Designing and operating a pilot plant for purification of industrial wastewater from toxic organic compounds by utilizing solar energy

The aim of the present project was to design and operate a solar reactor system and to analyze its performance for the removal of different types of toxic organic pollutants (e.g., synthetic methyl violet dye and phenol) from water with titanium dioxide as the photocatalyst. Various operating parameters were studied to investigate the behavior of the designed reactor like initial substrate concentration, loading of catalyst, pH of solution, and H₂O₂ concentration. The operating parameters were optimized to give higher efficiency to the reactor performance. Results showed that a photocatalysis system, operating at optimum conditions, offered within one hour of operation degradation up to 95.27% for synthetic dye, while a conversion of 99.95% was obtained in three hours. With phenol, degradation was up to 80.0% and 98.0%, respectively. The removal of TOC for the two toxic materials was also at high levels. This confirmed the feasibility of the designed solar system. The kinetics of dye degradation was first order with respect to dye concentration and could be well described by Langmuir-Hinshelwood model. A preliminary design of a solar photocatalysis system as an alternative treatment method for wastewater effluents from an Iraqi textile mill was introduced.     

Probing the spectrally selective property of NbB2-based tandem absorber coating for concentrated solar power application

Solar selective coating with good thermal stability is the primary requirement for a concentrated solar power (CSP) plant to function with better photothermal efficiency. In recent years, ultra-high-temperature ceramic-based coatings have been explored as potential materials for solar selective coatings. In this context, NbB₂/Nb(BN)/Al₂O₃ tandem absorber coating was designed to be fabricated on a stainless-steel substrate by the radio frequency magnetron sputtering of spark plasma sintered ceramic target. In the bulk form, the NbB₂ ceramic exhibits high solar absorptance (α = 0.756) and thermal emissivity (ε = 0.43), whereas the amorphous single NbB₂ coating exhibits α/ε = 0.716/0.13. Reactive sputtering of NbB₂ in nitrogen produced a semi-transparent coating with an optical bandgap of ∼2.80 eV and was used as the secondary absorber layer. Raman and X-ray photoelectron spectroscopy analyses reveal mild oxygen incorporation in the absorber layers. The developed SS/NbB₂/Nb(BNO)/Al₂O₃ tandem absorber exhibits a good solar absorptance of 0.950 and a moderate thermal emissivity of 0.15 at room temperature. The coatings exhibited good thermal stability when heated in vacuum for 5 h up to 700°C, and the selectivity (α/ε) remains above 6. The present work shows the possibility of exploring NbB₂-based tandem absorber coatings for CSP applications.     

Fabrication of Sb2S3 thin films by sputtering and post-annealing for solar cells

The semiconductor antimony sulfide (Sb₂S₃) is a potential absorber materials for the top sub-cell of Si-based tandem solar cells because of its appropriate band-gap, simple binary composition, nontoxic elements, and long-term stability. In this study, polycrystalline Sb₂S₃ films were fabricated by post-annealing of radio frequency (RF) magnetron sputtered precursors using an Sb2S3 target. The effects of the post-annealing temperature and atmosphere on Sb₂S₃ film properties and device performances were investigated. A high-performance device having a 2.41% power conversion efficiency was obtained by making use of a uniform Sb2S3 absorber layer. This preliminary experimental study shows that Sb2S3 thin films could be used as top sub-cell absorber materials for third-generation high efficiency, stable, and environmentally friendly Sb₂S₃/Si tandem solar cells.     

Adsorption characteristics of Ru(II) dye on carbon nanotubes for organic solar cell

We present a study on the adsorption properties of ruthenium(II) dye (Ru(II) dye) on multi-walled carbon nanotubes (MWNTs). To fabricate dye sensitized solar cells (DSCs) using dye coated MWNTs, we have developed a method to form covalently linked adducts of MWNTs and Ru(II) dye. MWNTs were functionalized by sonication in hydrogen peroxide solution. Ru(II) dye can be attached to the functionalized MWNTs by a synthetic route using Thionyl chloride (SOCl₂) followed by ethylenediamine. The adsorption characteristics were affected by parameters such as chemical oxidation of MWNTs, sonication process, processing temperature and time. The amount of adsorbed Ru(II) dye was effectively affected by treatment temperature of SOCl₂ than any other parameters.     

