Titania nanowires as substrates for sensing and photocatalysis of common textile industry effluents

Sensing and photocatalysis of textile industry effluents such as dyes using mesoporous anatase titania nanowires are discussed here. Spectroscopic investigations show that the titania nanowires preferentially sense cationic (e.g. Methylene Blue, Rhodamine B) over anionic (e.g. Orange G, Remazol Brilliant Blue R) dyes. The adsorbed dye concentration on titania nanowires increased with increase in nanowire dimensions and dye solution pH. Electrochemical sensing directly corroborated spectroscopic findings. Electrochemical detection sensitivity for Methylene Blue increased by more than two times in magnitude with tripling of nanowire average length. Photodegradation of Methylene Blue using titania nanowires is also more efficient than the commercial P25-TiO₂ nanopowders. Keeping illumination protocol and observation times constant, the Methylene Blue concentration in solution decreased by only 50% in case of P25-TiO₂ nanoparticles compared to a 100% decrease for titania nanowires. Photodegradation was also found to be function of exposure times and dye solution pH. Excellent sensing ability and photocatalytic activity of the titania nanowires is attributed to increased effective reaction area of the controlled nanostructured morphology.     

A Comparative study on synthesis, characterization and photocatalytic activities of MgO and Fe/MgO nanoparticles

MgO and Fe/MgO particles in the nanometer-size regime have been successfully synthesized by a hydrothermal crystallization process using dodecyl benzenesulphonic acid as a surfactant. The prepared catalysts were characterized in details by multiform techniques: XRD, SEM, TEM, UV-DRS, TGA-DSC, BET surface area, and EPR spectroscopy. Comparative photocatalytic activity of the samples was evaluated through the photodegradation of Acid Blue 80 dye under sunlight. The results of the photocatalytic degradation of Acid Blue 80 dye in aqueous solution demonstrated that Fe ions doping greatly improved the photocatalytic efficiency of MgO nanoparticles. Most interestingly, this is the first time that it has been observed that the Fe/MgO system is quite an effective visible light active catalyst.     

Study of the influential factors in the simultaneous photocatalytic degradation process of three textile dyes

The influence of several factors in the simultaneous photocatalytic degradation of three textile dyes - Acid Red 97, Acid Orange 61 and Acid Brown 425 - has been studied using a fractional factorial design 2^5-1. The considered factors were: the initial concentration of each dye, the catalyst concentration (TiO₂) and pH.First, we developed a rapid analytical methodology based on recording UV-visible spectra during the degradation process and a data treatment using multivariate curve resolution with alternating least squares (MCR-ALS), which enabled the three dyes to be quantified simultaneously despite the overlap of their spectra.The kinetic constant of degradation for each dye in all the experiments was evaluated. In all cases the degradation followed a first order kinetics. For a significance level of 5%, the most important factor in the photodegradation of each dye is the concentration of Acid Red 97, the degradation is more effective at higher pHs and, in the studied range, the concentration of the catalyst is not important.     

Photodegradation of a textile dye catalyzed by sol–gel derived nanocrystalline TiO2 via ultrasonic irradiation

Nanocrstalline pure anatase titania were prepared by sol–gel process at room temperature followed by ultrasonication (Ti–US). The photocatalytic activity of Ti–US has been evaluated by the degradation of textile dye, Methylene Blue in presence and absence of common inorganic salts (NO₃⁻, C₂O₄²⁻, SO₄²⁻, citrate). It was observed that, in presence of anions, the degradation of the dye increases significantly. The influence of the presence of H₂O₂ on the degradation rate was studied. The dependence of photodegradation of the dye rates on various parameters such as dye concentration, photocatalyst concentration and pH were also investigated. The photodegradation rate follows first order kinetics. H₂O₂ and UV light have a negligible effect in absence of Ti–US catalyst. The relative photonic efficiency of the system is reported using phenol as a standard organic compound.     

