-Fe[sub]2O[sub]3 thin films for efficient photoelectrocatalytic degradation of basic blue 41 dye
Manel Machreki, Takwa Chouki, Mitja Martelanc, Lorena Butinar, Branka Mozetič Vodopivec, Saim Emin, 2021, original scientific article

Abstract: A novel method was developed for the preparation of porous hematite (α-Fe2O3) thin films. First, a solution containing iron precursor was spin-coated on fluorine-doped tin oxide substrate and later short heat-treated at 750 °C. The prepared α-Fe2O3 thin films were applied as dual-function catalyst in photoelectrochemical (PEC) water oxidation and textile dye degradation studies. For the first time, α-Fe2O3 thin films were used in efficient PEC degradation of a textile dye (Basic Blue 41 – B41) using in-situ generated reactive chlorine species. In comparison with photocatalytic and electrocatalytic approaches, the PEC technique allows faster degradation of B41 dye at an applied bias potential of 1.5 V versus reversible hydrogen electrode and under visible light illumination. In the presence of Cl− using the PEC approach the degradation of B41 reaches 99.8%. High-performance liquid chromatography coupled with UV–VIS system confirmed the degradation of B41 dye using PEC. Gas-chromatography coupled to mass spectrometry was used to study the by-products obtained during PEC degradation. Chemical oxygen demand analyses confirmed that the mineralization level of B41 is in the order of 68%. The α-Fe2O3 films developed in this study give a higher level of PEC degradation efficiency compared to other iron oxide-based systems.
Keywords: thin films, photoelectrocatalysis, kinetics, visible light, degradation, textile dye
Published in RUNG: 10.05.2021; Views: 2255; Downloads: 12
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2.
Bi2O3-BASED PYROCHLORE NANOSTRUCTURES AND THEIR CRYSTALLOGRAPHIC, OPTOELECTRONIC AND PHOTOCATALYTIC PROPERTIES
Metka 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 in RUNG: 26.06.2015; Views: 8755; Downloads: 210
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