Photocatalytic degradation of oxytetracycline using TiO2 under natural and simulated solar radiation

The main objective of the present study was to assess the photocatalytic degradation over TiO₂ of an aqueous solution containing 20 mg L⁻¹ of the antibiotic Oxytetracycline (OTC) using simulated solar radiation, seconded by a solar radiation experiment carried out in a pilot plant equipped with Compound Parabolic Collectors (CPCs) under the optimal conditions found in preliminary lab-scale experiments. These comprehended a set of 1 L aqueous experiments with TiO₂ loads ranging from 0.1 to 0.5 g L⁻¹ starting from different initial pH values. These experiments were carried out in a Solarbox equipped with a 1000 W Xe-OP lamp. OTC degradation was followed by HPLC-DAD, while its mineralization was followed by the removal of Total Organic Carbon.Results suggested that 0.5 g L⁻¹ of TiO₂ with no initial pH adjustment (pH ∼ 4.4) was the best combination for the removal of both OTC (100% after 40 min of irradiation; 7.5 kJ L⁻¹ of UV dose) and TOC (>90% after 180 min of irradiation; 38.3 kJ L⁻¹ of UV dose). Under these conditions, the BOD₅/COD ratio rose from almost 0 to nearly 0.5, showing a remarkable improvement in biodegradability, while inhibition percentage of bioluminescence of Vibrio fischeri after 15 min of exposition measured by Microtox® decreased significantly from 35% down to 7%. A scheme of the OTC degradation pathway is proposed, based on the results obtained from this particular experiment.The solar photocatalytic experiment done under the same conditions was carried out in a solar pilot plant equipped with CPCs. OTC and TOC removal was followed as a function of accumulated UV energy entering the reactor. Results showed a 100% OTC and almost 80% TOC removal with 1.8 kJ L⁻¹ and 11.3 kJ L⁻¹ of photo treatment energy, respectively.     

Treatment of textile wastewaters by solar-driven advanced oxidation processes

Heterogeneous (TiO₂/UV, TiO₂/H₂O₂/UV) and homogenous (H₂O₂/UV, Fe²⁺/H₂O₂/UV) solar advanced oxidation processes (AOPs) are proposed for the treatment of recalcitrant textile wastewater at pilot-plant scale with compound parabolic collectors (CPCs). The textile wastewater presents a lilac colour, with a maximum absorbance peak at 516 nm, high pH (pH = 11), moderate organic content (DOC = 382 mg C L⁻¹, COD = 1020 mg O₂ L⁻¹) and high conductivity (13.6 mS cm⁻¹), associated with a high concentration of chloride (4.7 g Cl⁻ L⁻¹). The DOC abatement is similar for the H₂O₂/UV and TiO₂/UV processes, corresponding only to 30% and 36% mineralization after 190 kJ_UV L⁻¹. The addition of H₂O₂ to TiO₂/UV system increased the initial degradation rate more than seven times, leading to 90% mineralization after exposure to 100 kJ_UV L⁻¹. All the processes using H₂O₂ contributed to an effective decolourisation, but the most efficient process for decolourisation and mineralization was the solar-photo-Fenton with an optimum catalyst concentration of 100 mg Fe²⁺ L⁻¹, leading to 98% decolourisation and 89% mineralization after 7.2 and 49.1 kJ_UV L⁻¹, respectively. According to the Zahn-Wellens test, the energy dose necessary to achieve a biodegradable effluent after the solar-photo-Fenton process with 100 mg Fe²⁺ L⁻¹ is 12 kJ_UV L⁻¹.     

Bleaching and photodegradation of textile dyes by H2O2 and solar or ultraviolet radiation

The photooxidation of textile dyes Yellow Procion H-4R, Bright Blue Remazol (blue reagent-19), Red Procion H-E7B, and the mixture of the two last dyes were investigated. The efficiency of photooxidation were compared using hydrogen peroxide (30%) as a bleaching reagent, solar and ultraviolet radiation, common glass borosilicate, quartz assay tubes, and no solid catalysts. The colour of blue dye and a mixture of blue and red dyes were almost completely removed after 3 h, either by solar or ultraviolet radiation. The best results of colour removal (93%) for the red and yellow dyestuffs were obtained only after 6 h, using quartz tubes, hydrogen peroxide and ultraviolet radiation. Using non-parametrical statistical tests (χ²), the treatment showed significant differences among the processes investigated (P<0.01).     

