Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Degradation mechanism and the toxicity assessment in TiO2 photocatalysis and photolysis of parathion

The photocatalytic degradation of methyl parathion was carried out using a circulating TiO2/UV reactor. The experimental results showed that parathion was more effectively degraded in the photocatalytic condition than the photolysis and TiO2-only condition. With photocatalysis, 10mg/l parathion was completely degraded within 60 min with a TOC decrease exceeding 90% after 150 min. The main ionic byproducts during photocatalysis were measured. The nitrogen from parathion was recovered mainly as NO3-, NO2- and NH4+, 80% of the sulfur as SO4(2-), and less than 5% of the phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and paraoxon were also identified, and these were further degraded. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by photocatalysis and photolysis. A Microtox test using V. fischeri showed that the toxicity, expressed as the relative toxicity (%), was reduced almost completely after 90 min under photocatalysis, whereas only an 83% reduction was achieved with photolysis alone. Another toxicity test using D. magna also showed that the relative toxicity disappeared after 90 min under photocatalysis, whereas there was a 65% reduction in relative toxicity with photolysis alone. The pattern of toxicity reduction parallels the decrease in parathion and TOC concentrations.     

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.     

Enhanced photocatalysis of pentachlorophenol by metal-modified titanium (IV) oxide

The effects of four metals (Ag, Au, Pt, and Cu) doped on TiO2 on the photocatalysis of pentachlorophenol (PCP) were investigated. The results of this study indicated that all four metals-doped TiO2 catalysts were able to enhance the efficiency of PCP photocatalysis with an optimum metallic content of 0.1 wt%. For the metal-doped TiO2 samples (Au, Pt, and Cu), the patterns of light absorption were significantly extended toward visible light spectra in the wavelengths between 400 and 800 nm. The photocatalysis of PCP was pH dependent with the maximum degradation rate achieved in the solution at pH 3. The formation of chloride ion corresponded with the concentration of PCP degraded which confirmed that dechlorination was the major pathway of PCP photocatalysis. The overall toxicities of PCP samples were reduced with the extension of light exposure using the microtox test. The results of PCP photocatalysis are also discussed based on the characteristics of metal/TiO2 including X-ray differential (XRD) patterns, Brunquer Emmett Teller (BET) specific area analysis, and Ultra Violet (UV)-Vis absorption spectra.     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

Photocatalytic degradation of p-nitrophenol on nanometer size titanium dioxide surface modified with 5-sulfosalicylic acid

The surface of nanometer size TiO(2) was simply and fast modified by chemical adsorption in saturated solution of 5-sulfosalicylic acid. After surface modification, a stable, yellow surface complex was formed quickly, the wavelength response range of TiO(2) was expanded, it has obvious absorption in the region from 320 to 450 nm; the adsorption efficiency of p-nitrophenol (PNP) by TiO(2) was enhanced from 42% to 84%. The photocatalytic activity was tested on the degradation of PNP. The influences of catalyst and its dosage, pH value, and PNP concentration on the degradation were investigated. On optimal photodegradation conditions, including initial pH 4.0, PNP 5 mg l(-1), catalyst 100 mg, irradiation time 120 min with 160 W high-pressure mercury lamp, the degradation efficiency of PNP was increased from 40% to 88% after surface modification. Surface modification led not only to an increase in the light utilization, but also improved the surface coverage of PNP in comparison with the pure TiO(2). Both of these factors are crucial for the photocatalytic activity of heterogeneous photocatalysis, especially for photodegradation of benzenoid pollutants.     

TiO2纳米管催化降解4，4’-二溴联苯的影响因素和动力学研究

利用TiO2纳米管催化降解水中的4，4’-二溴联苯，对催化降解过程和影响因素进行研究。结果表明，TiO2纳米管对其有较高的催化降解效率且降解过程符合Langmuir—Hinshelwood动力学模式。不同光源、4，4’-二溴联苯的初始浓度、纳米管添加量和pH值对催化降解过程都有较大影响，其中pH值的影响最为明显。反应液在中性状态下的降解率明显低于pH=1或11的情况。在pH=1时，4，4’一二溴联苯的降解率达86％。     

Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation

Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

Sonophotocatalytic degradation of alazine and gesaprim commercial herbicides in TiO2 slurry

The photocatalytic degradation of alazine and gesaprim commercial herbicides was carried out in aqueous TiO(2) suspensions under UV light (15W, 352 nm). Degradation of these herbicides was also observed by the combined effects of photocatalysis with sonolysis (sonophotocatalysis) using an ultrasound source of 20kHz. Degradation profiles were recorded by measuring the concentration of the active compounds present in the alazine (alachlor and atrazine) and gesaprim (atrazine) by HPLC as a function of irradiation time (sound and/or light). Over 90% of the active component in the gesaprim was abated and those in alazine were completely degraded. The content of total organic carbon and chemical oxygen demand was also monitored. Mineralization of the commercial herbicides was achieved. Over 80% of chemical oxygen demand abatement was attained for both herbicides with sonophotocatalysis at 150 min of irradiation time. The photocatalytic degradation of the herbicides followed a pseudo-first order kinetics and their rate constant was increased by the combined effects of sonolysis.     

