Phenol photonitration upon UV irradiation of nitrite in aqueous solution I: effects of oxygen and 2-propanol.

Nitrophenols are formed in aqueous solution upon UV irradiation of phenol and nitrite. The formation of nitrophenols is enhanced by dissolved oxygen and inhibited by the addition of 2-propanol. The mechanism of phenol photonitration involves both .NO2 (or N2O4, reacting with phenol, and 4-nitrosophenol, which is oxidised to 4-nitrophenol. A reaction scheme is proposed based on experimental results.     

Formation of nitrophenols upon UV irradiation of phenol and nitrate in aqueous solutions and in TiO2 aqueous suspensions.

The formation of nitrophenols was studied as a consequence of ultra violet (UV) irradiation of aqueous solutions of phenol and nitrate in the range of pH 1-12. The study was performed both in homogeneous phase and in the presence of water-suspended TiO2. The effects of pH, dissolved oxygen and 2-propanol as .OH scavenger have been evaluated. A reaction mechanism is proposed, based on the experimental results.     

On the effect of pH in aromatic photonitration upon nitrate photolysis

This paper studies the pH effect on the photonitration of catechol, 1-naphthol, naphthalene, and benzene. The pH trend is influenced by the generation of HNO(2) and peroxynitrous acid (HOONO) upon nitrate photolysis. HNO(2) can be involved in a direct and an indirect nitration process. Direct nitration follows the pH distribution of HNO(2) (flexus around 3). Indirect nitration, possibly involving nitrosation+oxidation, would be highest around pH3. HOONO can be involved in electrophilic nitration, where the initial formation rate of the nitroderivatives is proportional to [H(+)], or take part in nitration directly, in which case a less important pH effect in photonitration is observed. The relative importance of the various nitration pathways for each substrate determines the resulting pH effect in photonitration upon nitrate photolysis.     

Photocatalytic degradation of AZO dyes by supported TiO2 + UV in aqueous solution

The photocatalytic degradation performance of photocatalysts TiO2 supported on 13-X, Na-Y, 4A zeolites with different loading content was evaluated using the photocatalytic oxidation of dyes direct fast scarlet 4BS and acid red 3B in aqueous medium. The results showed that the best reaction dosage of TiO2-zeolite catalysts is about 2 g/l and the photocatalytic kinetics follows first order for all supported catalysts. The photocatalytic activity order of the three series catalysts is 13X type >Y type >4A type. The physical state of titanium dioxide on the supports is evaluated by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD), BET, and FTIR.     

UV/TiO2光催化降解水体中的邻苯二甲酸二甲酯

酞酸酯是环境中普遍存在的有机污染物(内分泌干扰物)之一。利用UV/TiO2光催化降解水体中的邻苯二甲酸二甲酯(DMP),讨论了溶液pH、TiO2投加量及DMP初始浓度等因素对DMP降解的影响。结果表明,DMP为10mg/L左右时,TiO2投加量为0.2～0.5g/L、pH=7是比较理想的降解条件;DMP初始浓度越高,其降解率则越低。研究了Langmuir-Hinshelwood模式下DMP在TiO2表面的吸附与催化活性的关系,发现DMP主要通过吸附在催化剂的表面而非在溶液本体中发生降解。线性回归计算所得光照条件下的吸附常数远大于无光照条件下的吸附常数,可能是由于UV和TiO2体系之间产生协同效应,提高了UV/TiO2体系对DMP的降解效果。另外,初步分析了可能的降解反应机制。     

Degradation pathways of PCBs upon UV irradiation in hexane.

The photodegradations of eight individual PCB congeners (5, 31, 52, 77, 87, 126, 138, 169) in hexane have been investigated employing a mercury lamp. All degradation reactions of the above mentioned PCB congeners are of the pseudo first order. The principal products of PCB decomposition are the less chlorinated biphenyls, and no PCB-solvent adducts are found. Symmetrical and coplanar PCB congeners show lower photoreactivities. The reactivities of the chlorine atoms at various positions of PCB rings are generally in the order: ortho > meta > para. Photodechlorinations occur mainly on the more substituted rings, when the numbers of chlorine atoms on the two phenyl rings are unequal. During photodegradation, some coplanar PCB congeners are formed, which make the TEQ of solutions to decrease slowly or even to increase.     

Photolysis of PAHs in aqueous phase by UV irradiation.

The photooxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated in an aqueous ethanolic solution irradiated with a medium-pressure mercury lamp in laboratory photoreactors equipped with a quartz immersion well. Degradation photolysis of fluorene was more efficient than sensitized photolytic oxidation in the presence of TiO2 suspensions. Photolysis kinetics was dependent on molecular weight and the presence and type of substituents. During the photolytic degradation of fluorene and its derivatives, 9-fluorenone and its corresponding derivatives, which were more resistant to photolysis, were formed.     