Photoelectrocatalytic generation of H2 and S from toxic H2S by using a novel BiOI/WO3 nanoflake array photoanode

In this paper, a photoelectrocatalytic (PEC) recovery of toxic H₂S into H₂ and S system was proposed using a novel bismuth oxyiodide (BiOI)/ tungsten trioxide (WO₃) nano-flake arrays (NFA) photoanode. The BiOI/WO₃ NFA with a vertically aligned nanostructure were uniformly prepared on the conductive substrate via transformation of tungstate following an impregnating hydroxylation of BiI₃. Compared to pure WO₃ NFA, the BiOI/WO₃ NFA promotes a significant increase of photocurrent by 200%. Owing to the excellent stability and photoactivity of the BiOI/WO₃ NFA photoanode and I^–/{\mathrm{I}}_{\mathrm{3}}^{-} catalytic system, the PEC system toward splitting of H₂S totally converted S^2– into S without any polysulfide ({\mathrm{S}}_x^{n-}) under solar-light irradiation. Moreover, H₂ was simultaneously generated at a rate of about 0.867 mL/(h·cm). The proposed PEC H₂S splitting system provides an efficient and sustainable route to recover H₂ and S.     

CO2 and H2O reduction by solar thermochemical looping using SnO2/SnO redox reactions: Thermogravimetric analysis

The thermochemical dissociation of CO₂ and H₂O from reactive SnO nanopowders is studied via thermogravimetry analysis. SnO is first produced by solar thermal dissociation of SnO₂ using concentrated solar radiation as the high-temperature energy source. The process targets the production of CO and H₂ in separate reactions using SnO as the oxygen carrier and the syngas can be further processed to various synthetic liquid fuels. The global process thus converts and upgrades H₂O and captured CO₂ feedstock into solar chemical fuels from high-temperature solar heat only, since the intermediate oxide is not consumed but recycled in the overall process. The objective of the study was the kinetic characterization of the H₂O and CO₂ reduction reactions using reactive SnO nanopowders synthesized in a high-temperature solar chemical reactor. SnO conversion up to 88% was measured during H₂O reduction at 973 K and an activation energy of 51 ± 7 kJ/mol was identified in the temperature range of 798-923 K. Regarding CO₂ reduction, a higher temperature was required to reach similar SnO conversion (88% at 1073 K) and the activation energy was found to be 88 ± 7 kJ/mol in the range of 973-1173 K with a CO₂ reaction order of 0.96. The SnO conversion and the reaction rate were improved when increasing the temperature or the reacting gas mole fraction. Using active SnO nanopowders thus allowed for efficient and rapid fuel production kinetics from H₂O and CO₂.     

Decolouration of textile dyes in wastewaters by photocatalysis with TiO2

The photocatalytic removal of colour of a synthetic textile effluent, using TiO₂ suspensions under solar radiation, has been studied at pilot plant scale. A synthetic dye solution was prepared by a mix of six commercial textile dyes. A photochemical reactor of parallel CPC reflectors with UV-transparent tubular receivers was used. The study of photodegradation was carried out using the Taguchi’s parameter design method. Following this methodology, the reaction was conducted under different flow conditions, pH and H₂O₂ concentrations. The results show that all dyes used in the experiences can be degraded successfully by photo-oxidation. The process shows a significant enhancement when it is carried out at high flows, alkaline media and high H₂O₂ concentration. Colour removal from the effluent was reached at 55 min operating time.     