Kinetics of heterogeneous photocatalytic degradation of reactive dyes in an immobilized TiO2 photocatalytic reactor

The photocatalytic degradation of two reactive dyes has been investigated by UV/TiO2/H2O2 using an immobilized TiO2 photocatalytic reactor. Reactive Blue 8 (RB 8) and Reactive Blue 220 (RB 220) textile dyes were used as model compounds. Photocatalytic degradation processes were performed using a 5-L solution containing dyes. The initial concentrations of dyes were 50 mg/L. The radiation source was two 15 W UV-C lamps. A batch mode immersion photocatalytic reactor was utilized. UV-vis and ion chromatography (IC) analyses were employed to obtain the details of the photodegradation of the selected dyes. Colored synthetic waters were completely decolorized in relatively short time after UV irradiation in the presence of various concentrations of hydrogen peroxide. Formate, acetate, oxalate, and glyoxylate anions were detected as dominant aliphatic intermediates where they were further oxidized slowly to CO2. The UV/TiO2/H2O2 process was able to oxidize the dyes with partial mineralization of carbon, nitrogen, and sulfur heteroatoms into CO2, NO3-, and SO4(2-), respectively. Kinetics analysis indicates that the photocatalytic decolorization rates of the dye can be approximated by a pseudo-first-order model. The UV/TiO2/H2O2 process proved to be capable of decolorization and mineralization of the reactive dyes (RB 8 and RB 220).     

Blue dye degradation in an aqueous medium by a combined photocatalytic and bacterial biodegradation process

This paper aimed at implementing a treatment system for polluted water with textile dyes, starting with a photocatalytic decomposition process using sunlight as a source of energy and continuing with a bacterial biodegradation process, in order to reach degradation percentages higher than those obtained using only one of the processes mentioned above. When water treatment with the dye in the combined system was over, an acute ecotoxicity test was performed to make sure that toxic metabolites were not produced due to biodegradation. Solophenyl Blue azoic dye, and Erionyl Blue and Terasil Blue anthraquinone dye-colored solutions were treated with the Pd/Al ₈₀ Ce ₁₀ Zr ₁₀ catalyst in a solar collector for the photocatalytic process. On the other hand, the waste dye, which was obtained from photocatalysis with a bacterial consortium from polluted areas by metals and hydrocarbons in aerobic conditions, was inoculated for biodegradation. Biodegradation was obtained for the dyes after both processes as 90.91% for the Solophenyl Blue azoic dye, and 87.80% and 87.94%, respectively, for the Erionyl Blue and Terasil Blue anthraquinone dyes. After the degradation processes, it was proven, via an ecotoxicity test with Daphnia magna , that toxic metabolites had not been produced.     

Modeling and optimization of simultaneous photocatalysis of three dyes on ceramic-coated TiO2 nanoparticles using chemometrics methods: phytotoxicological assessment during degradation process

In this paper, ceramic plates were used as a support of TiO₂ nanoparticles for photocatalytic decolorization of a mixture of three dyes. The three textile dyes (C.I. Basic Red 46, C.I. Basic Blue 3 and Malachite Green) were quantified simultaneously during the photocatalytic degradation process. The partial least squares modeling was successfully applied for the multivariate calibration of the spectrophotometric data. Also, the central composite design has been applied to the optimization of photocatalytic decolorization of the dye solution containing three dyes using an immobilized UV/TiO₂ process. The optimum initial concentration of three dyes, reaction time, and UV light intensity were found to be 5 mg/L, 240 min, and 47.2 W/m², respectively. The chronic phytotoxicity of mixture of dyes was evaluated using aquatic species Spirodela polyrhiza (S. polyrhiza) prior to and after photocatalysis. The phytotoxicity results revealed that the photocatalysis process could effectively reduce the phytotoxicity of the dyes from their aqueous solutions.     

Photocatalytic degradation of waste water pollutants. Titanium dioxidemediated oxidation of a textile dye, Acid Blue 40

The photocatalyzed degradation of Acid Blue 40, a textile dye, in aqueous suspension of TiO₂ has been studied by monitoring the change in dye concentration and formation of carbon dioxide as a function of irradiation time. Mechanistic studies suggest that in addition to the reaction of the hydroxyl and superoxide radicals with the dye, electron transfer from the photoexcited TiO₂ to the dye forms a significant pathway in the photodegradation process. Contribution No RRLT-PRU-76 from the Regional Research Laboratory.     

