TiO<Subscript>2</Subscript> photocatalytic degradation of 4-chlorobiphenyl as affected by solvents and surfactants

Purpose  

TiO₂ photocatalytic degradation of 4-chlorobiphenyl (PCB3) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including initial PCB3 concentration, TiO₂ content, UV intensity, H₂O₂ concentration, cosolvents, and surfactants.     

The Oxidation of Di-(2-Ethylhexyl) Phthalate (DEHP) in Aqueous Solution by UV/H2O2 Photolysis

The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in solution using UV/H₂O₂ and direct UV photolysis are analyzed in this study. It was found that DEHP was 100% removal in the solution by 180-min UV/H₂O₂ treatment and 73.5% removal by 180-min direct UV photolysis. The effect of different factors, such as DEHP concentration, H₂O₂ concentration, and UV light intensity, on photochemical degradation was investigated. The degradation mechanism of DEHP and the acute toxicity of intermediates were also studied. The photochemical degradation process was found to follow pseudo-first-order kinetics. The results of our study suggested that the concentration with 40 mg/L H₂O₂ and 5 μg/mL DEHP in the solution at pH 7 with 10.0?×?10^?6 Einstein l^?1?s^?1 UV was the optimal condition for the photochemical degradation of DEHP. The photochemical degradation with UV/H₂O₂ can be an efficient method to remove DEHP in wastewater.     

Visible Light Induced Photocatalytic Degradation of Methyl Orange by Polythiophene/TiO2 Composite Particles

The adsorption and photocatalytic degradation of methyl orange (MO) aqueous solution under visible light illumination by polythiophene/titanium dioxide (PTh/TiO₂) composite particles were studied. The experimental observations from UV–vis spectrophotometer indicate that MO molecules were degraded in a different degree during the visible light-induced photocatalysis reaction. We propose a new degradation mechanism of MO during the photocatalytic reaction, based on blue shift of UV–vis absorption spectra of MO solution and other researches. The data from total organic carbon analyzer definitely prove that MO can be mineralized to CO₂ and H₂O, and some intermediate products are generated during the photocatalysis degradation of MO.     

Degradation of Hazardous Dyes in Wastewater using Nanometer Mixed Crystal TiO2 Powders under Visible Light Irradiation

The partial phase transformation of nanometer TiO₂ powder from anatase phase to rutile phase was realized by heat-treatment and a new TiO₂ photocatalyst which could be excited by visible light was obtained. The heat-treated TiO₂ powder at different stage of transition crystal was characterized and monitored by XRD, TEM, FT-IR and UV–vis DRS methods. The test of photocatalytic activity of the heat-treated TiO₂ powder was carried out by the photocatalytic degradation of rhodamine B and acid orange II dyes, respectively, in aqueous solution under visible light irradiation. The results indicate that the nanometer TiO₂ photocatalyst heat-treated at 500°C for 60 min shows the highest photocatalytic activity, that is, it can effectively degrade the rhodamine B and acid orange II under visible light irradiation. The remarkable improvement of photocatalytic activity of heat-treated TiO₂ powder at 500°C for 60 min was mainly illustrated by the formation of special interphase between rutile and anatase phases, which not only restrains the recombination of photogenerated electrons and holes, but also reduces the adsorbability of nanometer anatase TiO₂ powder properly for various dyes. Additionally, the effects of dye-assisting chemicals such as Na₂CO₃ and NaCl on the photocatalytic degradation were also studied.     

Preparation of Highly Efficient CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Composite Photocatalyst for the Degradation of Rhodamine B Dye from Aqueous Solution

CoFe₂O₄/Zn₂SnO₄ composite was synthesized using a simple two-step process and applied as a novel-efficient photocatalyst for the rhodamine B degradation from aqueous solution. Characterization techniques such as X-ray diffraction (XRD), N₂ adsorption-desorption isotherms, scanning electron microscopy (SEM), EDS analysis, and diffuse reflectance spectroscopy were employed in order to investigate the physical and chemical properties of composite. Higher values of the specific surface area, pore volume and diameter, and a smaller band-gap energy promoted a greater catalytic activity of CoFe₂O₄/Zn₂SnO₄ composite when compared to Zn₂SnO₄. A rapid decolorization of dye solution was observed at 40 min of reaction using the CoFe₂O₄/Zn₂SnO₄ catalyst, being 2.5 times faster than the Zn₂SnO₄ alone. Therefore, the CoFe₂O₄/Zn₂SnO₄ composite shows extraordinarily high photocatalytic activity toward the degradation of rhodamine B dye from aqueous solution.     