Electrochemically-tuned luminescence of a [Ru(bpy)2(tatp)]-sensitized TiO2 anode and its applications to photo-stimulated guanine/H2O2 fuel cells

A phenazine-containing Ru(II) complex [Ru(bpy)₂(tatp)]²⁺ (bpy = 2,2′-bipyridine and tatp = 1,4,8,9-tetra-aza-triphenylene) is first applied to a modification of the nano-TiO₂/indium-tin oxide (ITO) electrode by the method of repetitive voltammetric sweeping. The resulting [Ru(bpy)₂(tatp)]²⁺-modified TiO₂ electrode shows two pairs of well-defined redox waves and excellent electrocatalytic activity for the oxidation of guanine. [Ru(bpy)₂(tatp)]²⁺ on TiO₂ surfaces exhibits intense absorbance and photoluminescence in visible region, revealed by absorption spectra, emission spectra and fluorescence microscope. While [Ru(bpy)₂(tatp)]²⁺-sensitized TiO₂ is functionalized as an anode to combine with a continuous wave green laser via an optical microscope, the luminescence of Ru(II)-based excited states can be enhanced by the oxidation of guanine. Furthermore, the [Ru(bpy)₂(tatp)]²⁺-sensitized TiO₂ electrode is used as photoanode and hemoglobin-modified single-walled carbon nanotubes (SWCNTs) as cathode for the elaboration of a photo-stimulated guanine/H₂O₂ fuel cell with a saturated KCl salt-bridge. It becomes evident that the photo-stimulated fuel cell performance depends strongly on the excited states of Ru(II) complex-sensitized anodes as well as the electrocatalytic oxidation of guanine. This study provides an electrochemically-tuned luminescence method for better evaluating contributions of the sensitizer excited states to photo-stimulated fuel cells.     

Effect of H2O2 on Pt electrode dissolution in H2SO4 solution based on electrochemical quartz crystal microbalance study

The effect of H₂O₂ on the Pt dissolution in 0.5 mol dm⁻³ H₂SO₄ was investigated using an electrochemical quartz crystal microbalance (EQCM). For the potential cycling at 50 mV s⁻¹, the Pt weight irreversibly decreases in a N₂ atmosphere with H₂O₂, while only a negligible Pt weight-loss is observed in the N₂ and O₂ atmospheres without H₂O₂. The EQCM data measured by the potential step showed that the Pt dissolution in the presence of H₂O₂ depends on the electrode potential and the H₂O₂ concentration. For the stationary electrolysis, the Pt dissolution occurs at 0.61–1.06 and 1.06–1.36 V vs. RHE. It should be noted that the Pt dissolution phenomenon in the presence of H₂O₂ is also affected by the potential scanning time. Based on these results, H₂O₂ is considered not only to contribute to the formation of Pt-oxide causing the cathodic Pt dissolution, but also to participate in the anodic Pt dissolution and the chemical Pt dissolution.     

Convenient storage of concentrated hydrogen peroxide as a CaO2·2H2O2(s)/H2O2(aq) slurry for energy storage applications

Prior investigations have proposed, and successfully implemented, a stand-alone supply of aqueous hydrogen peroxide for use in fuel cells. An apparent obstacle for considering the use of aqueous hydrogen peroxide as an energy storage compound is the corrosive nature of the nominally required 50 wt.% maximum concentration. Here we propose storage of concentrated hydrogen peroxide in a high weight percent solid slurry, namely the equilibrium system of CaO₂·2H₂O₂(s)/H₂O₂(aq), that mitigates much of the risk associated with the storage of such high concentrations. We have prepared and studied surrogate slurries of calcium hydroxide/water that are assumed to resemble the peroxo compound slurries. These slurries have the consistency of a paste rather than a distinct two-phase (liquid plus solid) system. This paste-like property of the prepared surrogates enable them to be contained within a 200 lines-per-inch. (LPI) nickel mesh screen (33.6% open area) with no solids leakage, and only liquid transport driven by an adsorbent material is placed in physical contact on the exterior of the screen. This hydrogen peroxide slurry approach suggests a convenient and safe mechanism of storing hydrogen peroxide for use in, say, vehicle applications. This is because fuel cell design requires only aqueous hydrogen peroxide use, that can be achieved using the separation approach utilizing the screen material here. This proposed method of storage should mitigate hazards associated with unintentional spills and leakage issues arising from aqueous solution use.     

