Heterogeneous photocatalyzed degradation of uracil and 5-bromouracil in aqueous suspensions of titanium dioxide

Photocatalyzed degradation of uracil (1) and 5-bromouracil (2) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation of the compounds under investigation was studied using various parameters such as, different types of TiO2 powders, pH, catalyst concentration, substrate concentrations, and in the presence of electron acceptors like hydrogen peroxide (H(2)O(2)) and potassium bromate (KBrO(3)) besides molecular oxygen. Photocatalyst Degussa P25 was found to be more efficient for the degradation of both compounds as compared with other TiO2 powders such as UV100, PC500 and TTP.     

Comparative photocatalytic study of two selected pesticide derivatives, indole-3-acetic acid and indole-3-butyric acid in aqueous suspensions of titanium dioxide

Heterogeneous photocatalysed degradation of two selected pesticide derivatives such as indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA) has been investigated in aqueous suspensions of titanium dioxide by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics was studied under different conditions such as pH, types of TiO_2, substrate and catalyst concentration, and in the presence of electron acceptor such as hydrogen peroxide (H₂O₂) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 showed comparatively highest photocatalytics. The pesticide derivative, indole-3-acetic acid was found to degrade slightly faster than indole-3-butyric acid.     

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives, amaranth and bismarck brown in aqueous suspension

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives such as amaranth (1) and bismarck brown (2) has been investigated in aqueous suspension by monitoring the change in substrate concentration employing UV spectroscopic analysis technique as a function of irradiation time. The degradation was studied under different conditions such as types of TiO(2), pH, substrate concentration, catalyst concentration, and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and ammonium persulphate (NH(4))(2)S(2)O(8) besides air. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 showed comparatively highest photocatalytic activity. The dye derivative, bismarck brown (2) was found to degrade faster than amaranth dye (1).     

Photocatalytic removal of hazardous dye cyanosine from industrial waste using titanium dioxide

In this paper, photocatalytic degradation studies of a hazardous water soluble xanthene dye cyanosine in aqueous suspensions of titanium dioxide under a variety of conditions, viz., catalyst concentration, substrate concentration, pH, temperature and electron acceptor hydrogen peroxide (H2O2) have been reported. It was observed that photocatalytic degradation by TiO2 is an effective, economic and faster mode of removing cyanosine from aqueous solution. The optimum conditions for the degradation of the dye was dye concentration 1x10(-4)M, pH 8, catalyst concentration 0.04g/L and temperature +/-30 degrees C. Chemical oxygen demand and dye absorbance of the photodegraded dye solution substantially decreased.     

Nanophotocatalysis using immobilized titanium dioxide nanoparticle: Degradation and mineralization of water containing organic pollutant: Case study of Butachlor

In this paper, the degradation and mineralization of Butachlor in aqueous solution by nanophotocatalysis using immobilized TiO₂ nanoparticles were investigated. Butachlor (N-butoxymethyl-2-chloro-2′,6′-diethylacetanilide) is a persistent organic pollutant in agricultural soil and watercourses. A simple and effective method was used for immobilization of titanium dioxide nanoparticles. UV-vis and Ion Chromatography (IC) analyses were employed to obtain the details of the photocatalytic degradation and mineralization of Butachlor. The effects of operational parameters such as H₂O₂, inorganic anions (NO₃⁻, Cl⁻ and SO₄²⁻) and pH were investigated. The lack of any absorbance in 254 nm was indicative of the complete degradation of aromatic intermediates. The mineralization of Butachlor was evaluated by monitoring of the formed inorganic anions (NO₃⁻ and Cl⁻). Butachlor is effectively degraded following first order kinetics model. Results show that the immobilized titanium dioxide nanoparticle photocatalysis is an effective method for treatment Butachlor from contaminated water.     

硅藻土微粒负载纳米TiO2的制备

以硫酸氧钛为原料,硅藻土微粒为载体,尿素为沉淀剂,通过改变硫酸氧钛的浓度、硅藻土与二氧化钛质量比、尿素浓度、pH值、水解温度、反应时间和焙烧温度等工艺条件,采用混合均匀沉淀法制备出了硅藻土基负载型纳米二氧化钛．利用SEM和XRD对样品的结构性能进行测定,得出在最佳制备条件下,二氧化钛在硅藻土表面的最大覆盖率为75％,二氧化钛平均粒径为150nm,并初步探讨了二氧化钛粒子和载体之间的结合机理．该产品对模拟室内甲醛的降解实验表明,在可见光范围内本产品对甲醛的处理效果是明显的。     