Semi-transparent thin film solar cells by a solution process

Easily processed, low cost, and highly efficient solar cells are desirable for photovoltaic conversion of solar energy to electricity. We present the fabrication of precursor solution processed CuInGaS2 (CIGS) thin film solar cells on transparent indium tin oxide (ITO) substrates. The CIGS absorber film was prepared by a spin-coating method, followed by two successive heat treatment processes. The first annealing process was on a hot plate at 300 °C for 30 min in air to remove carbon impurities in the film; this was followed by a sulfurization process at 500 °C in an H₂S(1%)/Ar environment to form a polycrystalline CIGS film. The absorber film with an optical band-gap of 1.52 eV and a thickness of about 1.1 µm was successfully synthesized. Because of the usage of a transparent glass substrate, a bifacial CIGS thin film device could be achieved; its power conversion efficiency was measured to be 6.64% and 0.96% for front and rear illumination, respectively, under standard irradiation conditions.     

Thermal stress durability and optical characteristics of a promising solar air receiver based black alumina ceramics

In solar thermal technology, solar receiver materials with high solar absorptivity and photocatalytic efficiency have recently become a mandatory requirement for promoting and maximizing the released thermal and electrical energy. This paper presents a detailed study of the optical performance and thermal stress durability of the promising solar receiver material, black Al₂O₃/CuO ceramics. Different Al₂O₃/CuO ceramics with different CuO content (10–40 wt%) were obtained by the pressureless sintering method. Optical properties such as solar absorbance and reflectance, band gap energy and photoluminescence are inclusively investigated. The thermal stress resistance of the obtained ceramic receivers is simulated using the finite element modeling (FEM) method at different temperatures. Results indicated that adding and increasing the content of CuO to Al₂O₃ has a significant role in transforming alumina from a non-solar light-absorbed material to a solar absorber material with high absorptivity in the Ultraviolet–Visible-Near Infrared (UV-VIS-NIR) spectrum. Composite with 40 wt% CuO has recorded the maximum absorbance of 75% in the visible light region. Moreover, Al₂O₃/CuO ceramics gave multiple graded band-gaps in the range of (1.6–5 eV). Composites with high wt% of CuO have the most increased photocatalytic activity and light emissivity efficiency. Thermal stress analysis of the different ceramics showed outstanding stress durability with uniform heat distribution. Hence, black Al₂O₃/CuO ceramics can be considered ideal solar absorber materials with high sustainability and durability at high temperatures.     

A comparative study of thermal conductivity and thermal emissivity of high temperature solar absorber of ZrO2 /Fe2O3 and Al2O3/CuO ceramics

Oxide ceramics are considered as promising high temperature solar absorber materials. The major aim of this work is the development of a new solar absorber material with promising characteristics, high efficiency and low-cost processing. Hence, this work provides a comparative and inclusive study of densification behavior, microstructure features, thermal emissivity and thermal conductivity values of the two new high temperature solar absorbers of ZrO₂/Fe₂O₃ and Al₂O₃/CuO ceramics. Ceramic composites of ZrO₂/(10–30 wt%) Fe₂O₃ and Al₂O₃/(10–30 wt%) CuO were prepared by pressureless sintering method at a temperature of 1700 °C/2hrs. Identification of the solar to thermal efficiency of the composites was evaluated in terms of their measured thermal emissivity. Thermal efficiency and heat transfer homogeneity were investigated in terms of thermal conductivity and diffusivity measurement. The results showed that both composites exhibited comparable densification behavior, homogenous and harmonious microstructure. However, Al₂O₃/10 wt% CuO composite showed higher thermal and solar to thermal efficiencies than ZrO₂/Fe₂O₃ composites. It gave the lowest and the best thermal emissivity of 0.561 and the highest thermal conductivity of 15.4 W/m. K. These values proved to be the best amongst all those of the most known solar absorber materials made from the expensive SiC and AlN ceramics. Thus, Al₂O₃/CuO composites have succeeded in obtaining outstanding properties at a much lower price than its other competitive materials. These results may strongly identify Al₂O₃/CuO composites as promising high-temperature solar absorber materials instead of ZrO₂ and the other carbide and nitride ceramics.     

