Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: an experimental and theoretical examination of hydrazine derivatives

The photocatalytic oxidation of oxalyldihydrazide, N,N'-bis(hydrazocarbonyl)hydrazide, N,N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N2 gas, NH4+ (and/or NO3-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrazo group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrazo groups were photoconverted mainly into N2 gas (in mineralization yields above 70%) and partially to NH4 ions (below 10%). The formation of NO3- ions was scarcely recognized.     

Photocatalytic degradation of imazethapyr herbicide at TiO2/H2O interface

The photocatalytic degradation of imazethapyr, a herbicide of the imidazolinone family, was investigated in an aqueous suspension of titanium dioxide used as a catalyst. A pseudo-first order kinetic model was employed to discuss the results. The effect of catalyst loading, initial concentration of imazethapyr, hydrogen peroxide, pH value, and temperature were investigated. Imazethapyr disappearance as a function of irradiation time was analyzed by HPLC. The ammonium ion formation was determined spectrophotometrically at 694 nm. The degradation was observed to proceed more favorably at natural pH (ca. 4.4) when the pH was varied in the range from 2 to 11. The addition of hydrogen peroxide to the TiO2 suspension enhanced the degradation rate constant up to 5.0x10(-3) mol l-1, but decreased it at higher concentrations. The degradation rate constants decreased by 19% with a temperature increase from 20 to 40 degrees C in the TiO2 suspension, whereas a 16% increase in imazethapyr direct photolysis was observed for the same temperature range. This behavior indicates the occurrence of physisorption between TiO2 and imazethapyr molecules.     

UV/H2O2工艺降解水中双酚A影响因素的研究

研究了UV/H2O2工艺对双酚A(BPA)的降解效果及影响田素.结果表明,UV/H2O2工艺可以有效降解水体中BPA,降解过程符合一级反应动力学模型;紫外光强对BPA的降解速度影响较小;H2O2浓度对BPA的降解具有促进和抑制的双重作用;BPA初始浓度对BPA降解没有影响;在酸性条件下,有利于BPA降解;NO-3、Cl-、HCO-3对BPA降解有抑制作用;当HCO-3、NO-3、Cl-摩尔浓度均为5mmol/L时,对BPA降解的抑制程度为HCO-3>NO-3>Cl-.腐殖酸在低浓度时,促进BPA降解反应进行;在高浓度时,BPA的降解受到抑制.     

Degradation of bisphenol A using UV and UV/H2O2 processes

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol) is a substance typically used in the plastic industry. It is used in the production of epoxy resins, polycarbonate, or fire retardants or as a stabilizer and an antioxidant in numerous types of plastics. Bisphenol A is introduced into the environment via municipal and industrial wastewater. Because of its hydrophobic properties, BPA has the potential for sorption on activated sludge during the biological wastewater treatment processes. This study investigated the degradation of BPA by means of UV-radiation and in the UV/H2O2 process with the presence and absence of hydrocarbonate ions (HCO3(-)) as hydroxyl radicals (OH*) scavengers. The calculated value of quantum yield was equal to 0.18, and the value of BPA rate constant with hydroxyl radicals was equal to 3.3 x 10(9) M(-1) s(-1).     

Photocatalytic reactions of phenanthrene at TiO2/water interfaces

The photocatalytic oxidation of phenanthrene was investigated in aqueous TiO2 suspensions under UV light irradiation. Chemical oxygen demand (COD) measurements, UV-Vis spectrophotometer, IR spectrometer and gas chromatography-mass spectrometry (GC-MS) analytical techniques were used to monitor the reaction process. Some factors affecting the photodegradation rate were studied and some aromatic intermediates were detected during the reaction process. Fast and complete mineralization of phenanthrene was achieved in this reaction system.     

Photocatalytic reactions of pyrene at TiO2/water interfaces

The photocatalytic oxidation of pyrene preadsorbed on TiO2 is examined in aqueous suspension under UV irradiation. Chemical oxygen demand measurements, UV-VIS spectrophotometer, infrared spectrometer and GC-MS analytical techniques were used to monitor the formed intermediates. During the oxidation processes, the ring-open reaction, hydroxylation and ketolysis occurred to produce some intermediate products (4-oxapyrene-5-one, 1,6- or 1,8-pyrenediones, 4,5-phenanthrenedialdehyde, cyclopenta[def]phenanthrene). Some factors affecting the photodegradation rate were also studied. The results were different from other studies: The pH of the dispersion, ratio of Py/TiO2:water had little effect on the photooxidation rate of pyrene catalyzed by TiO2, while the surface coverage, addition of Fe3+ affected it greatly.     