Influence of operational parameters on photocatalytic degradation of a genotoxic azo dye Acid Violet 7 in aqueous ZnO suspensions

The photocatalytic degradation of a genotoxic azo dye Acid Violet 7 (AV 7) using ZnO as a photocatalyst in aqueous solution has been investigated under UV irradiation. The degradation is higher with UV/ZnO process than with UV/TiO(2)-P25 process at pH 9. The effects of different parameters such as pH of the solution, amount of catalyst, initial dye concentration and the influence of cations, anions and oxidants on photodegradation of AV 7 were analyzed. Addition of oxidants except H(2)O(2) has no significant effect on degradation. The degradation of AV 7 follows pseudo-first order kinetics according to the Langmuir-Hinshelwood model. The degradation of AV 7 has also been confirmed by COD and CV measurements.     

Photocatalytic disinfection of bacterial pollutants using suspended and immobilized TiO2 powders

The photocatalytic disinfection of Enterobacter cloacae and Enterobacter coli using microwave (MW), convection hydrothermal (HT) and Degussa P25 titania was investigated in suspension and immobilized reactors. In suspension reactors, MW‐treated TiO₂ was the most efficient catalyst (per unit weight of catalyst) for the disinfection of E. cloacae. However, HT‐treated TiO₂ was approximately 10 times more efficient than MW or P25 titania for the disinfection of E. coli suspensions in surface water using the immobilized reactor. In immobilized experiments, using surface water a significant amount of photolysis was observed using the MW‐ and HT‐treated films; however, disinfection on P25 films was primarily attributed to photocatalysis. Competitive action of inorganic ions and humic substances for hydroxyl radicals during photocatalytic experiments, as well as humic substances physically screening the cells from UV and hydroxyl radical attack resulted in low rates of disinfection. A decrease in colony size (from 1.5 to 0.3 mm) was noted during photocatalytic experiments. The smaller than average colonies were thought to occur during sublethal ^?OH and O₂^?? attack. Catalyst fouling was observed following experiments in surface water and the ability to regenerate the surface was demonstrated using photocatalytic degradation of oxalic acid as a model test system.     

Photodegradation of methyl green using visible irradiation in ZnO suspensions: determination of the reaction pathway and identification of intermediates by a high-performance liquid chromatography-photodiode array-electrospray ionization-mass spectrometry method

Heterogeneous photocatalytic treatment of a dye called methyl green (MG), which was simulating textile wastewater from associated auxiliary chemicals, was investigated using ZnO. A detailed investigation of the photodegradation of MG has been carried out in the ZnO suspension irradiated with visible light. The effects of various factors - viz. pH values, amount of catalyst, initial dye concentration, and the presence of NaCl, Na(2)CO(3), H(2)O(2), and Na(2)S(2)O(8) - on the degradation efficiency were studied. Thirty-two intermediates were separated, identified, and characterized by high-performance liquid chromatography-photodiode array-electrospray ionization-mass spectrometry (HPLC-ESI-DAD-MS) technology, giving us insight into the pathways of the degradation process.     

Adsorption of Acid Blue 193 from aqueous solutions onto Na-bentonite and DTMA-bentonite

Dodecyltrimethylammonium bromide-modified bentonite (DTMA-bentonite) was prepared and tested as an adsorbent for an acid dye (Acid Blue 193, AB193) removal from aqueous solution in comparison with Na-bentonite. The effect of various experimental parameters was investigated using a batch adsorption technique. In this manner, the adsorption isotherms, adsorption kinetics, and temperature and pH effects upon Acid Blue 193 adsorption on Na-bentonite and DTMA-bentonite were thoroughly examined. Results show that a pH value of 1.5 is favorable for the adsorption of Acid Blue 193. The isothermal data could be well described by the Freundlich equation. The dynamical data fit well with the pseudo-second-order kinetic model. The adsorption capacity of DTMA-bentonite (740.5 mg g(-1)) was found to be around 11 times higher than that of Na-bentonite (67.1 mg g(-1)) at 20 degrees C. Thermodynamic parameters such as activation energy (E(a)) and change in the free energy (DeltaG(0)), the enthalpy (DeltaH(0)), and the entropy (DeltaS(0)) were also evaluated. The overall adsorption process was exothermic but it is only spontaneous at 20 degrees C. The results indicate that Na-bentonite and DTMA-bentonite could be employed as low-cost alternatives to activated carbon in wastewater treatment for the removal of color which comes from textile dyes.     