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.     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO2作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO2催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明,活性炭纤维与TiO2的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO2溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37%;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

Titanium dioxide mediated photocatalytic degradation of monochlorobenzene in aqueous phase

The reaction sequence for the photocatalytic degradation of monochlorobenzene (MCB) in UV/TiO2 process, including substrate adsorption, degradation, and mineralization, was studied. The theoretical maximum quantity of MCB that could be adsorbed onto TiO2 surface in aqueous phase was 0.18+/-0.04 micromol m(-2) of TiO2. In accordance with the upper limit of the relative surface coverage of MCB molecules to surface hydroxyls of TiO2 was around 2.2%, the water molecules as the major adjacent species near TiO2 surface would compete with MCB molecules. Increasing the initial substrate concentration to an appropriate value or enhancing the affinity between the MCB and the TiO2 surface by adjusting the solution pH would promote the photocatalytic degradation. Experimental results revealed that the neutral medium was beneficial for the degradation of MCB. In comparison, the mineralization was most improved at acidic condition. Generally, 90% of the total organic carbon (TOC) was mineralized after 240 min illumination time in the examined pH range except solution pH 11. The suppressed mineralization of MCB at solution pH 11 was ascribed to the lack of adsorption. A simplified 2-step consecutive kinetic model was used to simulate the mineralization.     

The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources

Direct photolysis and photocatalytic degradations of alachlor, a widely used herbicide, were studied using three different monochromatic UV lamps (254, 300 and 350 nm) and two TiO(2) sources. Both the direct photolysis and photocatalytic degradations of alachlor follow pseudo-first-order decay kinetics. TiO(2)-P25 was found to be an effective photocatalyst compared to TiO(2)-BDH. The direct photolysis of alachlor was dominant at 254 nm even if TiO(2) was present in the solution. Among the three UV wavelengths used, the highest photocatalysis quantum yield was obtained at 300 nm. The photocatalytic degradation rate of alachlor increased with the dosages of TiO(2), but an overdose of TiO(2) would retard the reaction due to light attenuation. Photocatalytic reactions were slightly enhanced in an alkaline medium, and the different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. This effect was diminished at a later stage after the reaction intermediates were formed.     

Photocatalytic degradation of phenol using Ag core-TiO<Subscript>2</Subscript> shell (Ag@TiO<Subscript>2</Subscript>) nanoparticles under UV light irradiation

Ag@TiO₂ nanoparticles were synthesized by one pot synthesis method with postcalcination. These nanoparticles were tested for their photocatalytic efficacies in degradation of phenol both in free and immobilized forms under UV light irradiation through batch experiments. Ag@TiO₂ nanoparticles were found to be the effective photocatalysts for degradation of phenol. The effects of factors such as pH, initial phenol concentration, and catalyst loading on phenol degradation were evaluated, and these factors were found to influence the process efficiency. The optimum values of these factors were determined to maximize the phenol degradation. The efficacy of the nanoparticles immobilized on cellulose acetate film was inferior to that of free nanoparticles in UV photocatalysis due to light penetration problem and diffusional limitations. The performance of fluidized bed photocatalytic reactor operated under batch with recycle mode was evaluated for UV photocatalysis with immobilized Ag@TiO₂ nanoparticles. In the fluidized bed reactor, the percentage degradation of phenol was found to increase with the increase in catalyst loading.     

UV-TiO_2光催化氧化降解双酚A的动力学研究

采用自制光催化氧化反应器,研究了双酚A(BPA)在纳米TiO_2悬浆体系中的光催化氧化特性.结果表明:(1)UV-TiO_2对水中BPA有较强光催化氧化降解作用.在10 W低压汞灯照射下,当纳米TiO_2用量为1.0 g/L、pH为5.5、BPA初始质量浓度为10 mg/L、曝气量为4.0 mL/min、温度为室温、反应时间为120 min时,BPA去除率可达97.1%.当pH≥9.5时,120 min后BPA已经基本光催化氧化降解完全.(2)BPA的光催化氧化降解曲线均很好地符合一级反应动力学方程.其速率常数与纳米TiO_2用量、pH、BPA初始浓度、曝气量有关;促进·OH和电子-空穴对的生成是提高光催化氧化反应速率的重要途径.     

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.     

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。     

TiO2纳米管催化降解4，4’-二溴联苯的影响因素和动力学研究

利用TiO₂纳米管催化降解水中的4，4’-二溴联苯，对催化降解过程和影响因素进行研究。结果表明，TiO₂纳米管对其有较高的催化降解效率且降解过程符合Langmuir-Hinshelwood动力学模式。不同光源、4，4’-二溴联苯的初始浓度、纳米管添加量和pH值对催化降解过程都有较大影响，其中pH值的影响最为明显。反应液在中性状态下的降解率明显低于pH=1或11的情况。在pH=1时，4，4’-二溴联苯的降解率达86%。