Photocatalytic Activity of Combustion Synthesized Nanocrystalline CeAlO3

The photocatalytic activity of combustion synthesized nanocrystalline CeAlO₃ was determined for the degradation of four anionic and four cationic dyes. The perovskite oxide showed high‐photocatalytic activity and a complete degradation of all the dyes was possible within 2 h. The photocatalytic activity of the compound was comparable with the activity of the commercial Degussa P‐25 TiO₂ catalyst. The degradation of dyes was found to follow first order kinetics and the first order degradation rate constants were determined.     

Solar Photocatalytic Decolorization and Detoxification of Industrial Batik Dye Wastewater Using P(3HB)‐TiO2 Nanocomposite Films

Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO₂) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO₂ removed 96% of the color under solar irradiation. P(3HB) and TiO₂, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO₂ film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.     

Development of Easy and Reproducible Immobilization Techniques Using TiO2 for Photocatalytic Degradation of Aquatic Pollutants

Two main routes of methods for the preparation of photocatalytic active titanium dioxide films on glass substrates were investigated: (1) the use of titanium dioxide powder and (2) the in situ generation of the catalyst via hydrolysis of titanium tetraisopropoxide (TTIP) or TiCl₄. The activities of the catalyst films were evaluated by measuring the degradation of dichloroacetic acid (DCA), clofibric acid, and terbuthylazine used as model organic compounds. The concentration decrease of DCA and the concentration increase of chloride ions as the decomposition product allowed to distinguish between photocatalytic degradation of DCA and adsorption onto the TiO₂ films. Furthermore, TiO₂ films of the commercially available materials P25 (Degussa) and Hombikat UV100 (Sachtleben Chemie) were used to investigate whether there was a difference in the degradation pathways of terbuthylazine as a model compound. For the experiments mini flow‐through reactors were constructed. The investigated immobilization techniques were easy to handle without need of any expensive equipment. All TiO₂ coatings showed good photocatalytic activities and mechanical stabilities with efficient long‐term stabilities. The best immobilization reproducibility was achieved by the spray coating technique and by the in situ method with the dipping sol‐gel process starting by TTIP. During the continuous use of the TiO₂ films no TiO₂ particles were found in the irradiated solutions.     

Supported TiO2 on Kaolin,Cordierite, and Calcite for Photocatalytic Removal of Dyes from Wastewater

Kaolin, cordierite, and calcite are investigated as supports for TiO₂. The prepared TiO₂/support samples are examined for the removal of organic dyes from wastewater. The samples are preliminarily investigated to identify the optimal loaded system using synthetic wastewater containing methylene blue (MB). Data indicate that the investigated support significantly affects the photocatalytic activity of the supported TiO₂. Low photocatalytic activity toward MB degradation is observed upon using TiO₂/calcite when compared to the unsupported TiO₂. Interaction between calcite and titania species probably occurrs to produce the less photoactive CaTiO₃ amorphous species. Anatase TiO₂ is obtained upon using kaolin and cordierite as supports. The low photocatalytic performance of the TiO₂/kaolin sample is also observed. A high concentration of MB on TiO₂/kaolin surfaces blocks the photoactive sites. TiO₂/cordierite shows the highest photocatalytic activity compared to the unsupported TiO₂ as well as the other TiO₂/support samples. Rigid cordierite particles suppress the agglomeration of TiO₂ particles during the preparation, leading to a high exposed surface of TiO₂ towards light illumination. TiO₂/cordierite is investigated for the removal of organic dye from real wastewater collected from a textile dyeing factory. Color removal of up to 46% is achieved upon UV irradiation.     

Photocatalytic Degradation of Dye C.I. Direct Blue 78 Using TiO2 Nanoparticles Immobilized on Recycled Wool‐Based Nonwoven Material

This paper discusses the possibility of immobilization of TiO₂ nanoparticles onto recycled wool‐based nonwoven material, which can be utilized for removal of dyes from wastewater. The photocatalytic activity of TiO₂ nanoparticles deposited on the nonwoven material was evaluated in the aqueous solution of direct dye C.I. Direct Blue 78 under the UV illumination. Nonwoven material modified with TiO₂ nanoparticles provides complete removal of dye from the solution already after 4–6 h of UV illumination. However, photodegradation of the dye adsorbed on the nonwoven material was obtained within 24 h of UV illumination. The rate of dye adsorption and photodegradation depends on the amount of deposited TiO₂ nanoparticles. The increase of initial dye concentration induced decrease in photocatalytic efficiency of immobilized TiO₂ nanoparticles. The highest photodegradation rate was achieved in acidic conditions. Elevated temperatures positively affected the removal of dye from solution. Photocatalytic activity of TiO₂ nanoparticles deposited on nonwoven material was preserved after three photodegradation cycles.     

