Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

Degradation of short-chain alkyl- and alkanolamines by TiO2- and Pt/TiO2-assisted photocatalysis

The photooxidation of C2H5NH2, (C2H5)2NH, HOC2H4NH2, (HOC2H4)2NH and (HOC2H4)3N using TiO2 and Pt/TiO2 as photocatalysts has been investigated. A laboratory set up was designed and a study on the influence of the concentration of the photocatalyst, the pH-value and the structure of the amine performed. The photocatalytic process was optimized with respect to the concentrations of the model substances during degradation. The decrease of the amine concentrations was found to be maximum at a pH of 10. The time-dependence of the formation of cationic breakdown products, such as NH3/NH4 and short-chain alkyl- and alkanolamines was studied by analyses with single column ion chromatography. The experimental data show that the photodegradation follows a Langmuir-Hinshelwood kinetic. The mineralization of the model substances also was monitored by measurements of the decrease of the TOC and of the formation of NO2 and NO3. The different mineralization efficiencies for the model substances studied are discussed with regard to their structure and adsorption behaviour on the photocatalyst. A possible breakdown mechanism involving the electrophilic attack of the hydroxyl radical is given. The applicability of the TiO2-assisted photocatalytic degradation of C2H5NH2 and (C2H5)2NH was tested at the pilot plant-scale with real solar radiation. The degradation rates and products obtained were similar to those found in the laboratory experiments.     

Photocatalysis of fluorene adsorbed onto TiO2

The adsorption of fluorene onto TiO2 has been investigated by conducting equilibrium and kinetic experiments. Adsorption isotherms have been evaluated at two different pHs in the range of temperatures 296-325 K. The type III isotherm shapes obtained were modelled by considering several expressions taken from the literature. Temperature exerted a positive influence in fluorene uptake. Addition of phosphates involved a negative effect when computing the final equilibrium fluorene removal. The kinetic experiments carried out at 296 K corroborated the competitiveness of phosphates to occupy the active sites on the titania surface. Nevertheless, equilibrium conditions are faster achieved at pH 2 than at pH 5. The photocatalysis of fluorene at different initial concentrations of the parent compound revealed a slight improvement of the process at pH 5 if compared to the results obtained at pH 2. A Langmuir-Hinselwood representation of the data confirms the previous statement. Catalyst load shows an optimum, concentration values of the photocatalyst above the optimum provoke a decrease in the fluorene abatement rate. Reutilisation of the catalyst indicates that fluorene is completely eliminated from the solid, i.e. it is suggested that fluorene and intermediates are surface oxidised.     

Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles

Fe-doped TiO₂ was prepared by the calcination of Fe_xTiS₂ (x = 0, 0.002, 0.005, 0.008, 0.01) and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible diffuse reflectance spectra. All the Fe-doped TiO₂ were composed of an anatase crystal form and showed red shifts to a longer wavelength. The activity of the Fe-doped TiO₂ for the degradation of phenol was investigated by varying the iron content during UV (365 nm) and visible light (405 nm and 436 nm) irradiation. The degradation rate depended on the Fe content and the Fe-doped TiO₂ was responsive to the visible light as well as the elevated activity toward UV light. The molar ratio of 0.005 was the optimum for both the UV and visible light irradiations. The result was discussed on the basis of the balance of the excited electron–hole trap by the doped Fe³⁺ and their charge recombination on the doped Fe³⁺ level. The Fe-doped TiO₂ (x = 0.005) was more active than P25 TiO₂ under solar light irradiation. The suspended Fe-doped TiO₂ spontaneously precipitated once the stirring of the reaction mixture was terminated.     

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.     

Dissolution studies on TiO2 with organics

In this work the effect of organic reducing reagents, namely, ascorbic acid, oxalic acid and L-cysteine on dissolution of commercial TiO(2) has been investigated. Kinetic studies showed that a maximum of about 45% of TiO(2) was dissolved by ascorbic acid in 4h when oxide:acid molar ratio was kept at 1:2. The dissolution of TiO(2) increased with increase in ascorbic acid and oxalic acid concentration up to 0.15M in 4h (corresponding to molar ratio of oxide to acid of 1:3) and further addition did not affect the dissolution. Nearly 45% TiO(2) dissolution was obtained with ascorbic acid alone while oxalic acid yielded 40% dissolution. When oxalic acid was added along with ascorbic acid in equi-molar concentrations, dissolution of TiO(2) was enhanced to 60% in 2.5h but when cysteine was added to ascorbic acid the dissolution was about 50% in just 1h.     

TiO2光催化剂在污水处理中的应用

在污水处理方面TiO2光催化剂以其独特的氧化活性、光学性能和无机化能力引起了人们极大的关注.对TiO2光催化原理、农药、染料和环境荷尔蒙等有机污染物的分解,提高催化效率的方法以及其实用技术等方面,分别作了综合评述.     