Radiolysis of aqueous phenol solutions with nanoparticles. 1. Phenol degradation and TOC removal in solutions containing TiO2 induced by UV,gamma-ray and electron beams

Aqueous phenol solutions containing TiO(2) nanoparticles were irradiated with ultraviolet (UV), gamma-ray and electron beams. Organic compounds were fully removed by each type of radiation in the presence of the particles. The absorbed energy of the ionizing radiation (gamma-ray and electron beams) needed for removal was much lower than that of UV photocatalysis. Phenol was decomposed by the ionizing radiation in the absence of the nanoparticles and the addition of TiO(2) had no significant effect on phenol decomposition rate. Instead, total organic carbon (TOC) removal using the ionizing radiation was accelerated drastically by TiO(2). It is suggested that TiO(2) particles affect the intermediate compounds produced through the decomposition of phenol. The amount of removed TOC per absorbed energy were compared in the absence and the presence of TiO(2) nanoparticles. Radiolysis with the nanoparticles showed consistently high rate and high efficiency of TOC removal.     

Decomposition of 2-nitrophenol in aqueous solution by ozone and UV/ozone processes.

The decomposition of 2-nitrophenol in aqueous solutions by ozone and UV/ozone processes was found to be technically feasible under adequate experimental conditions. Formation of nitrate ions was observed following the decomposition of 2-nitrophenol by ozone and UV/ ozone processes. Increasing ozone dosage and UV light intensity accelerated the decomposition rate of 2-nitrophenol in an aqueous solution. The species distribution of 2-nitrophenol under various solution conditions plays a significant role in determining decomposition behavior. In most experiments conducted in this study, the decomposition of 2-nitrophenol by ozone and UV/ozone processes was favored to occur in alkaline conditions. The addition of 2-butanol accelerated the rate of gaseous ozone transfer to an aqueous phase by reducing the surface tension of aqueous solution and therefore enhancing the decomposition rate of 2-nitrophenol by ozone and UV/ozone processes.     

The pH and anion effects on the heterogeneous photocatalytic degradation of o-methylbenzoic acid in TiO2 aqueous suspension

This investigation used UV light of 365 nm and titanium dioxide in aqueous suspension to study the photocatalytic reaction of o-methylbenzoic acid under the influence of pH values, anion additives and the varieties of titanium dioxide. From experimental results, under the condition of 5 g/l TiO2, pH 3 and light intensity of 2.45 mW/cm2, 0.1 mM of o-methylbenzoic acid could be completely decomposed in 2 h. The reaction was faster with lowering pH, and was found to be apparent first-order following Langmuir-Hinshelwood model. In the presence of anion additives, the inhibitive effect of chloride ions was larger than that of sulfate ions under acidic condition for Degussa brand titanium dioxide, but without influence using Janssen brand. Both brands, however, promoted the mineralization of o-methylbenzoic acid (o-MBA).     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO2 aqueous solution

5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO₂ heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.     

Photochemical nitrosation of dimethylamine in aqueous solution containing nitrite

Dimethylamine was found to be nitrosated photochemically in aqueous solution containing nitrite both by the irradiation with a high pressure mercury lamp and by the exposure to sunlight to give nitrosodimethylamine, a well-known carcinogen. The nitrosation occurred more readily at alkaline pH than at acidic and neutral pH. These findings suggest that nitrosodimethylamine is produced photochemically under natural environmental conditions.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

水中安替比林的紫外光降解研究

以波长为254 nm的紫外杀菌灯为光源,研究了水溶液中消炎镇痛药物安替比林（PZ）的光降解行为;考察了初始pH值及水中其他物质对PZ光降解的影响,探讨了PZ光解机制,并分析其降解产物及光解途径。结果表明,安替比林的光降解遵循拟一级反应动力学规律,pH值变化对光解速率基本没有影响。安替比林直接光降解占主导作用,活性氧类物种（ROS）对安替比林间接光解基本没有贡献。腐殖酸对安替比林光降解有抑制作用,而NO^-₃,HCO^-₃,Cl^-对安替比林光降解没有明显作用。GC-MS分析表明安替比林在紫外辐射下生成甲酰胺,乙酰胺,2-羟基吲哚-3-酮,2,4（1氢,3甲基）-喹唑啉二酮,1-甲基-2-羟基苯并咪唑,2-羟基苯并恶唑等一系列具有安替比林母体苯环结构的化合物,表明安替比林侧链上N—N键断裂导致其最终降解。     

Photochemical and photocatalytic degradation of gaseous toluene using short-wavelength UV irradiation with TiO2 catalyst: comparison of three UV sources

The feasibility of the use of short-wavelength UV (254+185 nm) irradiation and TiO2 catalyst for photodegradation of gaseous toluene was evaluated. It was clear that the use of TiO2 under 254+185 nm light irradiation significantly enhanced the photodegradation of toluene relative to UV alone, owed to the combined effect of photochemical oxidation in the gas phase and photocatalytic oxidation on TiO2. The photodegradation with 254+185 nm light irradiation was compared with other UV wavelengths (365 nm (black light blue lamp) and 254 nm (germicidal UV lamp)). The highest conversion and mineralization were obtained with the 254+185 nm light. Moreover, high conversions were achieved even at high initial concentrations of toluene. Catalyst deactivation was also prevented with the 254+185 nm light. Regeneration experiments with the deactivated catalyst under different conditions revealed that reactive oxygen species played an important role in preventing catalyst deactivation by decomposing effectively the less reactive carbon deposits on the TiO2 catalyst. Simultaneous elimination of photogenerated excess ozone and residual organic compounds was accomplished by using a MnO2 ozone-decomposition catalyst to form reactive species for destruction of the organic compounds.     

Superior photodecomposition of pyrene by metal ion-loaded TiO2 catalyst under UV light irradiation

Background

The photocatalytic degradation of pyrene under UV (125?W Hg-Arc, 10.4?mW/cm²) irradiation of TiO₂ aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu²⁺, Fe³⁺, Ag⁺, and Au³⁺, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1?eV) of TiO₂, the photoexcited electron transfer occurs more readily and reduces electron?Chole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO₂ because of rapid Fermi energy equilibrium between the CB of TiO₂ and its surface adsorbed metal ions.

Results and discussion

The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni²⁺ having more negative reduction potential (?0.25?eV) than the CB of TiO₂ imparts negligible co-catalytic activity to TiO₂ photoreaction. It also revealed that loading of Au³⁺ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe⁺³ and Au³⁺ ions gradually increases from 0.1 to 2?wt.%, the pyrene photodecomposition rate also become faster.     

Surfactant-assisted adsorption of uranyl ions in aqueous solution on TiO2/polythiophene nanocomposite

In this work, hexadecyltrimethylammonium-bromide (HTAB)-modified polythiophene (PTh)/TiO₂ nanocomposite (HTAB/PTh/TiO₂) was applied to remove uranyl ions (UO₂²⁺). FT-IR, XRD, ζ potential, TGA, SEM, and XPS were utilized to obtain the chemical and physical properties of HTAB/PTh/TiO₂. The effects of HTAB content, preparation temperature, and adsorption conditions on UO₂²⁺ removal were investigated comprehensively. And the UO₂²⁺ adsorption process on HTAB/PTh/TiO₂ was fitted to the Sips model with a saturated adsorption capacity of 234.74 mg/g, which was 6 times over TiO₂. The results suggested that the surfactant of HTAB can significantly improve the adsorption ability of TiO₂ for UO₂²⁺ ions. This work provides a strategy of surfactant modification for enhancing the separation and recovery ability of adsorbent toward UO₂²⁺ in the radioactive wastewater.

     

Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode

Titanium dioxide (TiO2) nanotube film electrodes are fabricated by the anodic oxidation method. Scanning electron microscopy (SEM) showed that these tubes were well aligned and organized into high-density uniform arrays. XRD analysis showed the TiO2 nanotubes to be in the anatase crystal form. The TiO2 nanotube film electrode exhibited increased photoelectrocatalytic (PEC) capability compared to a traditional TiO2 film electrode fabricated using the anodizing method for pentachlorophenol (PCP) degradation in aqueous solution. The bias potential, pH value, and electrolyte concentration were shown to be important factors influencing the degradation of PCP by the PEC method using the TiO2 nanotube film electrode as the working electrode.     

Photodegradation of perfluorooctanoic acid by synthesized TiO2-MWCNT composites under 365nm UV irradiation

Degradation of perfluorooctanoic acid (PFOA) is of great importance due to its global distribution, persistence and toxicity to bioorganisms. In present study, a composite TiO₂ with multiple wall carbon nano-tubes (MWCNTs) was synthesized using sol-gel method and it was used as photocatalyst to degrade PFOA in water. The prepared composite catalyst displayed significant absorption in UV to visible light region. The loading content of TiO₂ on MWCNTs could be adjusted by changing the ratio of precursor to MWCNTs. Due to the combined effect of the adsorption ability and e⁻ transport capacity of MWCNT, the composites displayed much higher photocatalytic ability to PFOA as compared to pure TiO₂ under UV irradiation. The photocatalyst prepared with 10:1 of tetrabutyl titanate/MWCNT was the most effective. With the optimal dosage at 1.6 g L⁻¹, almost 100% of PFOA was degraded in acid medium after irradiation for 8 h. It was proposed that PFOA were mainly degraded by stepwise losing a moiety of CF₂.