TiO2纳米管阵列薄膜光电催化降解甲基橙染料废水

采用电化学阳极氧化法在纯钛表面制备出TiO2纳米管阵列,应用FE-SEM和XRD表征其形貌。以该纳米管陈列薄膜为光阳极,比较了光解、光催化和光电催化对甲基橙溶液降解效率的差异,研究了pH值和外加偏压对甲基橙降解效率的影响,并建立了光电催化氧化反应的一级动力学模型来描述产生这种效果的主要因素。结果表明,在光电催化氧化体系中,TiO2纳米管阵列薄膜对甲基橙具有显著的降解作用;溶液中的电解质、溶液的pH值和外加偏压是影响光电催化效果的关键因素;最佳的降解条件为电解质存在下、pH值为3、外加偏压为1.5V,在该条件下紫外灯照射80min后降解率可达100%。     

Correlation of lattice distortion with photocatalytic activity of titanium dioxide

The photocatalytic activity of titanium dioxide dispersions on X-3B pigment degradation has been investigated. A variety of factors that would influence the photocatalytic activity such as crystallite size, lattice distortion, and anatase content are discussed in detail. It is found that lattice distortion is the most important one among these factors and is expected to inhibit the hole and electron pair recombination. It determines, to some extent, the photocatalytic efficiency of titanium dioxide dispersions.     

Evaluation of magnetic nanoparticles performance as photocatalyst for the catalytic treatment of direct red 28 dye in synthetic and real water effluents

Integrated water resources management practice is gaining popularity as an alternative water source due to the limited supply of freshwater. The present study was carried out on the photocatalytic degradation of Direct red 28 (DR-28) dye using magnetic nanoparticles (MNPs; Fe₃O₄) as a photocatalyst. The study was conducted on the photocatalytic degradation of DR-28 dye in synthetic dye effluent water, to understand the effects of different photoreaction parameters on the degradation kinetics. The influence of different parameters such as time, amount of photocatalyst, concentration of H₂O₂ and pH was investigated. At the optimum dosage of MNPs (0.6?g/L) with 4?mmol/L of H₂O₂, significant photocatalytic degradation of DR-28 dye (93.2%) was observed. The kinetic study revealed that the photocatalytic degradation followed pseudo-first-order kinetics. The degradation performance of Fe₃O₄ nanoparticles as a photocatalyst for DR-28 dye was compared with titanium dioxide (TiO₂) and it was found that the performance of Fe₃O₄ as a photocatalyst is superior to TiO₂ photocatalyst. The real dye effluent was also degraded at optimum conditions and promising results were achieved.     

Titanium dioxide-mediated heterogeneous photocatalytic degradation of terbufos: parameter study and reaction pathways

The photocatalytic degradation of terbufos in aqueous suspensions was investigated by using titanium dioxide (TiO(2)) as a photocatalyst. About 99% of terbufos was degraded after UV irradiation for 90 min. Factors such as pH of the system, TiO(2) dosage, and presence of anions were found to influence the degradation rate. Photodegradation of terbufos by TiO(2)/UV exhibited pseudo-first-order reaction kinetics, and a reaction quantum yield of 0.289. The electrical energy consumption per order of magnitude for photocatalytic degradation of terbufos was calculated and showed that a moderated efficiency (E(EO)=71 kWh/(m(3)order)) was obtained in TiO(2)/UV process. To obtain a better understanding of the mechanistic details of this TiO(2)-assisted photodegradation of terbufos with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. The probable photodegradation pathways were proposed and discussed.     

Destruction of chemical agent simulants in a supercritical water oxidation bench-scale reactor

A new design of supercritical water oxidation (SCWO) bench-scale reactor has been developed to handle high-risk wastes resulting from munitions demilitarization. The reactor consists of a concentric vertical double wall in which SCWO reaction takes place inside an inner tube (titanium grade 2, non-porous) whereas pressure resistance is ensured by a Hastelloy C-276 external vessel. The performances of this reactor were investigated with two different kinds of chemical warfare agent simulants: OPA (a mixture of isopropyl amine and isopropyl alcohol) as the binary precursor for nerve agent of sarin and thiodiglycol [TDG, (HOC(2)H(4))2S] as the model organic sulfur heteroatom. High destruction rates based on total organic carbon (TOC) were achieved (>99.99%) without production of chars or undesired gases such as carbon monoxide and methane. The carbon-containing product was carbon dioxide whereas the nitrogen-containing products were nitrogen and nitrous oxide. Sulfur was totally recovered in the aqueous effluent as sulfuric acid. No corrosion was noticed in the reactor after a cumulative operation time of more than 250 h. The titanium tube shielded successfully the pressure vessel from corrosion.     