A Comparative Study of Ozonation,Homogeneous Catalytic Ozonation,and Photocatalytic Ozonation for C.I. Reactive Red 194 Azo Dye Degradation

In this study, the decolorization, dearomatization, and mineralization efficiencies of different advanced oxidation processes (AOPs; namely O₃, O₃/Fe(II), O₃/Fe(II)/UVA, and O₃/TiO₂/UVA) were investigated for the azo dye C.I. Reactive Red 194 (RR194). The effects of pH (3–11), amount of TiO₂ (0.05–1 g/L), and concentration of Fe(II) (0.1–1.6 mM) were investigated for the applied methods. The decolorization and mineralization efficiencies of the photocatalytic ozonation system (O₃/TiO₂/UVA) were increased by decreasing the pH of the dye solution in contrast to the ozonation system (O₃). Decolorization of RR194 was increased in the photocatalytic ozonation system with an increasing amount of catalyst however, a decreasing was occurred for the homogeneous catalytic system (O₃/Fe(II)) when increasing the concentration of catalyst. The decolorization efficiency of the homogeneous catalytic system (O₃/Fe(II)) was enhanced when combined with UVA light. In our study, the most efficient method for dearomatization and mineralization was the O₃/TiO₂/UVA among the applied AOPs.     

Degradation of an Azo Dye with Homogeneous and Heterogeneous Catalysts by Sonophotolysis

This study illustrates the degradation of an azo dye, Reactive Yellow 81 (RY81), by the combined irradiation of UV‐C and ultrasound in the presence of homogeneous (Fe²⁺) and heterogeneous (TiO₂, ZnO) catalysts. The efficiency of homogeneous and heterogeneous oxidation systems was evaluated in regard of the decolorization and mineralization of RY81. Decolorization followed pseudo‐first‐order kinetics with homogeneous and heterogeneous catalysts. Complete color removal was accomplished by homogeneous sonocatalytic and sonophotocatalytic oxidation processes with apparent rate constants of 0.96 × 10^?3 and 46.77 × 10^?3 s^?1, respectively, in the presence of Fe²⁺. However, partial color removal was obtained by heterogeneous sonocatalytic, photocatalytic, and sonophotocatalytic oxidation processes with apparent rate constants of 2.32 × 10^?3, 3.60 × 10^?3, and 3.67 × 10^?3 s^?1, respectively, in the presence of ZnO. TiO₂ had the worst catalytic effect of all of the oxidation processes. The addition of hydrogen peroxide increased the rate constants of the heterogeneous oxidation processes and decreased the rate constants of the homogeneous oxidation processes. RY81 mineralization was 62.8% for the US/UV/Fe²⁺ homogeneous oxidation process, which was the best oxidation process, whereas it was 43.5% for the US/UV/ZnO/H₂O₂ heterogeneous oxidation process within 2 h reaction time.     

Optimization and Modeling of the Photocatalytic Degradation of the Insect Repellent DEET in Aqueous TiO2 Suspensions

Response surface methodology (RSM) and artificial neural networks (ANNs) based on a multivariate central composite design (CCD) were applied to model and optimize the photocatalytic degradation of N,N‐diethyl‐m‐toluamide (DEET). The individual and interaction effects of three main operating factors (mass of TiO₂, initial DEET concentration, and irradiation intensity) on process efficiency were estimated, proving their important effect on % DEET removal. Among the independent variables, TiO₂ concentration displayed the highest effect on DEET degradation followed by initial DEET concentration and UV intensity. The optimization and prediction capabilities of ANNs and RSM were compared on the basis of root mean squared error, mean absolute error, absolute average deviation, and correlation coefficient values. Results proved the usefulness and capability of the experimental design strategy for successful investigation and modeling of the photocatalytic process. Moreover, the selected ANN gave better estimation capabilities throughout the range of variables than RSM. Based on the models and the related experimental conditions, the optimal values of each parameter were determined. Under optimum conditions, DEET and total organic carbon (TOC) followed pseudo‐first order kinetics. Nearly complete degradation of DEET took place within 15 min whereas high TOC removal percentages (>85%) was achieved after 90 min irradiation time.     