Remediation of polychlorinated biphenyl-contaminated soil by soil washing and subsequent TiO2 photocatalytic degradation

Purpose

An efficient method was developed for treating polychlorinated biphenyl (PCB)-contaminated soil by soil washing and subsequent TiO₂ photocatalytic degradation, and the photocatalytic degradation mechanism of PCBs was explored.

Materials and methods

Hydroxypropyl-??-cyclodextrin (HP??CD) and polyoxyethylene lauryl ether (Brij35) were used to extract PCBs from contaminated soil at first, and then the degradation of PCBs in the soil extracts was performed by TiO₂ photocatalysis under UV irradiation.

Results and discussion

Washing conditions including washing time, the concentration of HP??CD/Brij35, and the ratio of soil mass to solution volume for extracting 2,4,4??-trichlorobiphenyl (PCB28) from a PCB28-spiked soil were investigated at first. The results indicated that both HP??CD and Brij35 exhibited good performance. The intermediates of photocatalytic degradation of PCB28 were from its dechlorination and hydroxylation in the HPCD and aqueous solutions, respectively. A field PCB-contaminated soil from e-waste recycling sites was treated by this method. The results showed that the extracting percentage was significantly affected by the chlorination degree of PCBs, and HP??CD slowed down the photocatalytic degradation efficiency of overall PCBs.

Conclusions

Soil washing and subsequent TiO₂ photocatalytic degradation was successfully applied for treating PCB-contaminated soil, and HP??CD strongly altered the pathways of the photocatalytic degradation of PCBs.     

Photodegradation of Bisphenol A with ZnO and TiO<Subscript>2</Subscript>: Influence of Metal Ions and Fenton Process

In this study, photocatalytic degradation of bisphenol A (BPA) was investigated using two types of catalysts (TiO₂ and ZnO) with various metal ion concentrations and amounts of added H₂O_2. A kinetic test was performed to observe the changes of BPA over time under UV irradiation in a photocatalytic reactor. Experimental results demonstrated that degradation efficiency of ZnO was higher than that of TiO₂. The degradation rate increased as catalyst dosage increased until reaching optimum dosage, after which degradation rate decreased. The addition of H₂O₂ improved the degradation efficiency of BPA, with the degradation efficiency increasing with the amount of H₂O₂. All metal ions, including Fe²⁺, Ni²⁺, and Cu²⁺, inhibited the degradation of BPA by ZnO at natural pH, whereas Fe²⁺ and Ni²⁺ enhanced degradation efficiency of BPA at acidic pH. Comparison of BPA degradation with H₂O₂ only, ZnO/H₂O₂, Fe²⁺/H₂O₂, and ZnO/Fe²⁺/H₂O₂ revealed that Fe²⁺/H₂O₂ was more efficient than other processes at lower pH (pH?=?3.44), whereas ZnO/H₂O₂ the most efficient at higher pH (pH?=?6.44). These results indicate that ZnO/H₂O₂ process was observed to be the most efficient of all processes. Degradation efficiency of BPA by ZnO was also influenced by additional parameters, including H₂O₂ concentration, metal ions, and solution pH.     