Synthesis of pyridine derivatives and their influence as additives on the photocurrent of dye-sensitized solar cells

New kinds of additive, 4-alkyloxypyridne derivatives, were synthesized by introducing an alkyloxy group into the 4-position of 2-methylpyridine. The influence of these electrolyte additives on the short-circuit photocurrent (J _sc) of dye sensitized solar cells was investigated by combining electrochemical and spectral techniques. With the addition of pyridine derivatives to the electrolyte, a decrease in the rate of dye regeneration was observed by laser flash photolysis measurements and cyclic voltammetry, whereas, measurement of electrochemical impedence spectra showed an increase in the charge transfer resistance due to the formation of a complex between the pyridine derivatives and iodine, as identified by an absorption peak around 378 nm in the UV–Vis spectra. This leads to a decrease in J _sc of dye-sensitized solar cells. This adverse effect on the J _sc can be attributed to reaction or coordination between the dye cations and the iodine in the electrolyte.     

太阳能电絮凝技术在水处理中的研究进展

太阳能电絮凝技术（SPEC）是一种水处理新技术,其结合了太阳能光伏发电可再生、可持续的特点和电絮凝处理废水无需添加化学药剂、产泥量少、设备易操作、占地小的优势,为太阳能丰富的地区带来了更加高效、环保和节能的水处理方法。本文阐明了电絮凝的原理,并分析了阳极材料、电极连接方式、电流密度、初始pH、电导率和极板间距对废水中污染物去除效率的影响。随后,重点综述了国内外学者对SPEC技术处理染料废水、含磷废水、含油废水、偏远地区分散式废水和SPEC与其他技术耦合处理废水的研究进展。最后,点明了SPEC技术当前存在的不足及挑战,并对未来的研究方向提出了展望。     

Angular absorptance and thermal degradation analysis of TiB2/Ti(B,N)/SiON/SiO2 multilayer solar absorber coating

Multilayer solar selective absorber coatings have been developed in the last few decades. The thermal stability in terms of microstructure gives an insightful understanding of the optical properties of such coatings. In this context, we extensively utilized transmission electron microscopy (TEM) analysis to establish the thermal stability of TiB₂/Ti(B,N)/SiON/SiO₂ coating, under thermal cycling/continuous heating to 500°C in vacuum for 250 h. In particular, this work reports the variation in the solar absorptance of TiB₂/Ti(B,N)/SiON/SiO₂ coating with different angles of incidence of the solar radiation. Extensive analysis using the TEM technique reveals the presence of oxide interlayers that act as diffusion barrier layers to enhance the thermal stability of the coating. Computational simulation using SCOUT software validates the measured reflectance spectrum of the developed multilayer coating. The minor changes in absorptance and emissivity after heat treatment in vacuum at 500°C, together with high solar absorptance over a broad angular variation, establish the potential application of TiB₂/Ti(B,N)/SiON/SiO₂ as a selective coating in concentrated solar power systems.     