Photocatalytic Decolorization Kinetics and Mineralization of Reactive Black 5 Aqueous Solution by UV/TiO2 Nanoparticles

The photocatalytic decolorization and mineralization of Reactive Black 5 (RB5) dye in presence of TiO₂ Degussa P25 has been studied using artificial light radiation in a shallow pond slurry reactor. The equilibrium adsorption of dye, influence of pH (3–11), catalyst load (0.5–3.0 g/L), and dye concentration (20–100 mg/L) on decolorization kinetics were studied. The effect of area to volume ratio of photoreactor on decolorization kinetics has been also studied. Mineralization studies were performed at optimized conditions of pH (3) and catalyst load (1.5 g/L). The maximum adsorption (26.5 mg/g) of dye was found to occur at pH 3. The apparent pseudo first order decolorization rate constant (k_app) value followed the order pH 3 > pH 11 > pH 9 > pH 7. As compared to available literature reduction in total organic carbon (TOC) was minimal by the time there was complete decolorization. Initial reduction in TOC was followed by subsequent increasing trend till complete decolorization. Final decreasing trend in TOC was observed only after complete decolorization. Twelve hours of treatment under experimental conditions reduced TOC content by 70% only. Discussion of results suggest that photocatalytic treatment of colored effluent under low UV intensity, and low A/V ratio may result in completely decolorized effluent but still having high COD.     

Degradation of Malathion and Parathion by Ozonation,Photolytic Ozonation,and Heterogeneous Catalytic Ozonation Processes

The oxidation of organophosphorus pesticides (OPPs), such as malathion and parathion, in aqueous solution was studied using conventional ozonation (O₃), photolytic ozonation (O₃/UV, O₃/UV/H₂O₂), and heterogeneous catalytic ozonation (O₃/TiO₂/UV) processes. Experiments were performed in batch mode at laboratory scale and processes were compared in terms of disappearance kinetics. The best results of pesticide mineralization were obtained when TiO₂ particles in combination with ozone (O₃) and UV photolysis (λ = 254 nm) were applied. Decomposition of 99% of parent compounds were achieved in 10 min and oxon derivatives were completely removed in 30 min. The initial reaction rate increases linearly with increasing catalyst amount. Toxicity measurements of the treated solutions were carried out in order to evaluate the efficiency of the treatment methods. No detoxification was achieved for O₃ and O₃/UV applications. Heterogeneous photocatalytic ozonation was shown to be feasible for achieving complete decomposition of OPPs and their oxon intermediates.     

Regeneration of Rhodamine B Loaded Modified Biosorbent by a Self‐Cleaning Eluent: TiO2 Hydrosol

Waste beer yeast was modified by pyromellitic dianhydride to improve its adsorption capacity for rhodamine B (RhB). Results showed that the adsorption capacity of the modified biomass for RhB was 600 mg g^?1, which was about five times than that obtained on the unmodified biomass. Dye loaded modified biomass was regenerated by (1) a common eluent: HNO₃ solution and (2) a self‐cleaning eluent: TiO₂ hydrosol, while the pH of both systems varied from 1 to 4. Desorption experimental results showed that low desorption rates were obtained in both systems after the first desorption cycle. A large volume of HNO₃ solution was needed to obtain high desorption rate, and a concentrated solution of RhB was left, which brought a secondary pollution. As a self‐cleaning eluent, acid TiO₂ hydrosol acted both as eluent and photocatalyst. The desorbed RhB could be photodegraded under sunlight irradiation and the same hydrosol could be used in the next desorption cycle without losing its activity, which could economize large volumes of solvent. The results showed an adsorption capacity of the regenerated biosorbent for RhB of 450 mg g^?1 by using hydrosol with pH 2 as eluent after four desorption/photodegradation cycles.     

