丝光沸石负载二氧化钛膜光催化降解邻氯苯酚

利用溶胶法将TiO2负载在天然丝光沸石上制成TiO2薄膜,在125 W高压汞灯照射下,对邻氯苯酚溶液进行光催化氧化反应,研究负载后的催化剂活性。通过实验得出,沸石作为一种多孔性的催化剂载体,在反应中通过吸附作用增加催化剂表面的邻氯苯酚浓度,可显著提高光催化剂活性。     

A comparative study of doped and un-doped sol-gel TiO2 and P25 TiO2 (photo)electrodes.

Doped and undoped titanium dioxide films have been deposited on indium tin oxide glass using the sol-gel technique. The percentage of rutile in the prepared TiO2, calcined at 823 K and determined by X-ray diffraction, was 23% compared to 24% of rutile in P25-TiO2. Cerium doped TiO2 showed mainly the anatase phase, as characterised by both X-ray diffraction and Raman spectroscopy. The electrochemical and photoelectrochemical properties of the films were studied by cyclic voltammetry and electrochemical impedance spectroscopy. The (photo)electrochemical characteristics of the different films are reported and discussed.     

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.     

Comparison of different TiO2 photocatalysts for the gas phase oxidation of volatile organic compounds.

Gas-solid photocatalyzed oxidation of air contaminants is being explored more and more for possible application to decontamination, purification and deodorization of enclosed atmospheres. Indoor air is characterized by a huge number of pollutants at low concentrations. Volatile organic compounds (VOC) represent the main indoor air pollutants category, and are of great concern since some of them can act negatively on human health. Several treatments exist to reduce VOC concentrations in gaseous effluents, but photocatalytic oxidation appears to be the most appropriate regarding indoor air specific constraints. It is then necessary to develop photocatalysts, which can possibly be used in an application such as indoor air-quality improvement. In the present work, three different TiO2-based materials were studied and compared for the photocatalytic oxidation of a typical pollutant of indoor air: methyl ethyl ketone. Kinetic studies were performed for each material in dry and humid air conditions, and the Langmuir-Hinshelwood model was satisfactorily applied in almost every case. A second approach consisted of determining methyl ethyl ketone degradation by-products. Acetaldehyde was found to be the main gaseous intermediate, and could be taken into account in the general Langmuir-Hinshelwood modeling.     

TiO2光催化氧化技术处理环境污染物的研究进展

阐述了TiO2光催化氧化法的原理、TiO2催化剂的制备以及粉末型和负载型两种形态的TiO2在光催化氧化有机污染物方面的应用情况,指出粉末型TiO2主要应用于废水处理,负载型TiO2主要应用于废水处理、垃圾填埋场渗滤液处理和环境净化。粉末型TiO2的研究发展方向是通过改性以提高其活性和可应用性,如表面沉积贵金属、表面耦合、表面敏化、过渡金属掺杂等;负载型TiO2的研究方向是通过改性以提高催化活性,选择合适的载体,充分发挥载体的优势,加强固定态光催化氧化技术与其他技术的联用,利用太阳能作用光源等。     

F/Ce掺杂Bi2WO6可见光光催化氧化甲基橙

针对新型光催化剂Bi2WO6在可见光条件下光生电子-空穴分离效率低的问题,本文采用液固相水热反应的方法制备了F/Ce掺杂改性的Bi2WO6光催化剂。通过X射线粉末衍射(XRD)、扫描电镜(SEM)和紫外-可见漫反射(UV-vis DRS)等分析表明,F/Ce掺杂Bi2WO6光催化剂具有明显的层状结构,可有效降低电子-空穴的复合率,且改性后的Bi2WO6吸收波长发生红移。光催化氧化处理甲基橙降解实验结果表明:F和Ce共掺杂下Bi2WO6在可见光下具有最高的光催化活性,主要活性物质为羟基自由基(·OH),甲基橙的降解率在50 min后可以达到97%,催化活性比纯Bi2WO6提高了近2倍。本研究为研发水环境中高浓度有机废水,特别是难降解有机污染物的高效治理技术提供了基础数据。     

Photocatalytic degradation of parathion in aqueous TiO2 dispersion: the effect of hydrogen peroxide and light intensity

The photodegradation of parathion in the direct photolysis, UV/TiO₂, UV/H₂O₂ and UV/TiO₂/H₂O₂ systems was investigated at 25°C. The effect of light intensity was also examined to clarify the relationship between the photo flux and decomposition rate of parathion. Results of the study demonstrated that no obvious degradation of parathion in dark reaction occurred within 24 hours. However, the addition of TiO₂ and/or H₂O₂ promotes the degradation efficiency of parathion. Adding H₂O₂ was more effective in the photocatalytic oxidation of parathion than TiO₂. Also, hydrogen peroxide was found as an intermediate with the maximum concentration of 55 μM in UV/TiO₂ system during the photodegradation of parathion. A higher intensity of lamp could increase the degradation rale of parathion. However, the quantum efficiency for degradation of parathion decreased from 0.053 to 0.006 when light intensity increased from 100 W to 450W. Photodecomposition followed a pseudo-first-order reaction. The rate constants of parathion ranged from 0.003 min^-1 for direct photolysis to 0.023 min^-1 for UV/TiO₂/H₂O₂ system. This study indicated that photocatalytic degradation is a highly promising technology for detoxifying parathion.     

Ability of humans to smell geosmin, 2-MIB and nonadienal in indoor air when using contaminated drinking water.

