A statistical experiment design approach for advanced oxidation of Direct Red azo-dye by photo-Fenton treatment.

Advanced oxidation of an azo-dye, Direct Red 28 (DR 28) by photo-Fenton treatment was investigated in batch experiments using Box-Behnken statistical experiment design and the response surface analysis. Dyestuff (DR 28), H(2)O(2) and Fe(II) concentrations were selected as independent variables in Box-Behnken design while color and total organic carbon (TOC) removal (mineralization) were considered as the response functions. Color removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. High concentrations of H(2)O(2) and Fe(II) adversely affected the color and TOC removals due to hydroxyl radical scavenging effects of high oxidant and catalyst concentrations. Both H(2)O(2) and Fe(II) concentration had profound effects on decolorization. Percent color removal was higher than TOC removal indicating formation of colorless organic intermediates. Complete color removal was achieved within 5min while complete mineralization took nearly 15min. The optimal reagent doses varied depending on the initial dyestuff dose. For the highest dyestuff concentration tested, the optimal H(2)O(2)/Fe(II)/dyestuff ratio resulting in the maximum color removal (100%) was predicted to be 715/71/250 (mgL(-1)), while this ratio was 1550/96.5/250 for maximum mineralization (97.5%).

Manganese dioxide nanoparticles/activated carbon composite as efficient UV and visible-light photocatalyst.

Manganese dioxide nanoparticles/activated carbon (MnO2/AC) composites and manganese dioxide nanoparticles (MnO2 NPs) are prepared through chemical reduction method. Morphological study shows that MnO2 NPs had cylindrical and spherical shape. The morphological study also revealed that MnO2 NPs were well dispersed on AC while neat Mn NPs present both in dispersed and in agglomerated form. The FT-IR study confirms the synthesis of MnO2 NPs. Zetasizer study presented that the Mn NPs had uniform size and below 100 nm in size and had zeta potential of - 20 mV, which represent its stability in the suspension form. The synthesized Mn/AC composite and Mn NPs were utilized as photocatalysts for the photodegradation of Congo red (CR) dye. The degradation study shows that MnO2/AC composite degraded CR dye more efficiently than MnO2 NPs under UV and normal light irradiation. The efficient degradation of dye by Mn/AC composite is due to the synergistic effect between dye adsorption on AC and rapid photodegradation by supported MnO2 NPs. The results revealed that Mn/AC composite degraded about 98.53% of CR dye within 5 min while MnO2 NPs degraded 66.57% of dye within the same irradiation time. The recycled catalyst also significantly degraded dye which verifies its sustainability. The effect of catalyst dosage and initial dye concentration was conducted. The degradation rate of dye was found drastically faster in tap water (in presence of catalyst), which might be due to the presence of various mineral ions in the tap water.

Visible light driven photo-degradation of Congo red by TiO2ZnO/Ag: DFT approach on synergetic effect on band gap energy.

In this paper, we report the combination of two metal oxides (TiO2ZnO) that allows mixed density of states to reduce band gap energy, facilitating the photo-oxidation of Congo red dye under visible light. For the oxidation, a possible mechanism is proposed after analyzing the intermediates by GC-MS, and it is consistent with Density Functional Theory (DFT). The nanohybrids were characterized comprehensibly by several analytical techniques such as X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS). For the addition of ZnO to TiO2, a dominance of anatase phase was found rather than other phases (rutile or brookite). A broad band (∼550 nm) is observed in UV-Visible spectra for TiO2ZnO/Ag NPs nm because of Surface Plasmon properties of Ag NPs. The band gap energy was calculated for TiO2ZnO/Ag system, and then it has been further studied by DFT in order to show why the convergence of two semiconductors allows a mixed density of states, facilitating the reduction of the energy gap between occupied and unoccupied bands; ultimately, it improves the performance of catalysts under visible light. Significantly, the interaction of crystal planes (0 0 I) of TiO2 anatase and (0 0 1) of ZnO crucially plays as an important role for the reduction of energy band-gap. Additionally, TiO2ZnOAg NPs were used recognize Saccharomyces cerevisiae cells by con-focal fluorescence microscope, showing that it develops bright bio-images for the cells; while for TiO2 or ZnO or TiO2ZnO NPs, no fluorescent response was seen within the cells.