Fly ash supported photocatalytic nanocomposite poly(3,4‐ethylenedioxythiophene)/TiO2 for azo dye removal under simulated solar irradiation

The main objective of this study was to develop a supported photocatalyst for wastewater treatment with extended efficiency under solar light. For that purpose titanium dioxide (TiO₂) was immobilized by sol–gel synthesis on the surface of the waste fly ash (FA). On such prepared composite material, conductive polymer poly(3,4‐ethylenedioxythiophene) was grafted by in situ chemical oxidative polymerization with different oxidants, ammonium persulfate (APS), and iron(III) chloride, FeCl₃. Characterization was performed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, and gas sorption analysis. Photocatalytic activity of composite photocatalyst was evaluated by testing removal efficiency of C.I. Reactive Red 45 (RR45) azo dye in three consecutive photocatalytic cycles under different pH. Discoloration of RR45 was measured using UV/Vis spectroscopy. It was determined that oxidant type plays major role in structure of composite as sample synthesized with APS had higher fraction of polymer and largest pore volume. The same composite had much better photocatalytic efficiency than sample synthesized with FeCl₃ oxidant. It was also determined that there is a very strong adsorption of dye molecules on the surface of photocatalyst that quickly causes saturation of photocatalyst and efficiency drop after first cycle. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46316.     

TiO2-B narrow nanobelt/TiO2 nanoparticle composite photoelectrode for dye-sensitized solar cells

In order to possess the merits of both building blocks, i.e. the rapid interfacial electron transport of TiO₂-B narrow nanobelts (NBs) and the high surface area of TiO₂ nanoparticles (NPs), the TiO₂-B NBs and TiO₂ NPs composites photoelectrodes were prepared with different weight ratios. The dye-sensitized solar cell prototypes were fabricated based on the composite photoelectrodes and the photoelectrical properties have been systematically studied. Although the amount of adsorption dye of composite solar cells decreased, the composite cells could obtain higher power conversion efficiency compared to pure TiO₂ NP solar cell by rational tuning the weight ratio of TiO₂-B NBs and TiO₂ NPs, which was due to the faster electron transfer rate. The dye adsorption amount and interfacial electron transport, which together determined the overall photoelectrical conversion efficiency, were investigated by the UV–vis spectra, the electrochemical impedance spectra (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS).     

Degradation of disperse azo dyes from waters by solar photoelectro-Fenton

Solutions of the azo dyes Disperse Red 1 (DR1) and Disperse Yellow 3 (DY3), commonly used in the Chilean textile industry, in 0.1 mol dm⁻³ Na₂SO₄ and 0.5 mmol dm⁻³ Fe²⁺ of pH 3.0 were comparatively degraded by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) using a 2.5 dm³ recirculation flow plant containing a BDD/air-diffusion cell coupled with a solar photoreactor. Organics were oxidized in EF with hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between electrogenerated H₂O₂ and added Fe²⁺. The oxidizing power of SPEF was enhanced by the additional production of hydroxyl radicals from the photolysis of Fe(III) hydrated species and the photodecomposition of Fe(III) complexes with intermediates by UV light of solar irradiation. Total decolorization, complete dye removal and almost overall mineralization for both dye solutions were only achieved using the most potent SPEF process, yielding higher current efficiencies and lower energy consumptions than EF. Final carboxylic acids like pyruvic, acetic, oxalic and oxamic were detected during the SPEF treatments. NO₃⁻ ion was released as inorganic ion. The use of a solution pH of 2.0–3.0 at 50 mA cm⁻² was found preferable for SPEF. Synthetic textile dyeing solutions containing the dyes were treated under these conditions yielding lower decolorization rate, slower dye removal and smaller mineralization degree than only using 0.1 mol dm⁻³ Na₂SO₄ due to the parallel oxidation of organic dyeing components. However, lower energy consumptions were obtained by the destruction of more amounts of total organic carbon, indicating that SPEF is a useful and viable method for the remediation of textile industrial wastewaters with high contents of disperse azo dyes.     

