Photocatalytic degradation of AZO dyes by supported TiO2 + UV in aqueous solution

The photocatalytic degradation performance of photocatalysts TiO2 supported on 13-X, Na-Y, 4A zeolites with different loading content was evaluated using the photocatalytic oxidation of dyes direct fast scarlet 4BS and acid red 3B in aqueous medium. The results showed that the best reaction dosage of TiO2-zeolite catalysts is about 2 g/l and the photocatalytic kinetics follows first order for all supported catalysts. The photocatalytic activity order of the three series catalysts is 13X type >Y type >4A type. The physical state of titanium dioxide on the supports is evaluated by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD), BET, and FTIR.     

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.     

The influence of FeCl3 on the photocatalytic degradation of dissolved azo dyes in aqueous TiO2 suspensions

The study concerned decolouration of solutions of azo, anionic (Acid Orange 7, Reactive Red 45, Acid Yellow 23) and cationic (Basic Blue 41 and Basic Orange 66) dyes during illumination with UV (lambdamax 366 nm) irradiation in the presence of TiO2 and FeCl3. The process of decolouration during illumination of the solutions studied containing FeCl3 underwent significant intensification in the case of anionic dyes and unfavourable inhibition in case of cationic dyes. It was also observed that FeCl3 had a diverse influence on the adsorption of the dyes studied on TiO2. The adsorption of anionic dyes and decolouration of solutions before the illumination was observed only in the presence of FeCl3. In case of cationic dyes the addition of FeCl3 caused elimination of these phenomena. An additional cause of decolouration of anionic dyes solutions before illumination was the precipitation of their poorly soluble compounds from Fe3+. The processes of degradation and mineralization of the dye that accompanied decolouration of Acid Orange 7 solutions were also observed. It was stated that similarly to the case of Acid Orange 7, the decolouration of the studied anionic dyes' solutions can depend on the concentration of FeCl3, the amount of TiO2 and the initial concentration of the dye in its solution.     

TiO_2胶体光催化降解罗丹明B染料

TiO2胶体从钛氧有机物水解制备,表征的方法有：X射线衍射光谱（XRD）、激光散射粒径分布、傅立叶变换红外光谱（FT-IR）、X射线光电子谱（XPS）和透射电子显微镜（TEM）。利用罗丹明B染料分子作为探针分子研究TiO2胶体的光催化活性,分析了pH、催化剂用量、外加氧化剂（H2O2）用量及罗丹明B初始浓度对TiO2胶体光催化活性的影响。结果表明：制备的TiO2胶体粒子平均粒径为13.8 nm（激光散法测定）,光催化降解罗丹明B染料的反应属于一级动力学反应,可以用Langmuir-Hinshewood模型加以描述,反应速率常数k1为0.08413 mg/（L.min）,平衡吸附常数k2为1.5305 L/mg;在pH为6,TiO2胶体用量为0.04%,H2O2（含量30%）用量为0.2%（V/V）,光照度为69.6μW/cm2时,5 h后罗丹明B染料的降解率可达到99%以上;相似的条件,0.2%的P25 TiO2粉体光催化处理染料水时,罗丹明B的降解率为90%。纳米TiO2胶体不仅可以提高罗丹明B的光催化降解率,还具有用量少,可有效降低水处理成本的特点。     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

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%。     

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.     

Photocatalytic degradation of cellulose bleaching effluent by supported TiO2 and ZnO

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.     

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.     

