Synthesis of Fe-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocatalyst and its sonophotocatalytic activity on synthetic dye and real textile wastewater

The catalysts such as Fe, Bi₂O₃, and Fe-doped Bi₂O₃ were synthesized for the sonophotocatalytic treatment of synthetic dye and real textile wastewater. The resultant catalysts were characterized for its size and uniform shape using x-ray diffractogram (XRD) and scanning electron microscopy (SEM) which signified the nanorod shape formed Bi₂O₃. The higher ultraviolet light absorbance capacity of the catalysts was also evident using diffuse reflectance spectroscopy (DRS). Initially, the effect of conventional parameters such as initial pH, gas bubbling (argon, oxygen, air and nitrogen) and oxidant addition (H₂O₂ and peroxymonosulfate) in the presence of sonolysis (22 and 37 kHz frequency) and photolysis (UV-C light) on 10 ppm Basic Brown 1 dye was studied. The results showed that highest decolorization of 62 % was attained for 3 g/L peroxymonosulfate under 37 kHz frequency sonolysis treatment. Secondly, with the catalyst study, highest of 46 % dye color removal was obtained with 4 g/L Fe under 37 kHz frequency sonolysis treatment. The sonophotocatalytic treatment of dye with Fe-doped Bi₂O₃ catalyst in combination with peroxymonosulfate showed highest color removal of 99 %. Finally, the sonophotocatalytic treatment of real textile wastewater in the presence of 3 g/L Fe-doped Bi₂O₃ and 6 g/L peroxymonosulfate reduced the total organic carbon (TOC) and chemical oxygen demand (COD) level to 77 and 91 %, respectively, in 180 min. The reported treatment process was found to treat the synthetic dye and real textile wastewater effectively.     

Catalytic oxidation for air pollution control

Bench-scale experiments have been conducted to evaluate a series of titania-supported Pt-Pd (as oxides) catalysts in the presence and absence of MoO₃ and Fe₂O₃ additives for their effectiveness in the complete catalytic oxidation of volatile organic compounds (VOCs) in air likely to be found in waste gases. Under oxidizing conditions, all of the catalysts promoted the complete oxidation of VOCs to CO₂ and H₂O. 99 % Conversion was achieved with a C₂H₄-C₂H₆ gas mixture in air at temperatures between about 160–450 °C and at a space velocity of 20,000 h^?1. Oxidation activity for the titania supported catalysts were found to decrease in the order Pt-Pd-Mo-Fe > Pt-Pd-Mo > Pt-Pd-Fe > Pt-Pd. However, the addition of MoO₃ and Fe₂O₃ increase the catalyst activity and reduce the reaction temperature for the complete destruction. Ageing was also performed in order to study the stability of the most active catalyst. Pt-Pd-Mo-Fe (as oxides) on titania catalyst is effective in oxidizing a wide range of volatile organic compounds at relatively low temperatures (220–405 °C) and and at a space velocity of 40,000 h^?1 and is resistant to poisoning by halogenated and amine volatile organic compounds.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Study on low-temperature plasma γ-Al2O3 catalytic viscosity reduction of polyacrylamide solution

The wide use of polyacrylamide (PAM) in enhanced oil recovery generates a large amount of polymer-bearing wastewater featuring high viscosity and difficult viscosity reduction, making the treatment of wastewater increasingly difficult. In this paper, the experimental study on reducing the viscosity of wastewater containing polyacrylamide by using the plasma generated by dielectric barrier discharge (DBD) and the synergistic effect of catalyst γ-Al₂O₃ is carried out. The law of plasma reducing the viscosity of wastewater containing polyacrylamide is studied under the different conditions of amounts of γ-Al₂O₃ catalyst, discharge voltages, and initial concentrations of polyacrylamide-containing wastewater. The mechanism of viscosity reduction of polyacrylamide is studied through environmental scanning electron microscope (ESEM), Fourier transform infrared (FTIR) spectrometer, and X-ray photoelectron spectroscopy (XPS). The results show that the catalytic viscosity reduction is the best when the discharge voltage is 18 kV and the discharge time is 15 min. With the increase in the input of the γ-Al₂O₃ catalyst, the viscosity of the PAM solution decreases gradually. When the amount of γ-Al₂O₃ is 375 mg, the shear rate changes from 0.5 1/sec to 28 1/sec, and the viscosity of the solution containing polyacrylamide changes from 434.5 mPa·s to 40.2 mPa·s. The viscosity reduction rate of the PAM solution is 90.7%. After the catalytic viscosity reduction, the functional groups of polyacrylamide do not change much. The elemental composition of the catalyst has not changed, which is still Al, C, and O.