Application of solar light for degradation of ammonia in petrochemical wastewater by a floating TiO2/LECA photocatalyst

In this study, photocatalytic degradation of ammonia in petrochemical wastewater was investigated by solar light/TiO₂ photocatalysis. The TiO₂ nanoparticles were used as photocatalysts which were immobilized on light expanded clay aggregate (LECA) granules as a new porous and light weight support. Maximum concentration of ammonia (975 mg/L) in petrochemical wastewater was selected, and to optimize the photocatalytic reaction, the effect of pH and catalyst dosage was investigated in two aerated and agitated reactor systems. Also, the morphology and chemical structure properties of the prepared catalysts were characterized by SEM and XRF analyses. The experimental results were shown that the performance of two types of aeration reactor systems was almost the same. Also, the ammonia removal efficiency was increased by increasing the pH value, and after solar light irradiation in three days, the solar reactor system lead degradation of ammonia in pH = 11–96.5%. The floating of photocatalyst can be reused at least three consecutive times with 14% decreases on the ammonia removal efficiency. The results suggest that the photocatalytic purification followed by solar photocatalytic reactor would be a promising method for the purification of chemical wastewater.     

Silica modification of titania nanoparticles for a dye-sensitized solar cell

Nanocomposites of commercially available titanium oxide (TiO₂) nanoparticles (P25) and a silane coupling agent, methacryloxypropyltrimethoxysilane (MPTS), were incorporated into a homogeneous porous material after UV treatment and heating at 450 °C in the air. A dye-sensitized solar cell utilizing this UV-polymerized MPTS-modified sample exhibited significant enhancements in total performance when compared with an analogous cell prepared without MPTS. The photovoltaic enhancement was mainly achieved due to a significant increase in photocurrent density. This improvement is believed to be caused by the increased contact achieved between the small nanoparticles when suspended in a homogeneous, multiporous structure, which in turn would optimize the paths for electron transport. The larger surface area and pore volume resulted in an increase in the dye uptake amount and in the fast redox activity of the electrolyte, enhancing dye regeneration. Furthermore, the measured diffuse reflectance indicated greater light scattering inside the TiO₂ multiporous structure.     

Application of CuCoMnO x coat by sol gel technique on aluminum and copper substrates for solar absorber application

Solar thermal heaters are used widely in domestic and industrial applications. The main part of solar thermal heaters is the absorber surface which must have a maximum absorptivity (α) and minimum emissivity (ε) of solar radiation. This is achieved by application of selective coating on the absorber surface. In the present work, solar selective CuCoMnO _x spinel films are deposited by sol gel technique using a dip-coating technique on copper and aluminum sheets. The precursor’s ratio Co:Cu:Mn applied is 1:3:3. Different precursor molar ratios were combined with a fixed amount of solvents for the coating process. Process parameters such as withdrawal rate, heat treatment, and substrate materials on the coat characteristics and optical properties were studied. The coated metallic samples were heat treated at 450°C for 30 min in the case of aluminum and at 200°C at different times in the case of copper. Optical properties of the coatings, namely absorptivity (α) and emissivity (ε) were measured and the deposition process parameters were optimized in order to produce the maximum selectivity (α/ε) values. The deposition parameters were found to influence both the thickness and surface roughness of the coatings. As the coating thickness decreases, the absorptivity increases while the emissivity decreases irrespective of the substrate material. It was also observed from the results that when applying the coat on aluminum substrates, a maximum selectivity value of (α/ε) = 31 was realized while for the copper substrates a maximum value of (α/ε) = 81.8 was obtained. The deposited coatings were analyzed using SEM, XRD, and AFM.     

