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.     

Enhanced photocatalytic reduction reaction over Bi(3+)-TiO(2) nanoparticles in presence of formic acid as a hole scavenger

A series of Bi(3+)-doped TiO(2) (Bi(3+)-TiO(2)) catalysts with a doping concentration up to 2wt% were prepared by a sol-gel method. The prepared photocatalysts were characterized by different means to determine their chemical composition, surface structure and light absorption properties. The photocatalytic activity of different Bi(3+)-TiO(2) catalysts was evaluated in the photocatalytic reduction of nitrate in aqueous solution under UV illumination. In the experiments, formic acid was used as a hole scavenger to enhance the photocatalytic reduction reaction. The experiments demonstrated that nitrate was effectively degraded in aqueous Bi(3+)-TiO(2) suspension by more than 83% within 150min, while the pH of the solution increased from 3.19 to 5.83 due to the consumption of formic acid. The experimental results indicate that the presence of Bi(3+) in TiO(2) catalysts substantially enhances the photocatalytic reaction of nitrate reduction. It was found that the optimal dosage of 1.5wt% Bi(3+) in TiO(2) achieved the fastest reaction of nitrate reduction under the experimental condition. Bismuth ions deposit on the TiO(2) surface behaves as sites where electrons accumulate. Better separation of electrons and holes on the modified TiO(2) surface allows more efficient channeling of the charge carriers into useful reduction and oxidation reactions rather than recombination reactions. Two intermediate products of nitrite and ammonia during the reaction were also monitored to explore the possible mechanisms of photoluminescence quenching and photocatalytic reduction in the context of donor-acceptor interaction with electron trapping centers.     

Photocatalytic degradation of dyes on a magnetically separated photocatalyst under visible and UV irradiation

A novel kind of magnetically separable photocatalyst of TiO2/SiO2/gamma-Fe2O3 (TSF) is prepared. Scanning tunnel microscope (STM) and X-ray diffractometer (XRD) were used to characterize the structure of the photocatalyst. In the TSF photocatalyst, a TiO2 shell is for photocatalysis, a gamma-Fe2O3 core as a carrier is for separation by the magnetic field and a SiO2 membrane between the TiO2 shell and the gamma-Fe2O3 core is used to weaken the adverse influence of gamma-Fe2O3 on the photocatalysis of TiO2. Three kinds of dyes, Fluoresein, Orange II and Red acid G, were used to examine the photocatalytic activity of TSF. Due to strong UV adsorption of the gamma-Fe2O3, the photocatalytic activity of TSF was lower than that of the pure TiO2. Deducting the light absorption of the gamma-Fe2O3 particles, the photocatalytic activity of TSF was found to be higher than that of the P25 under UV irradiation. On the other hand, the photocatalytic activity of TSF under visible irradiation was much lower than that of the P25 TiO2 even deducting the visible light absorption of the gamma-Fe2O3 particles. Differences in the photocatalytic mechanisms under UV and visible irradiation lead to the differences in the photodegradation characteristics of dyes on TSF. The recycled TSF exhibited a good repeatability of photocatalytic activity.     

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.     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

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.     

碘掺杂Ti02可见光光催化性能研究

在低于100℃温度条件下，采用溶胶一凝胶法以钛酸正丁酯为钛源，碘酸钾为碘源，制备了I掺杂纳米TiO2催化剂（I-TiO2），运用x-射线衍射（XRD）、透射电镜（TEM）及x-射线光电子能谱（XPS）等对催化剂进行表征，结果表明，TiO2及I-TiO2催化剂均为锐钛矿，I吸附并包裹在TiO2表面或以间隙进入的形式存在，并未进入TiO2晶格。通过在可见光照射下（A〉420nm）以罗丹明B（RhodamineB，RhB）的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能，结果表明，掺杂比为n1：n^ti=0．05：l，焙烧温度为400℃，降解介质条件pH=7时，l-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱（IR），总有机碳（TOC）跟踪测定，比较了TiO2掺杂前后降解RhB和对氯苯酚（4-CP）的光催化特性差异；同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种，表明在可见光下，I-TiO2光催化体系中产生·OH高活性氧化物种从而氧化降解目标化合物。     

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.     

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.     

Photocatalytic degradation of the herbicide erioglaucine in the presence of nanosized titanium dioxide: comparison and modeling of reaction kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO2 nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO2 system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir-Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm-1 and 0.984 ppm min-1, respectively. In this work, we also compared the reactivity between the commercial TiO2 Degussa P-25 and a rutile TiO2. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO2 for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO2 process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO2.     

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.     

溶胶-凝胶法制备复合光催化剂（MWNTs/TiO_2）工艺条件的研究

以多壁碳纳米管（MWNTs）为载体,在煅烧温度200~900℃、煅烧时间1~7 h、溶胶体系pH值为2~10的工艺条件下,采用溶胶-凝胶法制备复合光催化剂（MWNTs/TiO2）。通过其对甲基橙的光催化降解效果对比,评价各种复合光催化剂催化活性之间的差异,结果表明,随着煅烧温度的升高,复合光催化剂中纳米TiO2的晶型由锐钛型逐渐向金红石型转变,500℃时为2种晶型的混合相;pH值为2的强酸性条件有利于形成金红石晶型,pH值为5的中性及弱酸性条件则有利于形成锐钛型,而pH值为3时为2种晶型的混合相;在煅烧温度500℃、煅烧时间3 h、溶胶凝胶体系pH值为3的最佳制备工艺条件下,复合光催化剂催化活性最高,借助扫描电镜发现其TiO2均匀地包覆在多壁碳纳米管管壁上。     

Photodestruction of Acid Orange 7 (AO7) in aqueous solutions by UV/H2O2: influence of operational parameters

The photodestruction of Acid Orange 7 (AO7), an anionic acidic dye, was studied in the UV/H2O2 process. H2O2 and UV light have a negligible effect when they were used on their own. Removal efficiency of AO7 was sensitive to the operational parameters such as initial H2O2 concentration, initial AO7 concentration, pH and different light sources. The photodestruction of AO7 was inhibited by addition of EtOH as an electron scavenger. The semi-logarithmic graphs of the concentration of AO7 versus time (t<30 min) were linear, suggesting pseudo-first order reactions (k(optimum)=0.105 min(-1)). A simple kinetic model is proposed which is in agreement with experimental results.     