Radiation degradation of Congo Red in aqueous solution.

Radiation-induced degradation of Congo Red (an azo dye) in aqueous solution was studied both with steady-state radiolysis and time-resolve techniques of pulse radiolysis and laser flash photolysis. Decomposition and mineralization of Congo Red by gamma-rays was investigated with the changes of absorption spectra, degradation efficiency, TOC removal and pH changes of the solutions in different irradiation systems. The main radiolytic products resulting from steady-state radiolysis of Congo Red were examined by HPLC and LC-MS. Complete degradation of Congo Red was observed at different absorbed doses under diverse irradiation condition. The TOC removal of the solutions saturated with O2 or N2O reached 76% and 86% at the absorbed dose of 11.9 kGy, respectively. Pulse radiolysis and laser flash photolysis experiments were carried out to study the reaction of Congo Red with e(aq)- and ()OH. The reaction rate constants were determined.

Investigation on the rapid degradation of congo red catalyzed by activated carbon powder under microwave irradiation.

Azo dyestuff-congo red in aqueous solution can be degraded rapidly under microwave irradiation in the presence of activated carbon powder. The results showed that the degradation ratio could reach 87.79% for 25 mL total volume with 50mg/L congo red and 2.0 g/L activated carbon powder under 1.5 min microwave irradiation. Furthermore, within the same irradiation time, congo red could be degraded fully by increasing addition amount (e.g. 3.6g/L) of activated carbon powder and the degradation ratio was up to 96.49%. Otherwise, with the same addition amount, congo red also could be degraded completely by prolonging irradiation time (e.g. 2.5 min) and the degradation ratio was up to 97.88%. In addition, the influences of microwave irradiation time, initial concentration of congo red, addition amount and used times of activated carbon powder as well as solution acidity on the degradation were discussed in details adopting UV-vis spectra, FT-IR spectra, ion chromatography, high phase liquid chromatography (HPLC) and TOC analysis technologies. Here, the method using activated carbon powder as catalyst under microwave irradiation shows many advantages including high degradation ratios, short reaction time, low costs, no intermediates and no secondary pollution. Therefore, it may be fit for dealing with various azo dyestuff wastewaters on a large scale.

Efficient solar light-driven degradation of Congo red with novel Cu-loaded Fe3O4@TiO2 nanoparticles.

In this work, Cu-loaded Fe3O4@TiO2 core shell nanoparticles were prepared in a single pot by coating of TiO2 on Fe3O4 nanoparticles followed by Cu loading. X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), Brunauer-Emmett- Teller (BET), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), and valence band X-ray photoelectron spectroscopy (VB XPS) techniques were used for characterization of as prepared nanoparticles. Synergism between copper and titania was evaluated by studying the solar light-driven photodegradation of Congo red dye solution in the presence of Fe3O4@TiO2 nanoparticles on one side and Cu-loaded Fe3O4@TiO2 nanoparticles on the other side. The latter performed better than the former catalyst, indicating the enhanced activity of copper-loaded catalyst. Further photodegradation was studied by three means, i.e., under ultraviolet (UV), refluxing, and solar radiations. Cu-loaded Fe3O4@TiO2 enhanced the degradation efficiency of Congo red dye. Thus, Cu act possibly by reducing the band gap of TiO2 and widening the optical response of semiconductor, as a result of which solar light could be used to carry out photocatalysis. Graphical abstract Photodegradation of congo red over Cu-loaded Fe3O4@TiO2 nanoparticles.

Photocatalytic decomposition of Congo red under visible light irradiation using MgZnCr-TiO2 layered double hydroxide.