UV/H2O2/草酸铁络合物光降解邻苯二甲酸二丁酯研究

研究了邻苯二甲酸二丁酯(DBP)在UV/H2O2/草酸铁络合物体系中的光降解.结果表明,UV/H2O2/草酸铁络合物能有效地光解DBP;在pH值为4时,DBP光解速率最快,中性和碱性条件下光解效率降低;DBP的光解速率随H2O2浓度的升高而增大,但H2O2浓度较大时,其对·OH的清除作用使DBP的光解速率减慢;[Fe3 ]/[C2O42]＜1/10,DBP光解速率随Fe3 浓度增大明显提高,[Fe3 ]/[C2O42]＞1/10时,引起DBP光解速率的增加不明显.     

Degradation of bisphenol A by the UV/H2O2 process: a kinetic study

A theoretical and experimental study of bisphenol A (BPA) degradation by the UV/H₂O₂ process in water is presented. The effects of the H₂O₂ concentration and the specific rate of photon emission (E_P,0) on BPA degradation were investigated. A kinetic model derived from a reaction sequence was employed to predict BPA and hydrogen peroxide concentrations over time using an annular photochemical reactor in batch recirculation mode. The local volumetric rate of photon absorption (LVRPA) inside the photoreactor was computed using a Line Source with Parallel Plane emission model (LSPP). From the proposed kinetic model and the experimental data, the second order rate constants of the reactions between hydroxyl radicals and the main reacting species (H₂O₂ and BPA) were estimated applying a nonlinear regression method. A good agreement between the kinetic model and experimental data, for a wide range of operating conditions, was obtained. For BPA, H₂O₂, and TOC concentrations, the calculated root means square errors (RMSE) were 2.3?×?10^??2, 9.8?×?10^??1, and 9.0?×?10^??2 mmol L^??1, respectively. The simplified kinetic model presented in this work can be directly applied to scaling-up and reactor design, since the estimated kinetic constants are independent of the reactor size, shape, and configuration. Further experiments were made by employing low BPA initial concentration (100 μg L^??1) in water and real wastewater. A lower degradation rate of BPA was observed in the real wastewater, although the UV/H₂O₂ process has also been able to completely degrade the target pollutant in less than 1 h.

     

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo₂O₄ and TiO₂ were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo₂O₄/TiO₂/GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo₂O₄/TiO₂/GO dosage, and H₂O₂ concentration on BPA degradation. In a system with 0.5 g L⁻¹ of FeCo₂O₄/TiO₂/GO and 10 mmol L⁻¹ of H₂O₂, approximately 90 % of BPA (20 mg L⁻¹) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo₂O₄/TiO₂/GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸（4-CBA）和喹啉的试验研究.研究表明,（1）在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;（2）在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;（3）二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸(4-CBA)和喹啉的试验研究.研究表明,(1)在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;(2)在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;(3)二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

常见阴离子对TiO2/H2O2/O3体系氧化效能的影响

酸性条件下考察了常见阴离子对TiO2/H2O2/O3氧化效率的影响,目标化合物为羟基自由基的探针化合物乙酸。结果表明,硫酸根和硝酸根对体系氧化乙酸的效率几乎没有影响。加入磷酸盐可以减缓H2O2的分解速率,进而导致乙酸的降解效率下降,这可能与其在TiO2表面的吸附作用有关。在初始pH为3.0时,氯离子对子乙酸的降解速率具有明显的抑制作用,氯离子浓度越高,抑制作用越明显。当溶液初始pH大于4.4以上时,氯离子对乙酸的降解效率几乎没有影响。以上结果对推动TiO2/H2O2/O3体系处理酸性废水意义较为突出。     

一种光催化体系光催化降解苯胺的研究

以钛酸丁酯为原料．以膨润土为载体,用酸性溶胶法合成TiO2纳米复合物,并利用该复合物作催化剂,在H2O2存在下进行光催化降解苯胺溶液。结果表明,该催化剂在UV／H2O2系统中对苯胺溶液有很好的光催化降解效果,其效果优于纯TiO2;H2O2的存在提高了苯胺光催化降解速率,在本实验条件下其最佳摩尔浓度是5mmol／L;溶液pH是影响反应速率的重要因素．pH在中性范围内具有更强的光催化活性;该体系中苯胺能够有效地被降解,其光催化反应遵循一级反应动力学规律。     

Visible-light-induced photocatalytic reduction of Cr(VI) with coupled Bi2O3/TiO2 photocatalyst and the synergistic bisphenol A oxidation