     

Incinerating Volatile Organic Compounds with Ferrospinel Catalyst MnFe2O4: An Example with Isopropyl Alcohol

Abstract

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe₂O₄. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe₃O₄]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr^?1, an oxygen (O₂) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 °C.     

Presence of bacteria in aqueous solution influences virus adsorption on nanoparticles

Virus contamination in wastewater is usually accompanied by the existence of various bacteria. Nanoparticles (NPs) have been shown to efficiently remove virus. In this study, bacterial cells, supernatants, and cultures were harvested separately from three strains at the culture ages of 6 and 24 h, corresponding to the log and stationary phases, respectively. The aim is to investigate how their presence affects virus adsorption on the three Fe and Al oxide NPs (α-Fe₂O₃, γ-Fe₂O₃-B, and Al₂O₃) and how these effects change with bacterial growth phase. Bacteriophage phiX174 was used as a virus model. Results showed that bacterial cells, supernatants, and cultures harvested at 6 h generally reduced virus adsorption by an average of 0.75?±?0.84, 7.7?±?9.0, and 10.3?±?8.6 %, respectively, while those harvested at 24 h reduced virus adsorption by an average of 2.1?±?0.93, 21.5?±?6.6, and 24.6?±?6.9 %, respectively. Among the NPs, α-Fe₂O₃ showed more sensitivity to bacteria than the other two, probably because of its relatively higher value of point of zero charge. It was found that cell-induced and supernatant-induced reductions were combined to achieve added results, in which the supernatants contributed much more than the cells, implying that the bacterial exudates might be more crucial in the reduced virus adsorption than the bacterial cells. These results strongly demonstrated that the bacteria-induced reduction in virus adsorption became more significant with culture age. It is suggested that studies conducted in the absence of bacteria may not accurately evaluate the potential of virus removal efficiency of the NPs in bacteria-containing environments.     

Synthesis of α-Fe2O3 nanofibers for applications in removal and recovery of Cr(VI) from wastewater

Purpose

Nanomaterials such as iron oxides and ferrites have been intensively investigated for water treatment and environmental remediation applications. The purpose of this work is to synthesize α-Fe₂O₃ nanofibers for potential applications in removal and recovery of noxious Cr(VI) from wastewater.

Methods

α-Fe₂O₃ nanofibers were synthesized via a simple hydrothermal route followed by calcination. The crystallographic structure and the morphology of the as-prepared α-Fe₂O₃ nanofibers were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope. Batch adsorption experiments were conducted, and Fourier transform infrared spectra were recorded before and after adsorption to investigate the Cr(VI) removal performance and adsorption mechanism. Langmuir and Freundlich modes were employed to analyze the adsorption behavior of Cr(VI) on the α-Fe₂O₃ nanofibers.

Results

Very thin and porous α-Fe₂O₃ nanofibers have been successfully synthesized for investigation of Cr(VI) removal capability from synthetic wastewater. Batch experiments revealed that the as-prepared α-Fe₂O₃ nanofibers exhibited excellent Cr(VI) removal performance with a maximum adsorption capacity of 16.17 mg g^?1. Furthermore, the adsorption capacity almost kept unchanged after recycling and reusing. The Cr(VI) adsorption process was found to follow the pseudo-second-order kinetics model, and the corresponding thermodynamic parameters ΔG°, ΔH°, and ΔS° at 298 K were calculated to be ?26.60 kJ?mol^?1, ?3.32 kJ?mol^?1, and 78.12 J?mol^?1 K^?1, respectively.

Conclusions

The as-prepared α-Fe₂O₃ nanofibers can be utilized as efficient low-cost nano-absorbents for removal and recovery of Cr(VI) from wastewater.     

The use of artificial neural network (ANN) for the prediction and simulation of oil degradation in wastewater by AOP