TiO2半导体光催化反应器的研究进展

光催化氧化作为一种高级氧化技术,在环境污染控制方面得到了较快的发展.主要介绍了国内外近年来有关光催化反应中其反应器的设计与研究进展情况,按催化剂在反应器中的存在状态分类论述了各种反应器的结构原理和主要特点,以及反应器在设计中存在的问题和今后发展的方向.     

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.     

Solar heterogeneous photocatalytic degradation of phenol on TiO2/quartz and TiO2/calcite: a statistical and kinetic approach on comparative efficiencies towards a TiO2/glass system

Environmental Science and Pollution Research - Phenol is a widely used synthetic organic compound, which according to global estimations, is discharged into the environment at a rate of 10...     

掺Ni2+的TiO2颗粒光催化性能的研究

通过溶胶-凝胶法制备掺杂Ni2 的纳米TiO2,并用XRD和TEM进行了表征,发现Ni2 的掺杂减小了TiO2颗粒的粒径,Ni2 /TiO2晶型为锐钛型.通过对目标物罗丹明B的光催化降解实验,发现Ni2 的掺杂提高了TiO2的光催化活性,其降解罗丹明B的反应遵从一级反应动力学方程,Ni2 惨杂量为1.2%时的光催化活性最高.     

Photocatalytic degradation of pentachlorophenol on TiO2 sol-gel catalysts

The photocatalytic degradation of pentachlorophenol (PCP) in aqueous solution was investigated using TiO2 catalysts. The samples were prepared by the sol-gel method using different gelation pH and different calcination temperatures. The solids were characterized by specific surface area, X-ray diffraction, UV-Vis absorbance, FTIR and pentachlorophenol adsorption. The catalytic activity of the solids was evaluated in a conventional photoreactor at 298 K using 30 ppm of pentachlorophenol. It was found that the reaction follows a first-order reaction and the kinetic constant values change slightly with the pH of gelation and more significantly with the calcination temperature.     

溴掺杂TiO2光催化剂的制备与性能研究

以KBr和Ti（SO4）2为原料,通过水热法制备了高催化活性的溴掺杂纳米TiO2（Br-TiO2）光催化剂,利用XRD、XPS、TEM、BET和UV-Vis DRS等测试手段对其进行了表征。通过苯酚降解实验评价了Br-TiO2的光催化活性。结果表明,700℃焙烧、溴与钛的摩尔比为0.35∶1时,Br-TiO2具有最佳光催化活性。该催化剂为晶体发育完整的锐钛矿相TiO2,粒径平均大小为50 nm,比表面积为16.81 m2/g,在紫外区的吸收得到加强,光催化能力优于Degussa P-25。确定了降解苯酚的最佳条件：催化剂投加量为0.5 g/L,苯酚初始浓度为10 mg/L,pH值为6.0。     

TiO2／SiO2催化剂可见光降解偶氮染料的研究

以多孔硅胶作载体.通过酸性溶胶法制备了TiO2/SiO2催化剂.采用X射线衍射(XRD)、热重一差热分析(TG-DTA)、扫描电镜(SEM)和BET等方法对该催化剂进行了表征.以偶氮染料酸性橙7(A07)的可见光降解作为探针反应,研究了TiO2/SiO2的催化活性.结果表明,TiO2的平均晶粒尺寸为5.1 nm,晶型为锐钛矿;TiO2/SiO2具有大的比表面积,比P-25催化剂具有更高的光催化活性和更好的沉降性能,便于回收利用.     

TiO_2微球光催化降解腐植酸钠

以阳离子交换树脂为模板,采用溶胶-凝胶法以四氯化钛为原料制备TiO2微球,采用XRD,FTIR,SEM对样品进行了表征。微球中主要组分是锐钛矿型TiO2,同时掺杂有少量Na＋,SO24-等离子,比TiO2粉末具有更好的光催化性能,具备重复使用的能力,使用寿命较长,可作为一种有实用价值的光催化剂。在300 W高压汞灯下采用二氧化钛微球催化降解腐植酸钠,分析了催化剂投加量和反应时间对降解率的影响。腐植酸钠的光催化降解实验结果表明：初始浓度为10 mg/L的腐植酸钠在碱性条件,催化剂投加量为2.5 g/L,反应时间为3 h时最为适宜,最大降解率可达到96.51%。     

TiO2纳米管催化活性再生处理技术

采用H2O2、Fe2（SO4）3和Fenton溶液对失活的TiO2纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明,经H2O2溶液处理后TiO2催化活性能得到有效再生,经Fe2（SO4）3,和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H2O2和Fenton的强氧化作用,及进入TiO2纳米管的Fe3＋的阻止电子．空穴对再复合作用有关。     

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.     

TiO2光催化脱除NOx的研究进展

利用TiO2的光催化效应脱除大气污染物是近十年来国内外学术界的研究热点之一.本文对TiO2光催化脱除NOx方面的研究工作进行了综述,着重论述了光催化氧化反应及光催化还原反应脱除NOx的反应机理及影响因素,并对应用前景作出展望.     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.     

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.