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.     

The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment

In this study, conventional TiO2 powder was heated in hydrogen (H2) gas at a high temperature as pretreatment. The photoactivity of the treated TiO2 samples was evaluated in the photodegradation of sulfosalicylic acid (SSA) in aqueous suspension. The experimental results demonstrated that the photodegradation rates of SSA were significantly enhanced by using the H2-treated TiO2 catalysts and an optimum temperature for the H2 treatment was found to be of 500-600 degrees C. The in situ electron paramagnetic resonance (EPR) signal intensity of oxygen vacancies (OV) and trivalent titanium (Ti3+) associated with the photocatalytic activity was studied. The results proved the presence of OV and Ti3+ in the lattice of the H2-treated TiO2 and indicated that both were contributed to the enhancement of photocatalytic activity. Moreover, the experimental results presented that the EPR signal intensity of OV and Ti3+ in the H2-treated TiO2 samples after 10 months storage was still significant higher than that in the untreated TiO2 catalyst. The experiment also demonstrated that the significant enhancement occurred in the photodegradation of phenol using the H2-treated TiO2.     

Enhancement of photocatalytic oxidation of humic acid in TiO2 suspensions by increasing cation strength

This study aimed at improving the photocatalytic (PC) oxidation of humic acids (HA) in TiO2 suspensions by adding cationic ion such as calcium or magnesium. A set of tests was first conducted in the dark to study the adsorption of HA onto TiO2 in suspensions at different pH and calcium concentrations. The experiment demonstrated that the adsorption of HA onto the TiO2 particles was either pH-dependent or calcium strength-dependent due to electrostatic interaction and calcium ion bridging. The photodegradation of HA in the presence of UV irradiation was investigated as a function of pH and the concentration of calcium and magnesium ions. The results showed that the adsorption behavior between HA and TiO2 played a very important role during the PC oxidation process. The PC oxidation could be enhanced at neutral pH by increasing the cation strength. The kinetics of HA PC degradation in TiO2 suspensions with different initial concentrations was also studied using the Langmuir-Hinshelwood model.     

TiO2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。     

The photocatalytic disinfection of urban waste waters

In this paper we present the results of the photocatalytic disinfection of urban waste water. Two microbial groups, total coliforms and Streptococcus faecalis, have been used as indexes to test disinfection efficiencies. Different experimental parameters have been checked, such as the effect of TiO2, solar or UV-lamp light and pH. Disinfection of water samples has been achieved employing both UV-lamp and solar light in agreement with data shown by other authors. The higher disinfection rates obtained employing an UV-lamp may be explained by the stronger incident light intensity. Nevertheless no consistent differences have been found between TiO2-photocatalysis and direct solar or UV-lamp light irradiation at natural sample pH (7.8). At pH 5 the presence of TiO2 increases the relative inactivation rate compared with the absence of the catalyst. After the photocatalytic bacterial inactivation, the later bacterial reappearance was checked for total coliforms at natural pH and pH 5, with and without TiO2. Two h after the photocatalytic treatment, CFU increment was almost nill. But 24 and 48 h later an important bacterial CFU increment was observed. This CFU increment is slower after irradiation with TiO2 at pH 5 in non-air-purged samples.     

Photocatalytic degradation of the herbicide pendimethalin using nanoparticles of BaTiO3/TiO2 prepared by gel to crystalline conversion method: a kinetic approach

Photocatalytic degradation of the herbicide, pendimethalin (PM) was investigated with BaTiO3/TiO2 UV light system in the presence of peroxide and persulphate species in aqueous medium. The nanoparticles of BaTiO3 and TiO2 were obtained by gel to crystallite conversion method. These photo catalysts are characterized by energy dispersive x-ray analysis (EDX), scanning electron microscope (SEM), x-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) adsorption isotherm and reflectance spectral studies. The quantum yields for TiO2 and BaTiO3 for the degradation reactions are 3.166 Einstein m(-2) s(-1) and 2.729 Einstein m(-2) s(-1) and catalytic efficiencies are 6.0444 x 10(-7) mg(-2)h(-1)L2 and 5.403 x 10(-7) mg(-2)h(-1)L2, respectively as calculated from experimental results. BaTiO3 exhibited comparable photocatalytic efficiency in the degradation of pendimethalin as the most widely used TiO2 photocatalyst. The persulphate played an important role in enhancing the rate of degradation of pendimethalin when compared to hydrogen peroxide. The degradation process of pendimethalin followed the first-order kinetics and it is in agreement with Langmuir-Hinshelwood model of surface mechanism. The reason for high stability of pendimethalin for UV-degradation even in the presence of catalyst and oxidizing agents were explored. The higher rate of degradation was observed in alkaline medium at pH 11. The degradation process was monitored by spectroscopic techniques such as ultra violet-visible (UV-Vis), infrared (IR) and gas chromatography mass spectroscopy (GC-MS). The major intermediate products identified were: N-propyl-2-nitro-6-amino-3, 4-xylidine, (2, 3-dimethyl-5-nitro-6-hydroxy amine) phenol and N-Propyl-3, 4-dimethyl-2, 6-dinitroaniline by GC-MS analysis and the probable reaction mechanism has been proposed based on these products.     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。