Use of Chrysotile Fibres in the Degradation of Cationic and Nonionic Surfactants in Aqueous Solutions

It was previously observed that sodium dodecylbenzenesulfonate (SDBS) is degraded in the presence of chrysotile fibres. A higher catalytic efficiency was obtained than the reported values for TiO₂ under the same conditions. Chrysotile, a clay mineral fibre of low cost and relatively abundant, probably acts as a catalyst through an Advanced Oxidative Process (AOP) involving free radical formation. In this work, experiments with non‐ionic – Triton X‐45 (octil‐phenoxy polyethoxy ethanol) – and cationic – Herquat 3500 (alkyl dimethyl benzyl ammonium chloride) – surfactants were carried out. Diluted aqueous solutions (50 ppm) of these surfactants were kept in contact with chrysotile (4.0 g) in the dark at room temperature. The aromatic ring disappearance was followed through the absorbance peaks at 224 nm (Triton X‐45) and 208 nm (Herquat 3500) in the UV spectra. After 4 h, reductions in the surfactant solution concentration of 65.0% and 35.0% were observed for the Triton X‐45 and the Herquat 3500 surfactants, respectively. In both cases, reactions carried out without aeration showed a lower reduction of the aromatic ring concentration (30.0% less) when compared to the values obtained for the systems with airflow. The system containing the non‐ionic surfactant seems to achieve equilibrium after 2 h, what is not observed for the cationic surfactant system.     

Photocatalytic degradation of spill oils on TiO2 nanotube thin films

The nitrogen-doped TiO₂ nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623 K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNT h and 0.25 mg 1-hexadecene/gN-TNT h. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.     

Mineral chemistry and petrogenesis of chromitites from the Khoy ophiolite complex,Northwestern Iran: Implications for aggregation of two ophiolites

The Khoy ophiolitic complex in Northwestern Iran is a part of the Tethyan ophiolite belt, and is divided into two sections: the Eastern ophiolite in Qeshlaq and Kalavanes (Jurassic–Cretaceous) and the Western ophiolite in Barajouk, Chuchak and Hessar (Late Cretaceous). Our chromitites can be clearly classified into two groups: high‐Al chromitites (Cr# = 0.38–0.44) from the Eastern ophiolite, and high‐Cr chromitites (Cr# = 0.54–0.72) from the Western ophiolite. The chromian spinels in high‐Al chromitite include primary mineral inclusions mainly as Na‐bearing diopside and pargasite with subordinate rutile and their formation was probably related to reaction between a MORB (mid‐ocean‐ridge basalt)‐like melt with depleted harzburgite, possibly in a back‐arc setting. Their host harzburgites contain clinopyroxene with higher contents of Al₂O₃, Na₂O, Cr₂O₃, and TiO₂ relative to Western harzburgites and are possibly residue after moderate partial melting (~15 %) whereas the Western harzburgite is residue after high partial melting (~25 %). The chromian spinel in the Western Khoy chromitites contains inclusions such as clinopyroxene, olivine and platinum group mineral‐bearing sulfides. These Western chromitites were possibly formed at two stages during arc growth and are divided into the moderately high‐Cr# chromitites (Barajouk and Hessar) and the high‐Cr# chromitites (Chuchak A and C). The former crystallized from island‐arc‐tholeiite (IAT) melts during reaction with the host depleted harzburgites, whereas the latter crystallized from boninitic melts (second stage melt) during reaction with highly depleted harzburgite in a supra‐subduction‐zone environment. Based on the mineral chemistry of chromian spinels, pyroxenes, and mineral inclusions, the chromitites and the host peridotites from the Eastern and Western Khoy ophiolites were formed in a back‐arc basin and arc‐related setting, respectively. The Khoy ophiolitic complex is a tectonic aggregate of the two different ophiolites formed in two different tectonic settings at different ages.     

Photocatalytic Degradation of 17α‐Ethinylestradiol and Inactivation of Escherichia coli Using Ag‐Modified TiO2 Nanotube Arrays

Ag‐modified TiO₂ nanotube arrays (Ag/TiO₂ NAs) were prepared and employed as a photocatalyst for degradation of 17α‐ethinylestradiol (EE2) and inactivation of Escherichia coli. The as‐synthesized Ag/TiO₂ NAs were characterized by field‐emission scanning electron microscope (FESEM), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). It was found that metallic Ag nanoparticles were firmly deposited on the TiO₂ NAs with the pore diameter of 100 nm and the length of 550 nm. Photocatalytic degradation of EE2 and inactivation of E. coli were enhanced effectively in an analogical trend using Ag/TiO₂ NAs. In particular, Ag/TiO₂ NAs exhibited the antimicrobial activity even in the absence of light. The Ag acted as a disinfection agent as well as the dopant of the modified TiO₂ NAs photocatalysis by forming a Schottky barrier on the surface of TiO₂ NAs. Inorganic ions suppressed the rates of photocatalytic degradation of EE2, with HCO having a more pronounced effect than NO or SO. Humic acid (HA) was found to increase the rate of EE2 degradation.     

