Carbamazepine degradation by photolysis and titanium dioxide photocatalysis

We investigated the degradation of carbamazepine by photolysis/ultraviolet (UV)-C only and titanium dioxide photocatalysis. The degradation of carbamazepine by UV-only and titanium-dioxide-only (adsorption) reactions were inefficient, however, complete degradation of carbamazepine was observed by titanium dioxide photocatalysis within 30 min. The rate of degradation increased as initial carbamazepine concentration decreased, and the removal kinetics fit well with the Langmuir-Hinshelwood model. The addition of methanol, a radical scavenger, decreased carbamazepine removal, suggesting that the hydroxide radical played an important role during carbamazepine degradation. The addition of oxygen during titanium dioxide photocatalysis accelerated hydroxide radical production, thus improving mineralization activity. The photocatalytic degradation was more efficient at a higher pH, whereas the removal of carbamazepine and acridine (a major intermediate) were more efficient under aerobic conditions. The mineralization of carbamazepine during photocatalysis produced various ionic by-products such as ammonium and nitrate by way of nitrogen dioxide.     

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小（平均尺寸25nm）的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO2（Pt-TiO2）、稀土元素Ce掺杂TiO2（Ce-TiO2）和Pt、Ce共掺杂TiO2（Pt／Ce-TiO2）的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由ce掺杂的TiO2光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO2,2种元素进行共同掺杂时对应的TiO2光催化剂降解能力最大。     

Photocatalytic degradation of atrazine by porphyrin and phthalocyanine complexes

This study principally focused on a new kind of photochemical reaction catalyst: porphyrin and phthalocyanine complexes. In a first step, the preparation of the catalysts was optimized. A resin has been chosen to be the support of the complexes. Efficiency of catalytic activity is performed on the degradation of a pesticide: atrazine. The best atrazine degradation occurs with 4.6% of complexes versus substrate. The role of the surface has also been shown to be important. Then, their performances were demonstrated in terms of kinetics and degradation routes, compared to a classical catalyst: titanium dioxide. This study seeks to assess the efficiency of these systems both in a mercury lamp reactor and under solar irradiation which reduces energy costs. The best atrazine degradation half-life found for the complexes is about 200 min with the iron phthalocyanine. These catalysts exhibit particular oxidation activities. Indeed, the degradation routes have been found different between the semi-conductor and the metallic complexes. These complexes are able to cleave the triazinic ring more efficiently than the titanium dioxide.     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小(平均尺寸25 nm)的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO₂(Pt-TiO₂)、稀土元素Ce掺杂TiO₂(Ce-TiO₂)和Pt、Ce共掺杂TiO₂(Pt/Ce-TiO₂)的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由Ce掺杂的TiO₂光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO₂,2种元素进行共同掺杂时对应的TiO₂光催化剂降解能力最大。     

Photocatalytic degradation of amoxicillin from aqueous solutions by titanium dioxide nanoparticles loaded on graphene oxide

Environmental Science and Pollution Research - The photocatalytic degradation of amoxicillin (AMX) by titanium dioxide nanoparticles loaded on graphene oxide (GO/TiO2) was evaluated under UV light....     

Photodegradation of haloacetic acids in water

The global distribution and high stability of some haloacetic acids (HAAs) has prompted concern that they will tend to accumulate in surface waters and pose threats to humans and the ecosystem. It is important to study the degradation pathways of HAAs in aqueous systems to understand their ecotoxicological effects. Previous studies involving thermal degradation reactions show relatively long lifetimes for HAAs in the natural environment. Photolysis and photocatalytic dissociation are potentially efficient routes for the degradation of HAAs such as trichloroacetic acid to hydrochloric acid, carbon dioxide and chloroform, although such processes are poorly understood in surface waters. In our present study, we have used light to degrade the HAAs in the presence of titanium dioxide suspensions. All chloro and bromo HAAs degrade in photocatalysis experiments and the rate of degradation is directly proportional to the number of halogen atoms in the acid molecule. The half-lives of the HAAs from the photodegradation at 15 degrees C in the presence of suspended titanium dioxide photocatalyst are 8, 14, 83 days for the tri-, di- and mono-bromoacetic acids. Tri-, di- and mono-chloroacectic acids have half-lives of 6, 10 and 42 days respectively. The mixed bromochloro and chlorodifluoroacetic acids degrade with half-lives of 18 and 42 days respectively. Our results therefore suggest that the photocatalytic process can provide an additional degradation pathway for the HAAs in natural waters.     