Speciation of Phosphorus and Cadmium in a Contaminated Soil Amended with Bone Char: Sequential Fractionations and XANES Spectroscopy

In this work, photocatalytic degradation of two reactive dyes, Reactive Yellow 84 (RY 84) and Reactive Black 5 (RB 5), on FeTiO₃/TiO₂ heterojunction in the presence of UV–visible radiation and H₂O₂ has been reported. FeTiO₃/TiO₂ heterojunction has been prepared from ilmenite FeTiO₃ and anatase TiO₂ by employing oxalic acid as an organic linker. FeTiO₃/TiO₂ ratios have been varied from 1 to 5 wt.%, and the materials were characterized by X-ray diffraction, scanning electron microscope and diffused reflectance UV–visible spectroscopic analysis. The photocatalytic activity of FeTiO₃/TiO₂ heterojunction for the degradation of the organic dyes RY 84 and RB 5 in the presence of UV–visible light was found to be higher than that of pure TiO₂. The addition of H₂O₂ increases the rate of degradation of both dyes on FeTiO₃/TiO₂ heterojunction. It facilitates the fast degradation of dye solutions even when their concentration was above 100 mg/l, which is otherwise very slow due to the low transmittance of light by the dye solution. The extent of mineralisation of the reactive dye during photocatalytic degradation was estimated from chemical oxygen demand analysis. FeTiO₃/TiO₂ heterojunction photocatalyst was also found to have good photostability; the material retains almost 97 % of its initial activity even in the fifth cycle.     

Photocatalytic Degradation of Herbicide Quinmerac in Various Types of Natural Water

The efficiency of the photocatalytic degradation of the herbicide quinmerac in aqueous TiO₂ suspensions was examined as a function of the type of light source, TiO₂ loading, pH, temperature, electron acceptors, and hydroxyl radical (^?OH) scavenger. The optimum loading of catalyst was found to be 0.25?mg?mL^?1 under UV light at pH?7.2, with the apparent activation energy of the reaction being 13.7?kJ?mol^?1. In the first stage of the reaction, the photocatalytic degradation of quinmerac (50???M) followed approximately a pseudo-first order kinetics. The most efficient electron acceptor appeared to be H₂O₂ along with molecular oxygen. By studying the effect of ethanol as an ^?OH scavenger, it was shown that the heterogeneous catalysis takes place mainly via ^?OH. The results also showed that the disappearance of quinmerac led to the formation of a number of organic intermediates and ionic byproducts, whereas its complete mineralization occurred in about 120?min. The reaction intermediates (7-chloro-3-methylquinoline-5,8-dione, three isomeric phenols hydroxy-7-chloro-3-methylquinoline-8-carboxylic acids, and 7-chloro-3-(hydroxymethyl)quinoline-8-carboxylic acid) were identified and the kinetics of their appearance/disappearance was followed by LC?CESI?CMS/MS. Tentative photodegradation pathways were proposed and discussed. The study also encompassed the effect of quality of natural water on the rate of removal of quinmerac.     

TiO2 Immobilized Biodegradable Polymer for Photocatalytic Removal of Chlorophenol

This study concentrated on the direct immobilization of anatase nano titanium dioxide particles (TiO₂, 44?nm particle size) into or onto a biodegradable polymer, polycaprolactone, by solvent-cast processes. The photocatalytic properties of the produced materials were tested by photocatalytic removal of organic contaminant 4-chlorophenol. Produced TiO₂ immobilized polymer successfully removed 4-chlorophenol (4-CP, 20?ppm which is equal to 1.56?×?10^?4?M) from aqueous solution without additional pH arrangement employing a UV-A light (365?nm) source. Immobilization of n-TiO₂ onto polycaprolactone (PCL) produced improved 4-CP removal percentages, reaching to nearly 85?%. Increased PCL mass significantly increases the removal percentage of 4-CP. When a UVC lamp emitting 254?nm light is used, the removal percentage reaches to 89?%. UV irradiation did not cause any change in the microstructure of the polymeric material (confirmed with ATR-FTIR analysis). This is an important evidence that the material could be reused for further photocatalytic treatments. Produced material seems to be highly promising for successful removal of organic pollutants beside its biodegradable nature.     