Study of Pt electrode dissolution in H2O2-containing H2SO4 solution using an electrochemical quartz crystal microbalance

Pt electrode dissolution has been investigated using an electrochemical quartz crystal microbalance (EQCM) in H₂O₂-containing 0.5 mol dm⁻³ H₂SO₄. The Pt electrode weight-loss of ca. 0.4 μg cm⁻² is observed during nine potential sweeps between 0.01 and 1.36 V vs. RHE. In contrast, the Pt electrode weight-loss is negligible without H₂O₂ (<0.05 μg cm⁻²). To support the EQCM results, the weight-decrease amounts of a Pt disk electrode and amounts of Pt dissolved in the solutions were measured after similar successive potential cycles. As a result, these results agreed well with the EQCM results. Furthermore, the H₂O₂ concentration dependence of the Pt weight-decrease rate was assessed by successive potential steps. These EQCM data indicated that the increase in H₂O₂ accelerates the Pt dissolution. Based on these results, H₂O₂ is known to be a major factor contributing to the Pt dissolution.     

Thermochemical two-step water splitting by ZrO2-supported NixFe3−xO4 for solar hydrogen production

A thermochemical two-step water-splitting cycle using a redox metal oxide was examined for Ni(II) ferrites or Ni_xFe_3−xO₄ (0  x  1) for the purpose of converting solar high-temperature heat to hydrogen. The Ni(II) ferrite was decomposed to Ni-doped wustite (Ni_yFe_1−yO) at 1400 °C under an inert atmosphere in the first thermal-reduction step of the cycle; it was then reoxidized with steam to generate hydrogen at 1000 °C in the second water-decomposition step. Although nondoped Fe₃O₄ powders formed a nonporous, dense mass of iron oxide by the fusion of FeO and its subsequent solidification after the thermal-reduction step, Ni(II)–ferrite powders were converted into a porous, soft mass after the step. This was probably because Ni doping in the FeO phase raised the melting point of wustite above 1400 °C. Supporting the Ni(II) ferrites on m-ZrO₂ (monoclinic zirconia) alleviated the high-temperature sintering of iron oxide; as a result, the supported ferrites exhibited greater reactivity and assisted the repeatability of the cyclic water splitting process as compared to the unsupported ferrites. The reactivity increased with the doping value x, and was maximum at x = 1.0 in the Ni_xFe_3−xO₄/m-ZrO₂ system.     

Cu(In,Ga)Se2 solar cells with superstrate structure using lift-off process

Cu(In,Ga)Se₂ (CIGS) solar cells with a superstrate structure were fabricated using a lift-off process. To widen the variety of substrate choices for CIGS solar cells, a lift-off process was developed without an intentional sacrificial layer between the CIGS and Mo back-contact layers. The CIGS solar cells fabricated on Mo/soda-lime glass (SLG) were transferred to an alternative SLG substrate. The conversion efficiency of the CIGS solar cells with the superstrate structure was 5.1%, which was almost half that of the CIGS solar cells with a substrate structure prior to the lift-off process. The low conversion efficiency was caused by the high series resistance and low shunt resistance, which would be due to the junction resistance between the CIGS/back contact and cracks introduced during the lift-off process, respectively.     

CuIn(Ga)Se2-based devices via a novel absorber formation process

A novel pathway for the formation of copper–indium (gallium) diselenide has been developed. This two-stage process consists of (a) the formation of Cu–In–(Ga)–Se precursors, and (b) subsequent thermal treatment to form CuIn(Ga)Se₂. The morphology, structure and growth mechanism for several different precursor structures prepared under various conditions were studied and correlated to the deposition parameters as well as the structure and morphology of the annealed films. Photovoltaic devices prepared from CuInSe₂ and CuIn_0.75Ga_0.25Se₂ resulted in efficiencies of 10% and 13%, respectively.     

Inactivation of Clostridium perfringens spores and vegetative cells by photolysis and TiO2 photocatalysis with H2O2