A comprehensive systematic review of photocatalytic degradation of pesticides using nano TiO2

Environmental Science and Pollution Research - This study has systematically reviewed all of the research articles about the photocatalytic degradation of pesticides using titanium dioxide (TiO2)...     

Proton-induced accelerated decay of the fungicide,vinclozolin, on TiO2 surface under solar irradiation: Experimental and DFT study

The photochemical degradation of vinclozolin by addition of titanium dioxide on silica support has been examined both experimental and quantum-chemically. Solar irradiation of vinclozolin on silica with and without addition of titanium dioxide for 6 h resulted in 21% and 97.8% vinclozolin residues, respectively. In both these cases, phototransformation leads to the formation of (3,5-dichlorophenyl isocyanate) and (3,5-dichloroaniline). The presence of the intermediary product resulted from opening of the 2,4-oxazolidine-dione ring is also confirmed by GS-MS and LC-MS chromatography. The proton-induced mechanism of vinclozolin decay at the above experimental conditions is clarified on the base of DFT calculations.     

TiO_2晶体的微波水热法制备及光催化性能研究

以TiSO4和尿素为主要原料,EDTA为控制剂,采用微波水热法制备纳米TiO2光催化剂,并分析了纳米TiO2晶粒的最佳形成条件。利用XRD、TEM等技术对制备产物进行表征。结果表明,TiSO4和尿素混合物在微波水热条件下晶化150 min后,产物为锐钛矿型TiO2,且产物粒径小、大小均匀。在紫外光照射下,以自制的锐钛矿型纳米TiO2为催化剂,酸性橙为降解目标物,进一步研究了其光催化性能。结果表明,该TiO2在紫外光照射下表现出稳定的光催化活性。     

TiO2晶体的微波水热法制备及光催化性能研究

以TiSO4和尿素为主要原料,EDTA为控制剂,采用微波水热法制备纳米TiO2光催化剂,并分析了纳米TiO2晶粒的最佳形成条件。利用XRD、TEM等技术对制备产物进行表征。结果表明,TiSO4和尿素混合物在微波水热条件下晶化150min后,产物为锐钛矿型TiO2,且产物粒径小、大小均匀。在紫外光照射下,以自制的锐钛矿型纳米TiO2为催化剂,酸性橙为降解目标物,进一步研究了其光催化性能。结果表明,该TiO2在紫外光照射下表现出稳定的光催化活性。     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

日光下黄砂负载TiO2降解邻氯苯酚水溶液

研究了以黄砂为载体,ＴｉＯ２为催化剂,以太阳光为光源对邻氯苯酚水溶液进行光催化降解的可行性。结果表明,锐钛型ＴｉＯ２邓邻氯苯酚有显著的光催化降解作用;ＴｉＯ２的催化活性在焙烧温度３００℃时最高。     

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。     

超细TiO2粒子的超滤分离及回用特性

针对TiO2超细粒子的超滤分离特性进行了试验研究,探讨了操作压力、膜面流速、TiO2投量、pH、电解质等参数条件对膜通量的影响规律及作用机理,证实了浓差极化及滤饼层阻力是影响通量变化的主导因素,在此基础上确定了适宜的超滤工艺条件及膜清洗方式.以甲基橙为降解基质分别测试了经混凝与超滤分离后的TiO2光催化活性,结果表明,超滤不仅可实现TiO2粒子与水的彻底分离,且分离后TiO2催化活性与初次使用相当.研究表明超滤用于悬浮光催化体系的固液分离及催化剂再用是可行的.     