The application of advanced oxidation process (AOP) in the treatment of wastewater contaminated with oil was investigated in this study. The AOP investigated is the homogeneous photo-Fenton (UV/H₂O₂/Fe⁺²) process. The reaction is influenced by the input concentration of hydrogen peroxide H₂O₂, amount of the iron catalyst Fe⁺², pH, temperature, irradiation time, and concentration of oil in the wastewater. The removal efficiency for the used system at the optimal operational parameters (H₂O₂?=?400 mg/L, Fe⁺²?=?40 mg/L, pH?=?3, irradiation time?=?150 min, and temperature?=?30 °C) for 1,000 mg/L oil load was found to be 72 %. The study examined the implementation of artificial neural network (ANN) for the prediction and simulation of oil degradation in aqueous solution by photo-Fenton process. The multilayered feed-forward networks were trained by using a backpropagation algorithm; a three-layer network with 22 neurons in the hidden layer gave optimal results. The results show that the ANN model can predict the experimental results with high correlation coefficient (R ²?=?0.9949). The sensitivity analysis showed that all studied variables (H₂O₂, Fe⁺², pH, irradiation time, temperature, and oil concentration) have strong effect on the oil degradation. The pH was found to be the most influential parameter with relative importance of 20.6 %.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes

Different advanced oxidation processes (AOPs) were applied to the treatment of a real cotton-textile dyeing wastewater as a pre-oxidation step to enhance the biodegradability of the recalcitrant compounds, which can be further oxidized using a biological process. Tests were conducted on a lab-scale prototype using artificial solar radiation and at pilot scale with compound parabolic collectors using natural solar radiation. The cotton-textile dyeing wastewater presents a lilac color, with a maximum absorbance peak at 641 nm, alkaline pH (pH?=?8.2), moderate organic content (DOC?=?152 mg C L^?1, COD?=?684 mg O₂ L^?1) and low-moderate biodegradability (40 % after 28 days in Zahn–Wellens test). All the tested processes contributed to an effective decolorization and mineralization, but the most efficient process was the solar-photo-Fenton with an optimum catalyst concentration of 60 mg Fe²⁺ L^?1, leading to 98.5 % decolorization and 85.5 % mineralization after less than 0.1 and 5.8 kJ_UV L^?1, respectively. In order to achieve a final wastewater with a COD below 250 mg O₂ L^?1 (discharge limit into water bodies imposed by the Portuguese Legislation-Portaria no. 423/97 of 25 June 1997), considering the combination of a solar-photo-Fenton reaction with a biological process, the phototreatment energy required is 0.5 kJ_UV L^?1, consuming 7.5 mM hydrogen peroxide, resulting in 58.4 % of mineralization $ \left({t}_{30\mathrm{W}}=3.2\ \min; \overline{T}=30.7\ {}^{\circ}\mathrm{C};\overline{\mathrm{pH}}=2.80;{\overline{\mathrm{UV}}}_{G,n}={13\ \mathrm{W}\ \mathrm{m}}^{-2}\right). $      

Influence of exogenous urea on photosynthetic pigments, 14CO2 uptake, and urease activity in Elodea densa—environmental implications

This paper analyzes the effect of exogenous urea in increased concentration gradient (0, 100, 500 and 1,000 mg L^?1) on photosynthetic pigments (measured spectrophotometrically), uptake of ¹⁴CO₂ (using radioisotope), and urease activity (by measuring ammonia with Nessler’s reagent) in leaves of Elodea densa Planch. We have observed that low concentration of urea (100 mg L^?1) stimulates the accumulation of photosynthetic pigments and intensifies photosynthesis in E. densa, whereas high concentration (1,000 mg L^?1) suppresses these processes. Urease activity increased by approximately 2.7 and 8 fold when exogenous urea concentrations were 100 and 500 mg L^?1, respectively. However, exogenous urea in high concentration (1,000 mg L^?1) decreased urease activity by 1.5 fold compared to the control. The necessity of mitigating urea and other nitrogen-containing compounds (NH₃ from urea) in water bodies has been discussed with emphasis on the potential for phytoremediation of urea using common water weed viz. E. densa.     

Electrooxidation of industrial wastewater containing 1,4-dioxane in the presence of different salts

The treatment of 1,4-dioxane solution by electrochemical oxidation on boron-doped diamond was studied using a central composite design and the response surface methodology to investigate the use of SO₄ ^2? and HCO₃ ^? as supporting electrolytes considering the applied electric current, initial chemical oxygen demand (COD) value, and treatment time. Two industrial effluents containing bicarbonate alkalinity, one just carrying 1,4-dioxane (S1), and another one including 1,4-dioxane and 2-methyl-1,3-dioxolane (S2), were treated under optimized conditions and subsequently subjected to biodegradability assays with a Pseudomonas putida culture. Electrooxidation was compared with ozone oxidation (O₃) and its combination with hydrogen peroxide (O₃/H₂O₂). Regarding the experimental design, the optimal compromise for maximum COD removal at minimum energy consumption was shown at the maximum tested concentrations of SO₄ ^2? and HCO₃ ^? (41.6 and 32.8 mEq L^?1, respectively) and the maximum selected initial COD (750 mg L^?1), applying a current density of 11.9 mA cm^?2 for 3.8 h. Up to 98 % of the COD was removed in the electrooxidation treatment of S1 effluent using 114 kWh per kg of removed COD and about 91 % of the COD from S2 wastewater applying 49 kWh per kg of removed COD. The optimal biodegradability enhancement was achieved after 1 h of electrooxidation treatment. In comparison with O₃ and O₃/H₂O₂ alternatives, electrochemical oxidation achieved the fastest degradation rate per oxidant consumption unit, and it also resulted to be the most economical treatment in terms of energy consumption and price per unit of removed COD.     

