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–hole 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.     

Deactivation of titanium dioxide photocatalyst by oxidation of polydimethylsiloxane and silicon sealant off-gas in a recirculating batch reactor

We have studied deactivation of titanium dioxide (TiO2) photocatalyst by oxidation of polydimethylsiloxane and silicone sealant off-gas in a recirculating batch reactor. Polydimethylsiloxane vapor is a model indoor air pollutant. It does not adsorb strongly on TiO2 in the dark, but undergoes oxidation when the ultraviolet (UV) photons are also present. Commercial silicone (room-temperature vulcanizing) sealant off-gas is an actual indoor air pollutant subject to short-term spikes in concentration. It does adsorb on the TiO2 surface in the dark, but UV photons also catalyze its oxidation. The oxidation of the Si-containing vapors was monitored using a Fourier transform infrared spectroscope equipped with a gas cell. Subsequent to each incremental exposure, a hexane oxidation reaction was performed to track the titania catalyst's activity. The exposures were repeated until substantial deactivation was achieved. We have also documented the regenerative effect of washing the catalyst surface with water. Surface science techniques were used to view the topography of the catalyst and to identify the elements causing the deactivation. Procedural observations of interest in the context of our recirculating batch reactor include the following: the rate of oxidation of hexane was used to assess the activity of a photocatalyst sample; hexane is an appropriate choice of a probe molecule because it does not adsorb in the dark and it undergoes photocatalytic oxidation (PCO) completely, forming CO2; and hexane does not deactivate the photocatalyst surface.     

Effect of adsorbents coated with titanium dioxide on the photocatalytic degradation of propoxur

Photocatalytic oxidation of pesticides in aqueous media irradiated by UV light is a rapidly growing field of research. Therefore, the treatment technology for degradation of propoxur (an insecticide) using titanium dioxide coated on the supports such as activated carbon, zeolite, brick, quartz and glass beads, was performed in this research. Results show that GAC/TiO2 is the best complexing agent for oxidizing propoxur because of its adsorption properities. The others follow the sequence: plain TiO2 > glass beads > zeolite > brick > quartz. The degradation rate of propoxur with plain TiO2 is higher than that with TiO2/GAC complexing agent. But the mineralization rate of propoxur with plain TiO2 is lower than that with TiO2/GAC complexing agent. However, it can be concluded that using GAC as the support can improve the photocatalytic efficiency.     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.     

光催化氧化深度处理电镀有机废水的工程化实验

采用光催化氧化联用技术对电镀有机废水进行深度处理工程化实验。探讨了uV、uV＋H2O3、uV＋H2O2＋TiO2、uV＋H2O2＋FeSO4、uV＋H2O2＋FeSO4＋TiO2、uV＋O3＋TiO2和uV＋03＋TiO2＋H2O2等体系对废水有机污染物去除率的影响。结果表明,相较于其他反应体系,uV＋O3＋TiO2＋H2O2体系具有更好的氧化效果,经碳滤处理后去除率达到90％以上,最终出水水质满足GB18918-20O2-级标准（A标准）的要求。实际运行项目偿还期5．33年,NPV〉0,内部收益率大于基准值10％。研究表明,uV＋O3＋TiO2＋H2O,体系能降低加药量,工作量及运行成本。可为电镀企业实际废水处理提供现实依据,为优化电镀废水的处理工艺提供参考。     

TiO2-catalyzed photooxidation of arsenite to arsenate in aqueous samples

The TiO2-catalyzed photooxidation of arsenite (As(III)) to arsenate (As(V)) was studied in aqueous TiO2 suspensions using a solar simulator which emitted ultraviolet and visible radiations. The concentration of As(III) was varied between 50 microg l(-1) and 10 mg l(-1), and the concentration of TiO2 between 1 mg l(-1) and 50 mg l(-1). Total oxidation of As(III) to As(V) occurred within minutes. The concentration of As(III) declined exponentially which indicates first-order kinetics. In the pH range between 5 and 9 there was no significant influence of the pH of the suspension on the reaction rate. Batch experiments without irradiation showed that part of the arsenic was adsorbed on the TiO2 surface. When using 100 microg l(-1) As and between 1 mg l(-1) and 50 mg l(-1) TiO2, 8-39% of As(III) and up to 73% of As(V) were adsorbed by TiO2. As(III) was also oxidized by UV radiation in the absence of TiO2, but the reaction was slower than in the presence of TiO2 resulting in an irradiation time too long for practical use. In addition, oxidation of As(III) in the presence of TiO2 was also observed under solar irradiation within a few minutes.     