Due to public health concerns related to the generation of dangerous by-products from conventional systems of water disinfection, innovative technologies based on the generation of oxidant radicals are being developed. The aim of this work is to evaluate the bactericidal activity of different treatments with light (λ: 320-800 nm), TiO₂ (1 g L⁻¹) and H₂O₂ (0.04 mM) on the viability of vegetative cells and spores of Clostridium perfringens. After spiking a natural water sample (from the Ebro River, Zaragoza (Spain)), the population of vegetative cells was of 10⁸ CFU·100 mL⁻¹ and of spores about 10³ CFU·100 mL⁻¹. Treatments without radiation source (TiO₂, H₂O₂, TiO₂/H₂O₂) show a poor level of inactivation (<0.5 log) on both bacterial forms. The light treatment achieves a vegetative cell inactivation of 1.2 log after 5 min of treatment and <0.5 log on spores after 30 min. The combined light/TiO₂ system increases the level of disinfection with a vegetative cell removal in the order of 6 log after 5 min and 0.6 log of spores after 5 min. Light/H₂O₂ and light/TiO₂/H₂O₂ treatments also significantly increase the disinfection of vegetative cells of C. perfringens (>6 log). Regarding spores, light/H₂O₂ and light/TiO₂/H₂O₂ treatments achieve constant inactivation of 1 log after 5 min of treatment. The application of a light/TiO₂/H₂O₂ treatment does not increase the level of inactivation with regard to the level reached by the light/TiO₂ and light/H₂O₂ systems. This fact shows there is no a significant interaction between TiO₂ and H₂O₂ under the conditions studied.     

Ga homogenization by simultaneous H2Se/H2S reaction of Cu-Ga-In precursor

The compositional distribution of Ga and S in Cu(InGa)(SeS)₂ films fabricated by a simultaneous selenization and sulfization process was systematically investigated. At low H₂Se/H₂S reaction temperature (490 °C), most Ga remains at the back of the film adjacent to the Mo back contact. However, the Ga/III ratios at the top and bottom of the Cu(InGa)(SeS)₂ layer monotonically increase and decrease with reaction temperatures, respectively. At T>550 °C, homogeneous distribution of elemental Ga and In through film is achieved. Further increase of the reaction temperature (e.g., T>550 °C) causes phase segregation on the surface of the Cu(InGa)(SeS)₂ film confirmed by XRD, GIXRD and EDS analysis.     

Structure and optical properties of Ag-Al2O3 nanocermet solar selective coatings prepared using unbalanced magnetron sputtering

Ag-Al₂O₃ nanocermet spectrally selective solar absorber coatings were prepared at different Ag contents on copper, silicon and glass substrates using unbalanced magnetron sputtering technique. Asymmetric bipolar pulsed direct current power supply and radio frequency power supply were used to sputter Ag and Al₂O₃ targets, respectively. The optimized coating exhibited high absorptance (α=0.93) in the visible region and low emittance (ε=0.04-0.05 at 82 °C) in the infrared region of the solar spectrum. Presence of the strong absorption band in the absorber coating is due to the surface plasmon resonance, i.e., collective oscillation of the conduction band electrons under the influence of the optical excitation. Atomic force microscopy, field emission scanning electron microscopy (FESEM), X-ray diffraction, micro-Raman spectroscopy, spectroscopic ellipsometry and spectrophotometer were used to characterize the nanostructure, composition and optical properties of these coatings. The face centered cubic crystalline structure of Ag nanoparticles inclusion in the amorphous alumina dielectric matrix was confirmed using X-ray diffraction. The size distribution and concentration of Ag nanoparticles embedded in Al₂O₃ dielectric matrix was studied using FESEM image analysis. The variations of refractive index and extinction coefficient with wavelength were obtained using phase modulation spectroscopic ellipsometry. The variation of absorption with wavelength in the UV-vis region was characterized using spectrophotometer. In order to study the thermal stability of the absorber coatings, they were annealed in vacuum at different temperatures (i.e., 200-400 °C) for 2 h. For the vacuum annealed coatings (heated up to 400 °C), chemical/micro-structural changes were studied using micro-Raman spectroscopy and FESEM. No shift in the Raman peaks for the Al₂O₃ was observed, confirming its structural stability in the absorber coatings with annealing in vacuum up to 400 °C. However, FESEM image analysis confirmed that the degradation in the vacuum annealed coatings was due to defragmentation of the Ag nanoparticles.     