Sequential electrochemical treatment of dairy wastewater using aluminum and DSA-type anodes

Dairy wastewater is characterized by a high content of hardly biodegradable dissolved, colloidal, and suspended organic matter. This work firstly investigates the performance of two individual electrochemical treatments, namely electrocoagulation (EC) and electro-oxidation (EO), in order to finally assess the mineralization ability of a sequential EC/EO process. EC with an Al anode was employed as a primary pretreatment for the conditioning of 800 mL of wastewater. A complete reduction of turbidity, as well as 90 and 81 % of chemical oxygen demand (COD) and total organic carbon (TOC) removal, respectively, were achieved after 120 min of EC at 9.09 mA cm^?2. For EO, two kinds of dimensionally stable anodes (DSA) electrodes (Ti/IrO₂-Ta₂O₅ and Ti/IrO₂-SnO₂–Sb₂O₅) were prepared by the Pechini method, obtaining homogeneous coatings with uniform composition and high roughness. The ^·OH formed at the DSA surface from H₂O oxidation were not detected by electron spin resonance. However, their indirect determination by means of H₂O₂ measurements revealed that Ti/IrO₂-SnO₂–Sb₂O₅ is able to produce partially physisorbed radicals. Since the characterization of the wastewater revealed the presence of indole derivatives, preliminary bulk electrolyses were done in ultrapure water containing 1 mM indole in sulfate and/or chloride media. The performance of EO with the Ti/IrO₂-Ta₂O₅ anode was evaluated from the TOC removal and the UV/Vis absorbance decay. The mineralization was very poor in 0.05 M Na₂SO₄, whereas it increased considerably at a greater Cl^? content, meaning that the oxidation mediated by electrogenerated species such as Cl₂, HClO, and/or ClO^? competes and even predominates over the ^·OH-mediated oxidation. The EO treatment of EC-pretreated dairy wastewater allowed obtaining a global 98 % TOC removal, decreasing from 1,062 to <30 mg L^?1.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Kinetics of imidazolium-based ionic liquids degradation in aqueous solution by Fenton oxidation

In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50–90 °C), catalyst load (10–50 mg L^?1 Fe³⁺), initial IL concentration (100–2000 mg L^?1), and hydrogen peroxide dose (10–200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe³⁺]₀ = 50 mg L^?1; [H₂O₂]₀ = 100% of the stoichiometric amount), the complete removal of [C₄mim]Cl (1000 mg L^?1) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe³⁺ amount and H₂O₂ dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol^?1. The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.     

Response surface modeling for optimization heterocatalytic Fenton oxidation of persistence organic pollution in high total dissolved solid containing wastewater

The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N₂ adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, ²⁹Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H₂O₂ (4 mmol/L), FeSO₄?7H₂O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90 %, respectively.     

Improving the activity of Mn/TiO2 catalysts through control of the pH and valence state of Mn during their preparation

In this study, the authors investigated the influence of the valence state of Mn on the efficacy of selective catalytic reduction using a Mn-based catalyst. The nitrogen oxides (NO_x) conversion rate of the catalyst was found to be dependent on the type of TiO₂ support employed and on the temperature, as the catalyst showed an excellent conversion of > 80% at a space velocity of 60,000 hr^?1 when the temperature was above 200 °C. Brunauer-Emmett-Teller, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that catalyst displaying the highest activity contained the Mn⁴⁺ species and that its valence state was highly dependent on the pH during the catalyst preparation.

Implications Recently, various Mn catalysts have been evaluated as selective catalyst reduction (SCR) catalysts. However, in these previous studies, only the reaction characteristics and catalytic activity on the NH₃ SCR over Mn catalysts were evaluated. There have been no studies on the effect of pH during catalyst preparation. Therefore, in this study, the effect of pH during the catalyst preparation process was examined and a new application of the Mn catalysts was proposed based on the current findings.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.