The new nanophotocatalyst MgZnCr-TiO2 was prepared by co-precipitation under different molar ratio of metals (Zn:Cr) and the loaded amount of TiO2. And it was characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy et al. Langmuir model fitted well the adsorption isotherm with the value of R2 0.9765, the maximum adsorption capacity was 526.32 mg g-1, the adsorption followed pseudo second order kinetic by MgZnCr-TiO2 (1:1:2-0.05). The photocatalytic oxidation of Congo red was used to determine the photocatalytic performance of MgZnCr-TiO2 (1:1:2-0.05) under visible light irradiation, and the removal rate reached 98% after reaction for 40 min. The degradation mechanism of Congo red also was proposed, and the MgZnCr-TiO2 (1:1:2-0.05) was stable after five cycles. Compared to the adsorption, Congo red was removed fundamentally by photocatalysis and it is expected to be an effective way to eliminate Congo red.

The effect of operational parameters on the photocatalytic degradation of Congo red organic dye using ZnO-CdS core-shell nano-structure coated on glass by Doctor Blade method.

Photocatalytic degradation of Congo red was investigated using ZnO-CdS core-shell nano-structure coated on glass by Doctor Blade method in aqueous solution under irradiation. Field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques were used for the morphological and structural characterization of ZnO-CdS core-shell nanostructures. XRD results showed diffractions of wurtzite zinc oxide core and wurtzite cadmium sulfide shell. FESEM results showed that nanoparticles are nearly hexagonal with an average diameter of about 50 nm. The effect of catalyst loading, UV-light irradiation time and solution pH on photocatalytic degradation of Congo red was studied and optimized values were obtained. Results showed that the employment of efficient photocatalyst and selection of optimal operational parameters may lead to complete decolorization of dye solutions. It was found that ZnO-CdS core-shell nano-structure is more favorable for the degradation of Congo red compare to pure ZnO or pure CdS due to lower electron hole recombination. The results showed that the photocatalytic degradation rate of Congo red is enhanced with increasing the content of ZnO up to ZnO(0.2 M)/CdS(0.075 M) which is reached 88.0% within 100 min irradiation.

Photodegradation of Reactive Black 5, Direct Red 28 and Direct Yellow 12 using UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(2+): a comparative study.

The photodegradation of three commercially available dyestuffs (C.I. Reactive Black 5, C.I. RB5, C.I. Direct Yellow 12, C.I. DY12, and C.I. Direct Red 28, C.I. DR28) by UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(II) processes was investigated in a laboratory-scale batch photoreactor equipped with an 16W immersed-type low-pressure mercury vapour lamp. The experimental results were assessed in terms of absorbance and total organic carbon (TOC) reduction. The initial concentration was kept constant at 100 mg l(-1) for all dyes. Initial results showed that, color removal efficiencies by UV or H(2)O(2) alone were negligible for all dyes. Almost complete disappearance of C.I. RB5 (99%) and DY12 (98%) in UV/H(2)O(2) process was possible to achieve after 60 min of irradiation. The maximum color removal efficiency of C.I. DR28 after 60 min of irradiation, however, was only 40% and reached a maximum value of 70% after 120 min of irradiation. Corresponding mineralization efficiencies were 50, 55 and 7-12%, respectively. The addition of Fe(II) to the system, so-called the photo-Fenton process, greatly enhanced the color removal, the efficiencies being 98, 88 and 85% for C.I. RB5, C.I. DY12 and C.I. DR28 only after 5 min of irradiation. Corresponding mineralization efficiencies were 98% for 45 min irradiation, 100% for 60 min irradiation and 98% for 90 min irradiation, respectively. However, marginal benefit was less significant in the higher range of both H(2)O(2) and Fe(II). Furthermore, decreases in both decolorization and mineralization were observed at higher concentrations of oxidant and catalyst due to the scavenging effect of excess H(2)O(2) and OH radicals. The degradation of all dyes was found to follow first-order reaction kinetics.