Reactive ceramics of CeO2–MOx (M=Mn,Fe, Ni,Cu) for H2 generation by two-step water splitting using concentrated solar thermal energy

The addition of MO_x (M: di- or tri-valent transition metal ion) into cerium dioxide (CeO₂) enhanced the ability of CeO₂ for the oxygen (O₂)-releasing reaction at lower temperature and swift hydrogen (H₂)-generation reaction. CeO₂–MO_x (M=Mn, Fe, Ni, Cu) reactive ceramics having high melting points were synthesized with the combustion method from their nitrates for solar H₂ production. The prepared CeO₂–MO_x samples were solid solutions between CeO₂ and MO_x with the fluorite structure through the X-ray diffractometry measurement. Two-step water-splitting reactions with CeO₂–MO_x reactive ceramics proceeded at 1573–1773 K for the O₂-releasing step and at 1273 K for the H₂-generation step by irradiation of infrared image furnace as a solar simulator. The amounts of O₂ evolved in the O₂-releasing reaction with CeO₂–MO_x increased with an increase in the reaction temperature. The amounts of H₂ evolved in the H₂-generation reaction with CeO₂–MO_x systems except for M=Cu were more than that of CeO₂ system after the O₂-releasing reaction at the temperatures of 1673 and 1773 K. The amounts of H₂ evolved in the H₂-generation reaction with CeO₂–MnO and CeO₂–NiO systems were more than those of CeO₂–Fe₂O₃, CeO₂–CuO and CeO₂ systems after the O₂-releasing reaction at the temperature of 1573 K. The amounts of evolved H₂ after the O₂-releasing reaction at the temperature of 1773 K in cm³ per gram of CeO₂–MO_x were 0.975–3.77 cm³/g. The O₂-releasing reaction at 1673 K and H₂-generation reaction at 1273 K with CeO₂–Fe₂O₃ proceeded with repetition of 4 times stoichiometrically.     

Oxygen-releasing step of ZnFe2O4/(ZnO + Fe3O4)-system in air using concentrated solar energy for solar hydrogen production

The oxygen-releasing step of the ZnFe₂O₄/(ZnO + Fe₃O₄)-system for solar hydrogen production with two-step water splitting using concentrated solar energy was studied under the air-flow condition by irradiation with concentrated Xe lamp beams from a solar simulator. The spinel-type compound of ZnFe₂O₄ (Zn-ferrite) releases O₂ gas under the air-flow condition at 1800 K and then decomposes into Fe₃O₄ () and ZnO with a nearly 100% yield (ZnFe₂O₄ = ZnO + 2/3Fe₃O₄ + 1/6O₂). The ZnO was deposited as the thin layer on the surface of the reaction cell wall. A thermodynamic study showed that the ZnO was produced by the reaction between the O₂ gas in the air and the metal Zn vapor generated from ZnFe₂O₄. With the combined process of the present study on the O₂-releasing step and the previous one on the H₂ generation step (ZnO + 2/3Fe₃O₄ + 1/3H₂O = ZnFe₂O₄ + 1/3H₂) for the ZnFe₂O₄/(ZnO + Fe₃O₄)-system, solar H₂ production was demonstrated by one cycle of the ZnFe₂O₄/(ZnO + Fe₃O₄)-system, where the O₂-releasing step had been carried out in air at 1800 K and the H₂ generation step at 1100 K.     

Reduction characteristics of CuFe2O4 and Fe3O4 by methane; CuFe2O4 as an oxidant for two-step thermochemical methane reforming

The reduction characteristics of CuFe₂O₄ and Fe₃O₄ by methane at 600–900 °C were determined in a thermogravimetric analyzer for the purpose of using CuFe₂O₄ as an oxidant of two-step thermochemical methane reforming. It was found that the addition of Cu to Fe₃O₄ largely affected the reduction kinetics and carbon formation in methane reduction. In the case of CuFe₂O₄, the reduction kinetics was found to be faster than that of Fe₃O₄. Furthermore, carbon deposition and carbide formation from methane decomposition were effectively inhibited. In case of Fe₃O₄, Fe metal formed from Fe₃O₄ decomposed methane catalytically, that lead to the formation of graphite and Fe₃C phases. It is deduced that Cu in CuFe₂O₄ enhanced reduction kinetics, decreased reduction temperature and prevented carbide and graphite formation. Additionally, methane conversion and CO selectivity in the syngas production step with CuFe₂O₄ were in the range of 33.5–55.6% and 54.9–59.6%, respectively.