Degradation of dye wastewater in a thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO2/Ti anode

A thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO₂/Ti anode was developed and successfully applied to degrade Rhodamine B (RhB) and textile effluent. Using a 5–150 mg L⁻¹ RhB solution as the model system, thin-film PEC removed total color and TOC by 99–28% and 78–15%, respectively, in 1 h, which is much higher than 82–7% and 60% to zero by conventional PEC. The enhanced treatment efficiency achieved by thin-film PEC process was attributed to the significantly reduced path length of irradiation light source. The wastewater was kept circulating during the experiments to timely refresh the aqueous film on the TiO₂/Ti anode and promote the mass transfer of the target pollutants and the degradation products in the bulk solution. The thin-film PEC reactor can degrade both simulated and real dye wastewater efficiently under UV light irradiation. Results suggested that thin-film PEC was particularly superior for treating a high concentration solution. The thin-film PEC reactor was also applied to treat RhB solution efficiently under solar light irradiation. The recycle experiments demonstrated excellent stability and reliability of the slant-placed TiO₂/Ti anode. This study proposed a simple and effective method to design PEC reactor applicable for industrial dye wastewater treatment.     

Characterization and evaluation of ZnO/CuO catalyst in the degradation of methylene blue using solar radiation

Catalysts based on the combination of zinc oxide and copper oxide were synthesized at a 80:20 mass ratio by the Pechini method and calcined at 500, 600 and 700 °C for 1 h. These catalysts were characterized by XRD, SEM, FT-IR, BET, UV-Vis, TGA and XRF. They were subsequently tested for the removal of methylene blue dye by means of heterogeneous catalysis combined with solar radiation through a RCCD experimental design, analyzing the concentrations of H₂O₂ and methylene blue, as well as radiation exposure time and pH. The average crystallite size obtained was of 26.21, 28.21 and 35.91 nm for the respective calcined samples. The XRF was effective in determining the elements present in the catalyst, consisting of 75% zinc oxide and 25% copper oxide. The values of surface area were of 7.54, 7.19 and 3.92 m²/g, respectively. The experimental design showed that the catalyst calcined at 500 °C exhibited the highest removal efficiency (93%) of methylene blue with a dye concentration of 20 mg/L. Despite the need to carry out new studies to optimize the process, results suggest that the application of solar photocatalysis in the treatment of methylene blue with ZnO/CuO is a feasible alternative.     

Application of a polymer heterojunction in dye-sensitized solar cells

Using a blend heterojunction consisting of a C₆₀ derivative, [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), and poly(3-hexylthiophene) (P3HT) as a charge carrier transfer medium to replace the I₃⁻/I⁻ redox electrolyte, a novel TiO₂/dye/PCBM/P3HT dye-sensitized solar cell was fabricated and characterized. It was found that the P3HT/PCBM heterojunction widened the incident light harvest range from ultraviolet to visible light, and improved the photoelectrical response of the dye-sensitized solar cell. We investigated the influence of the PCBM/P3HT ratio and barrier layer on the photoelectric performance of the solar cell and proposed optimized preparation conditions. The optimized solar cell with a barrier layer and PCBM/P3HT ratio of 1:2 had a short circuit current density of 5.52 mA cm⁻², an open circuit voltage of 0.87 V, a fill factor of 0.640 and a light-to-electric energy conversion efficiency of 3.09% under a simulated solar light irradiation of 100 mW cm⁻².     

A packed‐bed solar reactor for the carbothermal zinc production – dynamic modelling and experimental validation

Integration of concentrated solar energy into the pyrometallurgical Zn production process as clean source of high‐temperature process heat could significantly reduce fossil fuels consumption and its concomitant CO₂ emissions. The solar‐driven carbothermal reduction of ZnO is investigated using a 10‐kW_th solar reactor featuring two cavities, the upper one serving as the solar absorber and the lower one containing a packed‐bed of ZnO and beech charcoal as the biogenic reducing agent. Experimentation in a high‐flux solar simulator is carried out under radiative fluxes of 2300–2890 suns, yielding a peak solar‐to‐chemical energy conversion efficiency of 18.4%. The reactor performance under variable operating conditions is analyzed via a dynamic numerical model coupling heat transfer with chemical kinetics. The model is validated by comparison to the experimental data obtained with the 10‐kW_th packed‐bed solar reactor and further applied to predict the effect of incorporating semi‐continuous feeding of reactants on the process efficiency. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4586–4594, 2016