Removal of Mixed Pesticides from Drinking Water System Using Surfactant-Assisted Nano-TiO2

The present study focused on the degradation of mixed pesticides using UV-induced photocatalytic degradation of lindane (1α,2α,3β,4α,5α,6β-hexachlorocyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate), and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate). Different grades of TiO₂ were prepared through the acid route (AR), alcohol route (AlR), and surfactant route (SR) and their photocatalytic activity were compared with commercially available Degussa P-25 TiO₂. The rate of degradation of pesticides was high for TiO₂ prepared through the SR compared to the other three catalysts. The crystalline structure and morphology of SR TiO₂ was identified with scanning electron microscope, energy dispersive X-ray analyzer, UV, and transmission electron microscope analyses and was compared with that of Degussa P-25 TiO₂. Degradation studies of individual as well as mixed pesticides were carried out. The intermediate formed during the photodegradation of methyl parathion, lindane, and dichlorvos were identified by gas chromatography–mass spectrometry analysis.     

TiO2纳米粒子气固相光催化降解乙烯初探

该文对TiO₂纳米粒子气固光催化降解果蔬贮藏环境乙烯技术进行了初步研究。采用溶胶-凝胶法制备的纳米TiO₂薄膜作光催化剂，利用自行设计的气固光催化实验系统，研究了乙烯浓度、紫外光作用时间对光催化降解反应的影响，探讨了乙烯的光催化降解的动力学。结果显示：该研究所制备的TiO₂锐钛矿型含量为48.766%，比表面积为47.186 m²/g，具有良好的光催化性能；光催化降解乙烯比直接紫外线光降解效果显著，光照10 min时光催化乙烯降解率比直接紫外线光降解提高23.76%；乙烯的降解率随着其浓度的增加而降低；乙烯的光催化降解的动力学可以用Langmuir-Hinshelwood动力学方程加以描述。     

钙和NO对NaCl胁迫下黄瓜幼苗生长和活性氧代谢的影响

采用营养液培养的方法,研究了Ca2+对外源一氧化氮(Nitric oxide,NO)所诱导的NaCl胁迫下黄瓜幼苗生长、活性氧代谢的影响。结果表明,添加外源NO或Ca2+显著缓解了NaCl胁迫对黄瓜幼苗生长的抑制,叶片和根系超氧化物歧化酶(SOD)、过氧化物酶(POD)、过氧化氢酶(CAT)活性较单独NaCl胁迫处理显著提高,丙二醛(MDA)和过氧化氢(H2O2)的含量、超氧阴离子(O.-2)产生速率明显下降;添加NO的同时添加Ca2+通道抑制剂La3+抑制了NO的这些调节作用。结果表明Ca2+对NO诱导的NaCl胁迫下黄瓜幼苗植株活性氧清除能力的提高起重要作用,NO的作用可能依赖于胞浆Ca2+。     

Enhanced Photocatalytic Activity of Co Surface Doped Nanocrystalline TiO2-SiO2 Composite Films

In order to enhance the photocatalytic activity of the TiO₂ films, Co surface doped TiO₂-SiO₂ composite films were synthesized by the improved sol-gel method, in which tetrabutyl titanate (Ti(OC₄H₉)₄) and tetraethyl orthosilicate were chosen as the precursors and cobaltous nitrate hexahydrate (Co(NO₃)₂·6H₂O) was chosen as cobalt source. The field emission scanning electron microscopy and X-ray diffraction results indicated that the films were composed of nanoparticles or aggregates. The photoluminescence results revealed that the recombination rate of the photogenerated electrons and holes was prohibited via SiO₂ composite and Co doping in TiO₂ film. The Brunauer?CEmmett?CTeller results showed that the surface area of the modified TiO₂ was 301.7?m²?g^?1, while that of the pure TiO₂ was 68.4?m²?g^?1. The photocatalytic activities of the films were evaluated by degradation of an organic dye in aqueous solution. With the SiO₂ composite and Co doping, the modified TiO₂ films with high photocatalytic activity and clearly responsive to the visible light were obtained. The mechanisms of photoactivity enhancement for composite films have also been discussed.     