Synthesis of nanocrystalline TiO2 thin films by liquid phase deposition technique and its application for photocatalytic degradation studies

A transparent, high purity titanium dioxide thin film composed of densely packed nanometer sized grains has been successfully deposited on a glass substrate at 30°C from an aqueous solution of TiO₂-HF with the addition of boric acid as a scavenger by liquid phase deposition technique. From X-ray diffraction measurement, the deposited film was found to be amorphous and turns crystalline at 500°C. The deposited film showed excellent adherence to the substrate and was characterized by homogeneous flat surface. TiO₂ thin films can be used as a photocatalyst to clean up organohalides, a class of compound in pesticides that pollute the ground water. Photocatalytic degradation experiments show that indanthrene golden orange dye undergoes degradation efficiently in presence of TiO₂ thin films by exposing its aqueous solution to ultraviolet light. The suitable surface structure and porosity increases the photocatalytic activity. It was also observed that hemin doped TiO₂ thin films break up organohalides at a surprisingly high rate under visible light.     

Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts

The present study involves the photocatalytic degradation of Methyl Orange (MO) and Rhodamine 6G (R6G), employing heterogeneous photocatalytic process. Photocatalytic activity of various semiconductors such as titanium dioxide (TiO(2)), zinc oxide (ZnO), stannic oxide (SnO(2)), zinc sulphide (ZnS) and cadmium sulphide (CdS) has been investigated. An attempt has been made to study the effect of process parameters viz., amount of catalyst, concentration of dye and pH on photocatalytic degradation of MO and R6G. The experiments were carried out by irradiating the aqueous solutions of dyes containing photocatalysts with UV and solar light. The rate of decolorization was estimated from residual concentration spectrophotometrically. Similar experiments were carried out by varying pH (2-10), amount of catalyst (0.25-2.0g/l) and initial concentration of dye (5-200mg/l). The experimental results indicated that the maximum decolorization (more than 90%) of dyes occurred with ZnO catalyst and at basic pH and the maximum adsorption of MO was noticed at pH 4 and of R6G at pH 10. The percentage reduction of MO and R6G was estimated under UV/solar system and it was found that COD reduction takes place at a faster rate under solar light as compared to UV light. In case of R6G, highest decolorizing efficiency was achieved with lower dose of catalyst (0.5g/l) than MO (1g/l) under similar conditions. The performance of photocatalytic system employing ZnO/solar light was observed to be better than ZnO/UV system.     

Photocatalytic activity studies of TiO2 thin films prepared by r.f. magnetron reactive sputtering

A series of transparent titanium dioxide thin films have been obtained on microscope glass slides by means of r.f. magnetron reactive sputtering using Ar and O₂ mixed gases. The photocatalytic activity of the TiO₂ thin films was evaluated by the degradation of rhodamine B dye wastewater. The influences of substrate temperatures and total sputtering pressures on the photocatalytic activity of the TiO₂ films were investigated. It was observed that substrate temperature had little influences on the photocatalytic activity, but the photocatalytic activity of the TiO₂ thin films was improved by decreasing the total sputtering pressure.     

Physical and biocompatibility studies of novel titanium dioxide doped phosphate-based glasses for bone tissue engineering applications

This study investigated doping titanium dioxide (TiO(2)) into phosphate glasses, 50 P(2)O(5)-30 CaO-20 Na(2)O, to control their degradation rate and enhance their biological response to be suitable scaffolds for bone tissue engineering applications. The thermal and structural properties were analysed using differential thermal analysis and X-ray powder diffraction. The effect of TiO(2) incorporation on degradation rate, ion release, and pH changes was also carried out. In vitro cyto-biocompatibility was assessed through MG63 human osteosarcoma cells attachment and viability using scanning electron microscopy and confocal microscopy, respectively. The results showed that addition of TiO(2) produced a significant increase in density and glass transition temperature. X-ray diffraction analysis showed the presence of NaCa(PO(3))(3) as a main phase of these glasses with titanium phosphate Ti-P(2)O(7) only detected for 5 mol% TiO(2) glasses. The degradation rate, however, was significantly reduced by one order of magnitude with incorporation of 5 mol% TiO(2) which has been reflected in released ions (cations and anions) and the minimal pH changes. Moreover, addition of TiO(2), 3 and 5 mol% in particular, supported the MG63 cells attachment and maintained high cell viability up to 7 days culture comparable to Thermanox. These results suggested that TiO(2) containing phosphate glasses can be a promising substrate for bone tissue engineering applications.     

Room-temperature deposition of amorphous titanium dioxide thin film with high refractive index by a filtered cathodic vacuum arc technique

Amorphous titanium dioxide (TiO2) thin film has been prepared by a filtered cathodic vacuum arc technique at room temperature. It was concluded from the core level of Ti 2p 3/2 (458.3 eV) and O 1s (529.9 eV) and their deviation in binding energy (deltaBE = 71.6 eV) that only one of Ti oxidation states, Ti4+, existed in the film and the film was of ideal stoichiometry. The film possessed high transmittance, which can reach as high as that of a quartz substrate, especially in the visible range, owing to its optical bandgap of 3.2 eV. The high refractive index (2.56 at 550 nm) and low extinction coefficient (approximately 10(-4) at 550 nm) suggested that the film had a high packing density and a low scattering-center concentration. These good optical properties implied the film prepared by this technique was a promising candidate for optical application. Besides, the film was found to transform in the structure from amorphous to anatase crystalline when it was annealed at 300 degrees C, as evidenced by Raman and x-ray diffraction.     