Coupled Bi₂O₃/TiO₂ photocatalysts were fabricated by sol–gel and hydrothermal methods and characterized using various spectroscopy techniques. Photocatalytic reduction of Cr(VI) in aqueous solution, together with the synergistic effect of photodegradation of bisphenol A (BPA), was investigated using these coupled Bi₂O₃/TiO₂ under visible-light irradiation. Coupling of Bi₂O₃ inhibited the phase transformation from anatase to rutile and extended absorption region to visible light. Bi ions did not enter TiO₂ lattice and were more likely to bond with oxygen atoms to form Bi₂O₃ on the surface of TiO₂. Photovoltage signals in visible range revealed the effective interfacial charge transfer between Bi₂O₃ and TiO₂. Two percent Bi₂O₃/TiO₂ exhibited the highest photocatalytic activity of visible-light-induced reduction of Cr(VI). The addition of BPA effectively increased the photocatalytic reduction of Cr(VI). Simultaneously, the presence of Cr(VI) promoted the degradation of BPA, which was demonstrated by the investigation of TOC removal yield and generated intermediates. A possible mechanism of photocatalytic reduction of Cr(VI) and degradation of BPA in Bi₂O₃/TiO₂ system was proposed. The synergistic effect, observed between reduction of Cr(VI) and degradation of BPA, provides beneficial method for environmental remediation and purification of the complex wastewater.     

O3／H2O2高级氧化技术H2O2加入量的简易控制方法

对与臭氧有着不同反应活性的3类有机污染物，探讨并建立了O3／H2O2高级氧化技术H2O2较优投加量的简易控制方法。结果表明，水中存在溶解臭氧是H2O2与臭氧降解效率具有协同作用的必要条件，另外，H2O2的较优加入量直接依赖于目标有机污染物与臭氧的反应活性。对于不同的有机物及在常规的臭氧化水处理时间内，H2O2加入量控制在单独臭氧化处理时水中溶解臭氧的20-30倍（质量比）之间为宜。这种简易控制H2O2加入量的方法对推广O3／H2O2技术在实际废水处理中的应用具有重要的意义。     

O3/H2O2高级氧化技术H2O2加入量的简易控制方法

对与臭氧有着不同反应活性的3类有机污染物,探讨并建立了O3/H2O2高级氧化技术H2O2较优投加量的简易控制方法.结果表明,水中存在溶解臭氧是H2O2与臭氧降解效率具有协同作用的必要条件,另外,H2O2的较优加入量直接依赖于目标有机污染物与臭氧的反应活性.对于不同的有机物及在常规的臭氧化水处理时间内,H2O2加入量控制在单独臭氧化处理时水中溶解臭氧的20～30倍(质量比)之间为宜.这种简易控制H2O2加入量的方法对推广O3/H2O2技术在实际废水处理中的应用具有重要的意义.     

超声和H2O2对双酚A模拟废水的毒性源头消减

对含双酚A模拟废水处理的序列间歇式活性污泥法(SBR)活性污泥系统,进行分别以超声破碎和投加H2O2氧化两种模式的污泥源头处理。分别以发光菌表征的微生物毒性和种子发芽率表征的植物毒性来衡量污泥毒性,通过对照污泥经源头处理前后的水相指标变化和以酶活性表征的污泥特性变化,考察污泥源头处理模式对污泥毒性消减效果和对污泥特性的影响。结果表明,污泥经源头处理后超声组污泥毒性最大,而H2O2组污泥毒性最小,空白组污泥毒性居中。种子发芽率表征的植物毒性与发光菌表征的微生物毒性成正相关关系。污泥经超声和H2O2源头处理后的脱氢酶活性和过氧化氢酶活性的变化趋势与污泥毒性显著相关。     

UV／TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜，研究了UV-Vis／TiO2以及UV／TiO2／H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明，TiO2在暗处对酞酸酯没有降解作用；UV／TiO2体系能有效光降解DBP和DEHP，TiO2具有明显的光催化作用，增强因子分别为，fDBP=2．06，fDEHP=1．53；在一定浓度范围内DBP在UV／TiO2体系中的降解速率与其初始浓度成负一级动力学关系；UV／TiO2／H2O2体系对DBP的光降解能力远大于UV／TiO2和UV／H2O2体系，H2O2能显著提高TiO2的光催化活性。     

UV/TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜,研究了UV-V is/TiO2以及UV/TiO2/H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明,TiO2在暗处对酞酸酯没有降解作用;UV/TiO2体系能有效光降解DBP和DEHP,TiO2具有明显的光催化作用,增强因子分别为fDBP=2.06,fDEHP=1.53;在一定浓度范围内DBP在UV/TiO2体系中的降解速率与其初始浓度成负一级动力学关系;UV/TiO2/H2O2体系对DBP的光降解能力远大于UV/TiO2和UV/H2O2体系,H2O2能显著提高TiO2的光催化活性。