Photodegradation of Diquat and Paraquat in aqueous solutions by titanium dioxide: evolution of degradation reactions and characterisation of intermediates

The titanium dioxide assisted photodegradation of Diquat and Paraquat herbicides solutions has been the subject of the present investigation, considering its direct application in the treatment of contaminated waters and soils. To have a better understanding of the photodegradation process, different types of TiO2, commercial and 'home prepared' Ti(1-x)FexO2 (x = 0% and 4%), were used as catalysts, using an UV light as radiation source. The degradation reactions were followed by UV spectroscopy and the intermediates and reaction products were characterised by electrospray ionisation mass spectrometry (ESIMS) combined with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS). The present study shows that, for photocatalytic degradation of Diquat and Paraquat solutions, a basic pH can be determinant, as well as the type of catalyst. The type of catalyst can also strongly influence the degradation pattern of the herbicide. Regarding complete degradation, we were able to show that Diquat is more persistent than Paraquat. During the photocatalytic processes, several intermediate and reaction products are sequentially formed, to which structures are proposed.     

超声波-光催化联合降解苯酚废水研究

超声降解和光催化降解均为自由基历程的高级氧化技术,同时,超声空化能够改善传质效果,因此,二者耦合能否产生协同效果是值得研究的。本文考察了苯酚溶液的超声降解、光降解、光催化降解、超声-光催化降解以及温度对光降解和光催化降解的影响。结果表明,40kHz,0.4w/cm2的超声波对苯酚没有明显的降解作用,而对光催化降解只有轻微的促进作用。光降解和光催化降解的过程曲线显著不同,但温度对二者均有显著的促进作用。     

Semiconductor-mediated photocatalysed degradation of two selected priority organic pollutants,benzidine and 1,2-diphenylhydrazine,in aqueous suspension

The photocatalysed degradation of two selected priority organic pollutants, namely benzidine (1) and 1,2-diphenylhydrazine (DPH, 2) has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions employing a pH-stat technique. The degradation was studied by monitoring the change in substrate concentration of the model compound employing HPLC analysis and the decrease in total organic carbon content, respectively, as a function of irradiation time. The degradation kinetics were studied under different conditions such as reaction pH, substrate and photocatalyst concentration, type of TiO2 photocatalyst and the presence of alternative additives such as H2O2, KBrO3 and (NH4)2S2O8 besides molecular oxygen. The degradation rates and the photonic efficiencies were found to be strongly influenced by the above parameters. Toxicity tests for the irradiated samples of benzidine measuring the luminescence of bacteria Vibrio fischeri after 30 min of incubation were also performed. 4-amino-biphenyl (7) and hydroquinone (13) were identified as intermediate products by GC/MS technique and probable pathways for the formation of the products are proposed.     

Assessment of in situ biodegradation of monochlorobenzene in contaminated groundwater treated in a constructed wetland

The degradation of monochlorobenzene (MCB) was assessed in a constructed wetland treating MCB contaminated groundwater using a detailed geochemical characterisation, stable isotope composition analysis and in situ microcosm experiments. A correlation between ferrous iron mobilisation, decreasing MCB concentration and enrichment in carbon isotope composition was visible at increasing distance from the inflow point, indicating biodegradation of MCB in the wetland. Additionally, in situ microcosm systems loaded with 13C-labelled MCB were deployed for the first time in sediments to investigate the biotransformation of MCB. Incorporation of 13C-labelled carbon derived from the MCB into bacterial fatty acids substantiated in situ degradation of MCB. The detection of 13C-labelled benzene indicated reductive dehalogenation of MCB. This integrated approach indicated the natural attenuation of the MCB in a wetland system. Further investigations are required to document and optimise the in situ biodegradation of MCB in constructed and natural wetland systems treating contaminated groundwater.