Acid dye adsorption onto cationized polyamide fibres. Modeling and consequent interpretations of model parameter behaviours

Experimental adsorption isotherms of four acid dyes named Acid Blue 25, Acid Yellow 99, Reactive Yellow 23, and Acid Blue 74 from aqueous solution onto cationized nylon-6,6 have been analyzed using a double layer adsorption model. The parameters involved in the analytical expression of this model such as the number or fraction of adsorbed dye molecule per site, n, the number of receptor sites per gram of adsorbent, N(M), and the concentration at half-saturation, c1/2, are determined from adsorption isotherms at four temperatures between 293 and 353 K. The evolution of these parameters with temperature is discussed in relation with adsorption process and the behaviours of the different dyes taking into account their particular structure. The results are compared with those already published dealing with the adsorption of these same dyes onto cationized cotton. The configurational entropy at various temperatures has been studied. This parameter allowed to deduce some results related to the evolution of the disorder during the adsorption process.     

Use of titanium dioxide photocatalysis on the remediation of model textile wastewaters containing azo dyes

The photocatalytic degradation of two commercial textile azo dyes, namely C.I Reactive Black 5 and C.I Reactive Red 239, has been studied. TiO(2) P25 Degussa was used as catalyst and photodegradation was carried out in aqueous solution under artificial irradiation with a 125 W mercury vapor lamp. The effects of the amount of TiO(2) used, UV-light irradiation time, pH of the solution under treatment, initial concentration of the azo dye and addition of different concentrations of hydrogen peroxide were investigated. The effect of the simultaneous photodegradation of the two azo dyes was also investigated and we observed that the degradation rates achieved in mono and bi-component systems were identical. The repeatability of photocatalytic activity of the photocatalyst was also tested. After five cycles of TiO(2) reuse the rate of colour lost was still 77% of the initial rate. The degradation was followed monitoring the change of azo dye concentration by UV-Vis spectroscopy. Results show that the use of an efficient photocatalyst and the adequate selection of optimal operational parameters may easily lead to a complete decolorization of the aqueous solutions of both azo dyes.     

MCM-41分子筛担载纳米TiO2复合材料光催化降解罗丹明B

采用溶胶-凝胶法将TiO2担载在介孔MCM-41分子筛上, 制备了不同TiO2含量的系列TiO2/MCM-41复合材料, 利用X射线衍射、N2吸附、紫外-可见光谱和透射电镜等方法对其进行表征. TiO2的晶型为锐钛矿相, 复合材料的比表面积和孔体积随其中TiO2担载量(复合材料中TiO2与MCM-41的质量比)的增加而减小, TiO2的平均粒径随其担载量的增加而增大. 以罗丹明B的光催化降解为探针反应, 评价了TiO2/MCM-41复合材料的光催化降解活性. 结果表明, 在紫外光照射下, 罗丹明B在该复合材料上的光催化降解反应遵循一级反应动力学, 复合材料对罗丹明B的光催化降解活性明显高于商用TiO2 (P-25), 复合材料的光催化降解活性由复合材料的吸附能力和所含TiO2的光催化活性共同决定.     

二氧化钛纳米管阵列的构建及其光电催化性能

利用阳极氧化法制备了TiO2纳米管阵列, 研究了其光电化学性能, 并且应用该电极对偶氮染料催化降解进行了初步研究.     