Photocatalytic oxidation of gaseous DMF using thin film TiO2 photocatalyst

The heterogeneous photocatalytic oxidation of gaseous N,N'-dimethylformamide (DMF) widely used in the manufacture of synthetic leather and synthetic textile was investigated. The experiments were carried out in a plug flow annular photoreactor coated with Degussa P-25 TiO2. The oxidation rate was dependent on DMF concentration, reaction temperature, water vapor, and oxygen content. Photocatalytic deactivation was observed in these reactions. The Levenspiel deactivation kinetic model was used to describe the decay of catalyst activity. Fourier transform infrared (FTIR) was used to characterize the surface and the deactivation mechanism of the photocatalyst. Results revealed that carbonylic acids, aldehydes, amines, carbonate and nitrate were adsorbed on the TiO2 surface during the photocatalytic reaction. The ions, NH4+ and NO3-, causing the deactivation of catalysts were detected on the TiO2 surface. Several treatment processes were applied to find a suitable procedure for the regeneration of catalytic activity. Among these procedures, the best one was found to be the H2O2/UV process.     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

Photocatalytic oxidation of xenobiotics in water with immobilized TiO2 on agitator

A novel photocatalytic oxidation reactor, using Degussa P-25 TiO2 as a stationary phase with a thickness of 1.5-2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20% after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo-first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to TiO2 film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing TiO2 film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Effect of CO on NO oxidation over platinum based catalysts for hybrid fast SCR process

The oxidation characteristics of NO over Pt/TiO2 (anatase, rutile) catalysts have been determined in a fixed bed reactor as a function of O2, CO and SO2 concentrations in the presence of 8% water. The conversion of NO to NO2 increases with increasing O2 concentration up to 12% and it levels off. This saturation effect is more pronounced over rutile-Pt/TiO2 (r-Pt/TiO2) than that of anatase-Pt/TiO2 (a-Pt/TiO2). The presence of CO increases NO oxidation significantly and this enhanced effect is more pronounced on a-Pt/TiO2 than that on r-Pt/TiO2 with increasing CO concentration at lower temperatures. The same effect is also observed on the catalysts with different Pt and tungsten oxide (WO3) loadings. With increasing Pt and WO3 loadings on TiO2 support (Pt-WO3/TiO2), formation of NO2 is high even at lower temperatures. The presence of SO2 significantly suppresses the oxidation of NO over both r-Pt/TiO2 and a-Pt/TiO2 catalysts but it is less pronounced due to low stability of sulfate on a-Pt/TiO2.     

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.     

亚甲基蓝表面修饰纳米TiO2降解造纸废水动力学

以亚甲基蓝(MB)作为表面修饰剂,采用简单的化学吸附法制备亚甲基蓝表面修饰的纳米TiO2光催化剂(TiO2-MB)。经表面修饰后,TiO2-MB光催化剂波长响应范围红移至可见光区575 nm处。探讨了光催化剂量、光照时间和溶液pH值对TiO2-MB光催化降解造纸废水的影响;研究了纳米TiO2-MB对造纸废水的暗吸附规律和光降解性能。结果表明:纳米TiO2-MB对造纸废水的吸附规律都较好地符合Langmuir和Freundlich吸附等温模型,属于吸热反应;光催化降解动力学符合Langmuir-Hinshelwood动力学模型。在160 W高压汞灯光照80 min,3.0 g/L纳米TiO2-MB光催化降解pH=2.0的造纸废水(COD:2 069.8 mg/L),COD去除率可达94.7%,处理效果远高于避光条件下。光催化剂经8次使用仍具有较高的催化活性。     

Photo-oxidation of cork manufacturing wastewater

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

Photocatalytic hydrogen generation in the presence of chloroacetic acids over Pt/TiO2

In the presence of chloroacetic acids, the photocatalytic hydrogen evolution and decomposition of the pollutants over Pt/TiO2 have been investigated. The Pt/TiO2 was prepared by photodeposition. Monochloroacetic acid and dichloroacetic acid enhance photocatalytic hydrogen generation, whereas trichloroacetic acid does not. The photocatalytic oxidation of monochloroacetic acid and dichloroacetic acid mainly produces CO2, HCl and formaldehyde, whereas the photocatalytic oxidation of trichloroacetic acid mainly produces CO2 and HCl. The effect of the concentration of monochloroacetic acid and dichloroacetic acid on the hydrogen generation rate is consistent with a Langmuir-Hinshelwood kinetic model. A possible reaction mechanism was discussed.     