Investigation of preparation conditions and photocatalytic efficiency of nano ZnO using different polysaccharides.

The development of a complete set of extensive studies combining both the preparation factors of catalysts and photocatalytic experimental factors for the photodegradation of methylene blue, crystal violet, and Congo red using effective nano zinc oxide (ZnO) obtained from polysaccharides (chitosans, corn starch, and sodium alginate) as chelating agents was the main objective of this study. The influence of nature of polysaccharides, ratio of reactants, calcination temperatures during preparation process, and effects of photocatalytic experimental conditions on photodegradation was investigated. Corn starch and sodium alginate were found to be effective chelating agents and optimum preparation parameters were set as 3:3 % ratio of reactants and 450 °C calcination temperature to prepare nano ZnO with good photocatalytic activity. The order of organic dyes based on their photodegradation rates was arranged as crystal violet > methylene blue > Congo red. Our findings shed light on the optimization of both preparation conditions of photocatalysts and photocatalytic experimental conditions.

Photocatalytic decolorization and degradation of Congo Red on innovative crosslinked chitosan/nano-CdS composite catalyst under visible light irradiation.

The crosslinked chitosan/nano-CdS (CS/n-CdS) composite catalyst prepared by simulating bio-mineralization process was extensively characterized by FT-IR spectra, XRD, SEM, TEM and TGA. An azo dye, Congo Red (CR), was used as model pollutant to study its photocatalytic activity under visible light irradiation. The influences of catalyst amount, initial CR concentrations, pH of the reaction solution and different anions on CR decolorization and degradation reaction kinetics were investigated. Results of characterization indicated the successful formation of hexagonal phase of CdS on raw chitosan under mild conditions. The photocatalytic degradation was found to follow a pseudo-first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The dye could be decolorized more efficiently in acidic media than alkaline media. The presence of NO(3)(-) accelerated evidently the degradation of CR, while the other chosen anions (Br(-), SO(4)(2-) and Cl(-)) had an inhibitory effect on the decolorization of CR, of which the inhibitory effect of Cl(-) was the most pronounced. UV-vis spectra were analyzed to indicate that degradation of CR in the solution was the break up of the NN bonds and degradation of aromatic fragment in this reaction system. The recycling experiments confirmed the relative stability of the catalyst.

Synthesis and characterization of TiO2-pillared Romanian clay and their application for azoic dyes photodegradation.

The synthesis and properties of metal oxide pillared cationic clays (PILCs) has been subject to numerous studies in the last decades. In order to obtain TiO(2)-pillared type materials, sodium montmorillonite from Romania-areal of Valea Chioarului, having the following composition (% wt): SiO(2)-72.87; Al(2)O(3)-14.5; MgO-2.15; Fe(2)O(3)-1.13; Na(2)O-0.60; K(2)O-0.60; CaO-0.90; PC-5.70 and cation exchange capacity, determined by ammonium acetate method, of 82 meq/100g, as matrix, was used. Sodium form of the clay was modified, primarily, by intercalation of cetyl-trimethylammonium cations between negatively charged layers which will lead to the expansion of the interlayer space. For the preparation of the TiO(2)-pillared clay, the alkoxide molecules, as titania precursor, were adsorbed onto/into clay samples (1 mmol Ti/g clay), in hydrochloric acid environment, the resulted species being converted into TiO(2) pillars by calcination. The as-prepared materials have been used as catalysts for Congo Red dye photodegradation, under UV. The photocatalytic activity of the pillared clays is a function of TiO(2) pillars size, their increase leading to the enhancement of the contact areas between dye solution and photoactive species present in the interlayer space. The structural characteristics and properties of the obtained materials were investigated by X-ray Diffraction, Thermogravimetry Analysis, UV-vis Diffuse Reflectance, Transmission Electron Microscopy and Energy Dispersive X-ray Analysis.