亚甲基蓝溶液的光催化脱色及降解

以高压汞灯为光源,在自ＴｉＯ２纳米粉末悬浮体系内,以在蓝溶液光催化降解脱色反应为模型,研究了其脱色降解动力学及其影响因素。研究表明,亚甲基蓝光催化反应动力学常数为４．５３μｍｏｌ／Ｌ．ｍｉｎ．吸附常数为３３．５５Ｌ／ｍｍｏｌ;随着ｐＨ值的上升以及Ｈ２Ｏ２的加入,其脱色降解速率加快。     

改性TiO_2光催化降解三苯甲烷类污染物

以硫酸钛为原料采用水热法制备了掺Fe3＋TiO2晶体粉末,采用X射线衍射仪（XRD）对样品的结构进行了表征。在可见光条件下,用溴酚蓝、甲基绿、甲基蓝、孔雀石绿、甲基紫和碱性品红等6种典型三苯甲烷类化合物为目标降解物,研究了以自制的掺Fe3＋TiO2晶体粉末对它们的催化降解作用。实验结果表明,制备的掺Fe3＋TiO2晶体属于锐钛矿型。6种化合物的光催化降解反应遵循拟一级动力学规律,且可用Langmuir-Hinshelwood（L-H）动力学模型描述,其表观反应速度常数（k）的大小顺序为：溴酚蓝〈甲基绿〈甲基蓝〈孔雀石绿〈甲基紫〈碱性品红,大小变化次序与其半衰期t1/2成反比,并从分子结构上对它们的降解规律进行定性解释。     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

TiO2、BiVO4、Cu2O光催化降解低浓度甲醛

比较研究了3种（TiO2,BiVO4,Cu2O）光催化剂对低浓度甲醛的降解过程,拟通过结构分析（晶粒尺寸、比表面积、禁带宽度）和实验评价其性能优劣,优选出光催化性能较好的材料。通过结构分析和降解甲醛实验发现,甲醛初始浓度较低时,BiVO4降解率优于其他,随甲醛浓度增加,催化剂降解率均呈上升趋势,TiO2-1（T-1）、TiO2-2（T-2）降解率增加显著。随环境湿度增大,降解率先上升后下降,BiVO4-1（B-1）、BiVO4-2（B-2）降解率下降的较为缓慢。同一物质当晶粒尺寸越小比表面积越大,其降解率越好。T-2比B-1有更好的稳定性。分析认为在较低甲醛浓度时,决定光催化降解率的主要因素是催化剂的表面反应速率。随着甲醛初始浓度的增加,吸附脱附成为主要限制步骤。随环境湿度增加,甲醛降解率先上升后下降,具有较小比表面积的BiVO4降解甲醛效率下降不显著。连续的工作产生甲醛分解副产物,不易堵塞具有大比表面积的T-2的活性位点,所以T-2有更好的稳定性。     

Degradation of azo dyes by algae

The degradation of azo dyes by algae was evaluated and it was found that certain algae can degrade a number of azo dyes to some extent. The reduction rate appears to be related to the molecular structure of the dyes and the species of algae used. The azo reductase of algae is responsible for degrading azo dyes into aromatic amine by breaking the azo linkage. The aromatic amine is then subjected to further metabolism by algae. It is proposed in this paper that in stabilization ponds, algae can play a direct role in the degradation of azo dyes, rather than only providing oxygen for bacterial growth.     

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/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩（EP）为载体的TiO2催化剂（TiO2/EP）,对使用较为广泛的抗生素磺胺嘧啶（SDZ）进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子（HCO3^-、SO4^2-和Cl^-）和腐殖酸（HA）对SDZ降解效果的影响。结果表明：SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm^2,反应时间为45 min时,SDZ的降解率达到96%;HCO3^-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO4^2-和Cl^-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO2 aqueous solution

5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO₂ heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

Non-enzymatic reduction of azo dyes by NADH

Nicotinamide adenine dinucleotide (NADH) reduces a variety of azo dyes by four electrons to generate the corresponding aromatic amines. This reduction is pH-dependent and increases with decreasing pH. Reduction of 4-(4'-sulfophenylazo)-phenol and 2-(4'-sulfophenylazo)-phenol, specifically substituted with methyl, methoxy, halo, and nitro groups, was examined to determine the susceptibility of azo dyes to reduction by NADH. Except for the nitro-substituted azo dyes, all other azo dyes were reduced. Possible mechanisms of reduction are proposed. The implications of our findings to microbial degradation and mammalian metabolism of azo dyes are discussed.