Photocatalytic properties of titania nanostructured films fabricated from Titania nanosheets

We examined the photochemical properties of well-ordered multilayer films of titania nanosheets prepared on quartz-glass substrate using the layer-by-layer deposition method. The photocatalytic decomposition of gaseous 2-propanol and bleaching of Methylene Blue dye under UV light illumination were measured to evaluate the photocatalytic oxidation ability. Photoinduced hydrophilicity was also studied by measuring the contact angle of water droplets on the film. The results indicated that titania nanosheets had good photoinduced hydrophilicity. The monolayer film of titania nanosheets showed almost identical activity compared with well investigated sol-gel derived anatase TiO(2) film, while its photocatalytic oxidation activity was low by more than an order of magnitude. This fact suggests that photoinduced hydrophilicity could not be explained simply in terms of the photocatalytic removal of hydrophobic organic species adsorbed on the surface. The photocatalytic oxidation activity and the photoinduced hydrophilic conversion rate decreased with increasing number of nanosheet layers, suggesting that photogenerated carriers produced in the internal part of the multilayer films can hardly diffuse to the surface layer. Photochemical properties of ultrathin anatase films obtained simply by heating the titania nanosheet films were evaluated as well, and also revealed high photoinduced hydrophilicity.     

A Novel Kinetic Approach for Photocatalytic Degradation of Azo Dye with CdS and Ag/CdS Nanoparticles Fixed on a Cement Bed in a Continuous‐Flow Photoreactor

Azo dyes are one of the synthetic dyes that have been used in many textile industries. Azo dye and their intermediate products are toxic, carcinogenic, and mutagenic to aquatic life. Removal of azo dyes is one of the main challenges before releasing the wastes discharged by textile industries. Photocatalytic degradation of azo dyes by nanoparticles is one of the environment‐friendly methods used for the removal of dyes from textile effluents. Therefore, this study focused on degradation of azo dye, Direct Red 264. Photocatalytic degradation of DR 264 azo dye was investigated using CdS and Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor under UV‐C exposure. The effect of the parameters of type and mass of catalyst, temperature, flow rate, dye concentration, and light intensity were evaluated for azo dye removal. Under optimal conditions, photocatalytic degradation of DR 264 azo dye using Ag/CdS nanoparticles immobilized on a cement bed in a continuous‐flow photoreactor obtained an efficiency of 99.99%. A developed kinetic model was proposed based on the intrinsic elementary reactions. The proposed model is in a good agreement with the Langmuir–Hinshelwood (L–H) equation. The pseudo–steady‐state approximation has considered for the concentration of hydroxyl radicals associated with the L–H model under certain conditions and explains consistently the dependence of the apparent kinetic parameter, k_obs (the reaction rate constant), and K_R (the adsorption equilibrium constant) with the light intensity. Based on the model, k_obs for Ag/CdS was greater than the CdS nanoparticles.     

Determination of the degradation products of selected sulfonated phenylazonaphthol dyes treated by white rot fungus Pleurotus ostreatus by capillary electrophoresis coupled with electrospray ionization ion trap mass spectrometry

The removal of water-soluble sulphonated phenylazonaphthol dye effluents generated by textile industries is an important issue in wastewater treatment. Microbial treatment of environmental pollutants including dyes, with white rot fungi has received wide attention as a potential alternative for conventional methods in wastewater treatment. Three sulphonated phenylazonaphthol dyes with similar molecular structures Acid Orange 7, Acid Orange 8 and Mordant Violet 5 were selected and degraded by the white rot fungus Pleurotus ostreatus. Chemical instrumental analysis methods such as high-performance liquid chromatography (HPLC) and capillary electrophoresis combined with electrospray ionization mass spectrometry (CE-ESI-MS) were used to identify the degraded dyes. Mordant Violet 5 had two degradation pathways when degraded by P. ostreatus. The first degradation pathway for Mordant Violet 5 was for trans structure and the cis-Mordant Violet 5 followed the second pathway. Acid Orange 8 and Acid Orange 7 had the same degradation mechanism as the first degradation mechanism for Mordant Violet 5, that is cleavage of azo bond at the naphthalene ring side where benzenesulfonic acid and 1,2-naphthoquinone are formed.     

Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity

Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria.