紫外—双氧水和亚铁离子体系对硝基苯光降解的研究

研究了以５００Ｗ直管高压汞灯为光源，在双氧水和亚铁离子的体系中，对硝基苯进行光降解的可能性。结果表明，在实验条件下，本系统对硝基苯有明显的降解效果。浓度为５０ｍｇ／Ｌ的硝基苯经过６０ｍｉｎ的光照，其降解率可达９１．７％。此外，还探讨 铁离子浓度、双氧水浓度、硝基苯浓度、ｐＨ值等因素对光降解的影响。     

水泥负载TiO2光催化降解染料水溶液的研究

研究了以ＴｉＯ２为催化剂，且将ＴｉＯ２涂布在模拟工业水处理浅池的水泥质池底表面，以直管高压汞灯为光源，对有机染料酸性玫瑰红Ｂ和晒化绿Ｂ进行光催化降解的可行性。结果表明，在实验条件下，本系统对以上染料有显著的光降解作用，浓度为２５ｍｇ／Ｌ的上述二种染料溶液，经３０ｍｉｎ光照，其降解率分别达８８．２％，此外，还探讨了染料浓度，染料体积、染料溶液ＰＨ值等因素对光降解的影响。     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.     

TiO2–PANI/Cork composite: A new floating photocatalyst for the treatment of organic pollutants under sunlight irradiation

A novel photocatalyst based on TiO_2–PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline(PANI)–modified TiO_2 on cork. The TiO_2–PANI/Cork catalyst shows the unique feature of floating on the water surface. The as-synthesized catalyst was characterized by X-ray diffraction(XRD),scanning electron micrograph(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), Fourier transform infrared spectroscopy(FT-IR), UV–vis diffuse reflectance spectra(UV–vis DRS) and the Brunauer–Emmett–Teller(BET) surface area analysis. Characterization suggested the formation of anatase highly dispersed on the cork surface. The prepared floating photocatalyst showed high efficiency for the degradation of methyl orange dye and other organic pollutants under solar irradiation and constrained conditions, i.e., no-stirring and no-oxygenation. The TiO_2–PANI/Cork floating photocatalyst can be reused for at least four consecutive times without significant decrease of the degradation efficiency.     

UV/H_2O_2/草酸高铁铵体系中孔雀石绿的光降解研究

研究了UV/H2O2/草酸高铁铵体系下孔雀绿(Malachite green,MG)光降解过程中的影响因素,包括MG的初始浓度、初始pH值、投加H2O2浓度和草酸高铁铵浓度等。结果表明:MG初始浓度越低光降解越快,碱性条件有利于MG的降解,其最佳降解pH为11.0;随H2O2浓度的增加,MG降解率先增加后减少,在100mmol/L时,降解率最高;MG降解率随草酸高铁铵浓度增加而增加,于10.0mmol/L时MG降解率最高;UV/H2O2/草酸高铁铵体系的降解效果较强,交叉实验结果表明H2O2:草酸高铁铵浓度比在1～20:1时降解率均高于。因此该体系具有快速、简单、经济并高效率等特点,可应用于染料废水的降解和脱色工艺中。     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Photodegradation of sulfonamide antibiotics in simulated and natural sunlight: Implications for their environmental fate

The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.     

Photodegradation of quinestrol in waters and the transformation products by UV irradiation

Quinestrol is synthetic estrogen used in contraceptive and hormone replacement therapy and occasionally for treating breast cancer and prostate cancer. It can make its way into the environment through sewage discharge and waste disposal produced by human excretions. In this study, the photodegradation kinetics of quinestrol in various conditions was investigated by UV and solar irradiation. The affecting factors were studied including concentration of hydrogen peroxide, different water types, and the initial concentrations of quinestrol. Concurrently, the transformation products and presumed pathways of quinestrol in distilled water by UV irradiation were identified and proposed. The results showed that the degradation of quinestrol in both irradiation conditions followed the pseudo-first-order kinetics. More rapid degradation was observed by UV irradiation (k = 0.018 min⁻¹) than solar irradiation (k = 0.004 h⁻¹), and the photodegradation rate of quinestrol depended on the concentration of hydrogen peroxide, the initial concentration of quinestrol and water types. The transformation products of quinestrol in distilled water were identified by gas chromatography/mass spectrometry. When exposed to UV irradiation, quinestrol in aqueous solution was rapidly degraded, giving at least ten photodegradation products. The chemical structures of ten degradation products were identified on the basis of mass spectrum interpretation and literature data.     

Photodegradation of tetraphenyltin contained in polychlorinated biphenyl-based transformer oil simulants in alkaline 2-propanol solution

The photodegradation of tetraphenyltin (TePT) contained in polychlorinated biphenyl (PCB)-based transformer oil simulants by ultraviolet (UV) irradiation in alkaline 2-propanol solutions was examined. In the absence of PCBs, the TePT level fell to below 1% of the initial concentration within 30 min. In the absence of both PCBs and an alkali, the concentrations of tri-, di-, and monophenyltins initially increased to a few milligrams per liter, and then reduced to below the detection limits within 90 min. The addition of an alkali to the reaction solution slightly accelerated the photodecomposition of TePT. The decomposition of other phenyltins (PTs) was also accelerated. When PCBs with concentrations of approximately 80 times the initial TePT concentration were added, only a small fraction of the TePT decomposed within 100 min. Moreover, the levels of PTs did not change during irradiation. TePT and other PTs did decompose when the level of PCBs was reduced to the same concentration as that of TePT; however, the decomposition rates were slower than those in the absence of PCBs. In the actual treatment process, TePT and other PTs in PCB-based transformer oil are decomposed by catalytic reduction, which is used after UV irradiation. Therefore, in the actual treatment of PCB-based transformer oil wastes, pollution due to PTs can be prevented.     

Synthesis, crystal structure, photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c= 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^-1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2- and NO₃^-, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography- mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.