Degradation of Leather Dye Using CeO2–SnO2 Nanocomposite as Photocatalyst Under Sunlight

Nanocomposite of CeO₂?CSnO₂ containing different CeO₂ contents was prepared by coprecipitation process. The material obtained was characterized by X-ray diffraction and N₂ adsorption?Cdesorption isotherms. Its photocatalytic activity was tested in the degradation of azo dye of leather, Direct Black 38, in aqueous solution under sunlight. The photocatalytic activity of the coupled CeO₂?CSnO₂ oxide ranged depending on the CeO₂ contents. The optimum amount of CeO₂ for the synthesis of CeO₂?CSnO₂ was 7?wt.% since the nanoparticles showed high photocatalytic activity in the degradation of the dye, similar to that of the TiO₂?CP25 photocatalyst. The kinetics of photocatalytic degradation and total organic carbon removal under sunlight were found to follow a first-order rate law. The results indicated that CeO₂?CSnO₂ can be used for the removal of dyes from wastewater.     

TiO2 photocatalytic degradation of tetracycline as affected by a series of environmental factors

Purpose

TiO₂ photocatalytic degradation of tetracycline (TC) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including cations, anions, organic acids, and surfactants.

Materials and methods

The solution of TC with TiO₂ was irradiated by medium mercury lamp. The concentrations of TC and metal ions were analyzed by HPLC and AAS, respectively. The degradation efficiency of TC was calculated based on TC disappearance.

Results and discussion

Photocatalysis was very effective for TC removal. The degradation efficiency of TC was significantly enhanced in the presence of Cu²⁺/Pb²⁺, SO₄ ^2?/Cl^?, and humic acid (HA) in the examined range, but did no change with Ni²⁺, Cd²⁺, or Zn²⁺. In addition, the results also showed that solution Cu²⁺ and Pb²⁺ ions could be reduced during the process, while Ni²⁺, Cd²⁺, and Zn²⁺ were still kept in the solution. However, tannic acid (TA), gallic acid (GA), citric acid (CA), salicylic acid (SA), hydroxypropyl-β-cyclodextrin (HPCD), polyoxyethylene lauryl ether (Brij35), or polyoxyethylenesorbitan monooleate (Tween80) significantly decreased the degradation efficiency of TC.

Conclusions

The photocatalytic approach could be successfully applied to remove TC, and environmental factors significantly influenced its degradation efficiency. It would be useful to understand the environmental behaviors of TC and for the implementation of remediation strategies of TC.     

Advanced Oxidation Processes in Triton X-100 and Wash-up Liquid Removal from Wastewater Using Modified TiO2/Al2O3 Photocatalysts

Photocatalytic methods were applied to remove the recalcitrant or toxic pollutants from the water. The two models of wastewater containing either non-ionic surfactant Triton X-100 or commercially available wash-up liquid were tested in a self-constructed band reactor during the laboratory studies. The photocatalyst, being typed TiO₂, was supported by porous Al₂O₃ and modified by the addition of Cu, Fe, Zn, Ni, Mo or Co. The photocatalysts were characterised by N₂ adsorption?Cdesorption, XRF, XRD, SEM-EDX, Raman and UV?CVis spectroscopy. All catalysts were efficient in the photocatalytic oxidation of surfactants, and they enabled at least 85?% COD reduction. TiO₂/Al₂O₃ photocatalysts modified by the transition metals were efficient only for more complicated compositions of surfactants. The effect of H₂O₂ (0.01?vol.%) addition was also examined and compared with a type of compound and catalyst used??in this case a positive effect for Triton X-100 was only observed over the photocatalyst modified by Ni. When it comes to the wash-up liquid photoremoval, all studied photocatalysts seem to be slightly influenced by H₂O₂ addition. It was also observed that it is not economically justified to conduct such treatment for more than 2?h.     