外负载Ce-TiO2/活性炭复合体对亚甲基蓝光催化

用超临界流体沉积法处理过的活性炭(AC)为载体,钛酸丁酯为前驱物,硝酸铈为掺杂剂,乙醇为溶剂,制备了外负载TiO2-Ce/Csurf复合材料。在紫外灯照射下,以亚甲基蓝溶液为标准模拟降解物,研究了复合体不同热处理温度、不同浓度、不同亚甲基蓝浓度、不同铈掺杂量以及不同反应温度对光催化性能的影响。结果表明:外负载催化剂的催化性能要高于纯TiO2和体负载催化剂。铈离子掺杂能抑制TiO2晶粒生长,阻碍了TiO2由锐钛矿型向金红石型的转变。当铈离子掺杂量为1.5%,热处理温度为600℃,亚甲基蓝溶液初始浓度为5.5 mg/L,样品浓度为1.5 g/L时,光催化性能最好。     

Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor

The photocatalytic oxidation of methyl orange under weak illumination conditions was carried out in two different types of fluidized bed reactors. TiO2 powder was employed as the photocatalysts and a 15 W low pressure mercury lamp was used as the light source and the reactor volume was 2.5 l. The parametric study of photocatalytic oxidation of methyl orange in two different types of fluidized beds was investigated; effect of catalyst loadings, pH, air flow rate, initial concentration and oxygen concentration on the oxidation reaction rate. The experimental results were analyzed in conjunction with the characteristics of fluidized bed and the reactor geometry effect on the reaction rate was analyzed.     

TiO2光催化氧化降解乳酸的工艺及机理研究

以TiO2为催化剂、紫外灯为光源对乳酸进行光催化降解实验,考察了乳酸初始浓度、TiO2用量、反应时间、曝气方式等因素对乳酸降解率的影响,并在此基础上应用正交实验对降解条件进行优化,同时对乳酸的降解机理进行了探索研究。实验结果表明：以300 W紫外汞灯为光源,在乳酸初始浓度为0.5 g/L、TiO2量为0.20 g/L、反应时间120 min、持续通入空气鼓泡的条件下,乳酸降解效果最佳,乳酸降解率为99.9%;降解12 h总有机碳去除率达91.2%。乳酸光催化降解的反应途径为：乳酸脱羧生成乙醇,乙醇被氧化生成乙醛,进而氧化为乙酸,所有的中间产物被继续降解,最终矿化为CO2和H2O等小分子物质。     

ClO2氧化/TiO2复合吸附剂协同体系处理印染废水的实验研究

利用ClO2 氧化/TiO2 复合吸附剂协同体系对处理实际印染废水进行了实验研究.结果表明,对于COD为750 mg/L、色度为250倍、SS为100 mg/L的1 000 mL印染废水,当溶液pH为4.0、ClO2 用量20 mg/L、TiO2 复合吸附剂用量2.5 g、反应时间和吸附时间分别为2、8 min时,处理后的废水COD＜100 mg/L、色度＜40倍、SS＜70 mg/L,达到了《纺织染整工业水污染物排放标准》(GB 4287-92)排放要求.并对两者的协同机理进行了理论上的探讨.     

Photoassisted bleaching of dyes utilizing TiO2 and visible light

Titanium dioxide was shown to be generally effective as a catalyst for photobleaching many structural classes of organic dyes in aqueous solution, using visible light. However, results from study of 15 dyes indicate that photobleaching rates differ significantly from families of dyes with different functionalities, and are dependent on the light source and crystalline form of TiO2 used. Sorption characteristic on the TiO2 surface and the aqueous solubility of the dyes also play an important role in the photobleaching rate. Kinetic analysis indicates that the dye photobleaching rates can usually be approximated as pseudo-first-order kinetics. In addition to the generally proposed photocatalytic oxidation mechanism for TiO2 reactions, we observed evidence for two kinds of electron transfer mechanisms that are "photosensitized reduction" and "photosensitized oxidation". Natural sunlight was effectively used to photobleach some of the dyes.