Post‐Synthesis of Ti‐SBA‐15 in Supercritical CO2‐Ethanol Solution

Ti‐SBA‐15 materials with Ti incorporated into the framework of SBA‐15 and controllable Ti contents were successfully prepared via a post‐treatment route in supercritical CO₂‐ethanol solution, followed by calcination. The resultant Ti‐SBA‐15 materials were characterized by means of different techniques including X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, IR analysis, and N₂ sorption analysis. It was demonstrated that the resultant materials retained a structure similar to that of the parent SBA‐15, and Ti was incorporated into the framework of SBA‐15. At high Ti content, i.e, Si/Ti = 5:1, a TiO₂ phase formed and was coated onto the inner surface of SBA‐15 in addition to the incorporation of the Ti in the framework. The BET surface areas of the Ti‐SBA‐15 samples decreased with increasing Ti content. The presence of small amounts of H₂O in the reaction medium may have resulted in some TiO₂ nanoparticles being uniformly distributed in the pores of the SBA‐15 accompanying the incorporation of Ti in the SBA‐15 framework.     

Assessment of the effectiveness of combined adsorption and photocatalysis for removal of the herbicide isoproturon

The aim of this research was to decompose isoproturon and adsorb its photoproducts by developing a carbon material from a juice industry waste. Carbon-TiO₂ hybrid materials were obtained by impregnating carbonized guava seeds with TiO₂ gels prepared from TiOSO₄⋅xH₂O and NH₄OH using glycerol as a binder and thermally treating the materials at 500 °C. Raman studies confirmed the anatase phase of TiO₂. SEM images showed isolated TiO₂ agglomerates firmly attached to the carbon surface. The adsorption behavior of isoproturon on guava carbon was studied and yielded S-type adsorption isotherms. The photocatalytic activities of the prepared hybrid materials were monitored to study the kinetics and elimination process both of the herbicide and its photoproducts. The reaction was monitored by UV–Vis spectrophotometry, LC-DAD and LC-MS, enabling identification of some intermediate species. Among the photoproducts produced by carbon-TiO₂ hybrid materials, amino-isopropylphenol was detected.     

Oxidative Degradation of Orange II Dye in Water with Raw and Acid‐Treated ZnO,and MnO2

Commercial ZnO, MnO₂, and their acid‐treated forms were used as catalysts for oxidative degradation of Orange II dye in water. ZnO and MnO₂ were treated with 0.5, 0.75, or 1.0 N aqueous H₂SO₄. The acid treated oxides were found to be highly effective in bringing about degradation of Orange II in water. As much as 68.7% of the dye in an aqueous solution of 1 mg/L concentration could be degraded with untreated ZnO as the catalyst. The degradation increased to 79.5% with 1.0 N acid treated ZnO as the catalyst when the reaction was carried out at room temperature for 240 min. The catalytic activity was slightly affected by the solution pH in the range of 2.0–8.0. With MnO₂ as the catalyst, there was only 12.7% degradation of the dye, but this increased up to 100% when 0.5 N acid treated MnO₂ was used as the catalyst. It was found that a catalyst loading of 5.0 g/L of raw and acid‐treated ZnO and a loading of 0.5 g/L of raw and acid‐treated MnO₂ could bring about almost 100% degradation of Orange II in water in an interaction time of 240 min at room temperature.     

Hospital Laundry Wastewater Disinfection with Catalytic Photoozonation

Wastewater production in a hospital laundry and the treatment of the most critical wastewater stream, are assessed. Hospital laundry wastewaters are hazardous to the environment due to their high pollutant concentrations and the chemicals added during the clothes washing process. Heterogeneous photocatalysis with UV, O₃ and TiO₂ and their possible combinations were used for disinfection purposes. A ramp‐type reactor was used for TiO₂ (P25 Degussa) fixation and for photochemical diffusion of the ozonized air. After assessing 5‐day biological oxygen demand, chemical oxygen demand, pH, turbidity, and surfactant content, and checking for the presence of thermotolerant coliforms and Escherichia coli, it was concluded that UV/O₃/TiO₂ was the best process/combination, yielding a 100% disinfection rate and a microbiological inactivation of 0.5070 min^–1 for E. coli and of 0.5505 min^–1 for thermotolerant coliforms.     

Mineralization of Catechol by Fenton and Photo‐Fenton Processes

Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe²⁺, 7.09 mM H₂O₂, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.