Synergistic Degradation of Eosin Y by Photocatalysis and Electrocatalysis in UV Irradiated Solution Containing Hybrid BiOCl/TiO2 Particles

The present work focused on treatment of eosin (EO) by photocatalysis (PC) combined with electrocatalysis (EC) process. Bismuth oxychloride/titanium dioxide (BiOCl/TiO₂) hybrid particles, which were used as new heterogeneous photocatalysts, were exploited in a reverse microemulsion approach and were characterized by XRD, UV?CVis diffuse spectra, BET, and SEM technologies. All degradation experiments were performed using a self-assemble experimental setup, in which PC and EC could be carried out simultaneously or individually. The results indicated that BiOCl/TiO₂ showed enhanced photocatalytic performance under UV irradiation, and 50% BiOCl/TiO₂ exhibited the best photoactivity due to its high degree of crystallization, the mesoporous structure and corresponding large special surface area, improved absorption ability in UV region, and the heterojunction formed between two coupling particles. The combined degradation process displayed synergistic effect on the degradation of EO owing to the generation of H₂O₂ at graphite cathode. The parameters such as, pH, reaction current, and initial concentration of EO were monitored in order to optimize the operating conditions. Pseudo-first-order kinetics was proposed and roughly fitted the combined degradation of EO. The combined system in this work suggested a new research idea for the degradation of dye wastewater.     

Efficient Photocatalytic Reduction of CO<Subscript>2</Subscript> Present in Seawater into Methanol over Cu/C-Co-Doped TiO<Subscript>2</Subscript> Nanocatalyst Under UV and Natural Sunlight

Photocatalytic reduction of CO₂ in seawater into chemical fuel, methanol (CH₃OH), was achieved over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. Photocatalysts with different Cu loadings (0, 0.5, 1, 3, 5, and 7 wt%) were synthesized by the sol–gel method and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. Co-doping with C and Cu into TiO₂ remarkably promoted the photocatalytic production of CH₃OH. This improvement was attributed to lowering of bandgap energy, specific catalytic effect of Cu for CH₃OH formation, and the minimization of photo-generated carrier recombination. Co-doped TiO₂ with 3.0 wt% Cu was found to be the most active catalyst, giving a maximum methanol yield rate of 577 μmol g-cat^?1 h^?1 under illumination of UV light, which is 5.3-fold higher than the production rate over C-TiO₂ and 7.4 times the amount produced using Degussa P25 TiO₂. Under natural sunlight, the maximum rate of the photocatalytic production of CH₃OH using 3.0 wt% Cu/C-TiO₂ was found to be 188 μmol g-cat^?1 h^?1, which is 2.24 times higher than that of C-TiO₂, whereas, no CH₃OH was observed for P25.     

Comparative Photocatalytic Performance on the Degradation of 2-Naphthol Under Simulated Solar Light Using α-Bi<Subscript>4</Subscript>V<Subscript>2</Subscript>O<Subscript>11</Subscript> Synthesized by Solid-State and Co-precipitation Methods

In this investigation, the photocatalytic activity of α-Bi₄V₂O₁₁ in the degradation of 2-naphthol under simulated solar light was evaluated. Bismuth vanadate α-Bi₄V₂O₁₁ was synthesized by the solid-state reaction method and by co-precipitation in aqueous media, with the aim of comparing their performance in the photodegradation of the aromatic pollutant. The latter method (co-precipitation) has not been previously reported for the synthesis of α-Bi₄V₂O₁₁. Structural evolution of the oxides precursors was determined by X-ray diffraction. Morphology and optical properties of the solids were analyzed by scanning electron microscopy (SEM) and UV-vis diffuse reflectance spectroscopy (UV-vis), respectively. The results showed that at 800 °C, only α-Bi₄V₂O₁₁ was formed in both preparations. The SEM micrographs revealed that the powders were composed of agglomerates with sizes between 0.8–2 μm for those synthesized by co-precipitation and 2–10 μm for those obtained by solid-state reaction. The optical properties indicated that α-Bi₄V₂O₁₁ was activated with visible light during the photocatalytic process. The photocatalytic degradation of 2-naphthol was largely influenced at basic pH, degrading 79% of the contaminant in 240 min, with the powder obtained by co-precipitation; meanwhile, for the solid-state preparation, the degradation reached only 55%.