A detailed insight into the preparation of nanocrystalline TiO<Subscript>2</Subscript> powders in supercritical carbon dioxide

This work reports detailed investigations for the preparation of nanostructured titania powders by a solvent-free sol–gel-derived process, operated in supercritical CO₂ (SC-CO₂) at high pressures (10–30 MPa) and large range of temperatures (373–823 K). Depending on the processing temperature, the reaction between Ti(OiPr)₄ and water performed in a single supercritical phase led to the formation of either amorphous (Ti(OH)₄—titanium hydroxide) or crystalline (TiO₂—titanium dioxide) nanostructured particles. Crystalline (anatase) mesoporous powders with high specific surface area were obtained directly in CO₂ solvent under supercritical conditions at temperatures as low as 523 K. The effect of hydrodynamic key process parameters such as stirring and water injection rate on both powder morphology and aggregation degree was also investigated in details. The optimized TiO₂ anatase powders exhibited attractive photocatalytic activity, with high potential for the degradation of water pollutants.     

Electrochemical degradation of 4-chloroguaiacol for wastewater treatment using PbO2 anodes

Electrochemical oxidation of 4-chloroguaiacol (4-CG) at Nb/PbO(2) anodes was studied under different experimental conditions such as initial concentration of substrate, electrolysis time, temperature and pH. We measured the concentrations of 4-chlorocatechol (4-CC), 2-methoxyhydroquinone (2-MHQ), maleic acid (MA) and carbon dioxide as the main products. Black solid particles consisting mainly of polymers were formed during electrolysis. A mechanism of electrochemical oxidation of 4-CG was investigated. The oxidation of 4-CG can generally be described by simple pseudo first-order kinetics. The degradation of 4-CG was favoured at high temperature and lower initial concentration of 4-CG and low solution pH. However, the increase of temperature has not a significant effect on the mineralization of carboxylic acids. Moreover, these products required long electrolysis time.     

Oxidation of triclosan by ferrate: reaction kinetics, products identification and toxicity evaluation

The Crystal Violet (CV) dye represented one of the major triphenylmethane dyes used in textile-processing and some other industrial processes. Various metals doped titanium dioxide (TiO(2)) photocatalysts have been studied intensively for the photodegradation of dye in wastewater treatment. In order to understand the mechanistic detail of the metal dosage on the activities enhancement of the TiO(2) based photocatalyst, this study investigated the CV photodegradation reactions under UV light irradiation using a Pt modified TiO(2) photocatalyst. The results showed that Pt-TiO(2) with 5.8% (W/W) Pt dosage yielded optimum photocatalytic activity. Also the effect of pH value on the CV degradation was well assessed for their product distributions. The degradation products and intermediates were separated and characterized by HPLC-ESI-MS and GC-MS techniques. The results indicated that both the N-de-methylation reaction and the oxidative cleavage reaction of conjugated chromophore structure occurred, but with significantly different intermediates distribution implying that Pt doped TiO(2) facilitate different degradation pathways compared to the P25-TiO(2) system.     

Investigation on the sonocatalytic degradation of parathion in the presence of nanometer rutile titanium dioxide (TiO2) catalyst

The nanometer rutile titanium dioxide (TiO2) powder was adopted to act as the sonocatalyst after treatment of high-temperature activation and the ultrasound of low power was used as an irradiation source to induce heat-treated TiO2 powder performing sonocatalytic degradation of parathion. Although there are many factors influencing sonocatalytic degradation of parathion, the experimental results demonstrate that the optimal degradation condition of parathion can be obtained when the experimental conditions such as initial concentration of 50 mg/L parathion, addition amount of 1000 mg/L nanometer rutile TiO2, ultrasonic of 30-50 kHz frequency and 50 W output power, acidity of pH 10.0 and temperature of 20 degrees C are adopted. The degradation ratio of parathion surpassed 90% within 120 min ultrasonic irradiation in these optimal experiment conditions. The total degradation process of parathion has been monitored by UV-vis spectra and ion chromatography. At last, the parathions in aqueous solution are completely degraded and become some simple inorganic ions such as NO3(-), PO4(3-), SO4(2-), etc. In addition, the sonocatalytic activities of reused TiO2 catalysts were also studied and found to decline gradually along with the reused times. In this paper, the research on sonocatalytic degradation kinetics was also been performed and found to follow pseudo first-order reaction. All experiments indicated that the sonocatalytic method in the presence of nanometer rutile TiO2 powder was an advisable choice for the treatments of non- or low-transparent organic wastewaters in future.