The most common compounds responsible for off flavours are geosmin, 2-MIB, and nonadienal which are poorly removed by conventional water treatment operations and hence result in customer complaints. Because these odourants are moderately volatile and have very low odour threshold values, it is necessary to determine their concentrations in air when water is used indoors. If the detectable aqueous concentrations for these odourants are known, the utilities may take action to treat their water at times when the concentration of the raw water exceeds the threshold concentration. To predict the concentration in the shower stall and bathroom air after showering, recently published Henry's law constants for the selected odourants and a model developed to determine the volatilization of the odourous compounds by applying two-resistance theory were used. Then the results were compared with the odour threshold concentration data to determine under which conditions the odourants become detectable. For parameters representing a typical bathroom and shower stall setting, the results showed that the odourants become detectable when the aqueous concentration of geosmin and nonadienal exceed 10 ng/L at 42 degrees C. As the aqueous concentration increases, geosmin and nonadienal become detectable at lower temperatures, however 2-MIB is only detectable above 20 ng/L and at 42 degrees C.     

A bifunctionalized dye-sensitized TiO(2) film for efficient degradation of methyl orange under visible light irradiation

A new bifunctionalized TiO(2) film containing a dye-sensitized region and a degradation region was described. A similar structure of dye-sensitized solar cell (DSSC) was fabricated in the dye-sensitized region to accomplish separation of electrons from positive charges, and separation of dye from pollutants to avoid dye decomposition. The bifunctionalized TiO(2) film electrode and anode electrode can degrade methyl orange (MO) in reactors A and B, respectively. The degradation efficiency was enhanced remarkably by an external electrical potential. The decolorization of MO reaches as high as 95% after 2 h visible light irradiation at an external potential of 0.5 V along with a loss of 41% total organic carbon (TOC). The possible reason for the improvement of degradation by external DC potential was discussed. Effects of pH and inorganic salts on the decolorization are present.     

The adsorption and photodegradation of oxalic acid at the TiO2 surface.

ATR-FTIR measurements in combination with quantum chemical calculations were performed to study chemical reactions taking place at the surface of a thin TiO2 layer immersed in an aqueous oxalic acid solution under UV(A) illumination. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexes for the anatase phase. Under UV(A) illumination, one of the adsorbed species on the anatase phase preferably undergoes photo-degradation and at the same time more molecules of oxalic acid are adsorbed at the TiO2 surface which is thus enriched in the second complexation mode. The spectral changes observed under UV(A) illumination are explained in the light of different theories: photo-desorption of water molecules as a thermal mechanism induced by the absorption of photons, surface reconstruction, and newly exposed surface area provided by the de-aggregation of the TiO2 particles.     

Determination of reaction rate constants for phenol oxidation using SnO2/Ti anodes coupled with activated carbon adsorption in the presence of TiO2 as catalyst

Series of experiments for phenol degradation with assistance of TiO2 catalyst at pH of 6.5 and temperature of 25 degrees C were conducted using a lab-scale electrochemical reactor constructed in our laboratory. According to the results, at the presence of the TiO2 catalyst the removal of phenol was increased and first-order kinetics could describe the evolution of phenol concentration. For inspecting the relationship between rate constants and dosage of TiO2, two possible kinetics were proposed in this study. Contrasted to the abundant experimental data, a reasonable kinetics was obtained for the estimation of phenol concentration effluent during continuous flow of raw wastewater, especially when the TiO2 dosage was less than 0.5g L(-1). The model obtained from these experiments could employed for the calculation of rate constants at different TiO2 dosage and the necessary dosage of catalyst when a discharge standard was designed.     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

Degradation of parathion and the reduction of acute toxicity in TiO2 photocatalysis.

Photocatalytic degradation of methyl parathion was done using a circulating TiO2/UV and TiO2/solar reactor. Indoor experimental results showed that, under the photocatalysis conditions, parathion was more effectively degraded than under the photolysis and TiO2 only conditions. Parathion (38 microM) was completely degraded under photocatalysis within 90 min, and more than 80% TOC decrease after 150 minutes. The main ionic byproducts during the photocatalysis were measured, and almost complete nitrogen recovery was achieved as mainly NO3- NO2-, and NH4+, and 80% of sulfur as recovered as SO4(2)-. Organic intermediates such as nitrophenol and methyl paraoxon were also identified during the photocatalysis of parathion, and these were further degraded after 90 minutes. Microtox bioassay using Vibrio fischeri was used in evaluating the toxicity of solutions treated by photocatalysis and photolysis of parathion. The results showed that the acute toxicity expressed as EC50 almost reduced after 90 min under the photocatalysis condition whereas only 40% reduction of toxicity as EC50 was achieved in photolysis condition. The outdoor results using a TiO2/solar system were similar to the TiO2 indoor system, indicating the possibility of applying TiO2/solar system for the treatment of parathion-contaminated water.     

Photocatalytic inactivation of Flavobacterium and E. coli in water by a continuous stirred tank reactor (CSTR) fed with suspended/immobilised TiO2 medium

A photocatalytic continuous stirred tank reactor (CSTR) was built at laboratory scale to inactivate two environmental bacteria strains (Flavobacterium and E. coli) in tap water. Several parameters were found to impact reactor efficiency. Bacterial initial concentration is an important factor in inactivation rate. After 30 minutes of irradiation at 10(8)-10(9) CFU mL(-1) starting concentration, a >5 log reduction was achieved while at 10(4)-10(6) CFU mL(-1) only a 2 log reduction was observed. Water hardness and pH have an important influence on the photocatalytic inactivation process. Soft water, with low Ca(+2) and Mg(+2) at low pH approximately 5.3 resulted in increased inactivation of Flavobacterium reaching >6 orders of magnitude reduction. E. coli and Flavobacterium at pH 5 were inactivated by 3 logs more as compared to pH 7 under similar conditions. pH below TiO2 isoelectric point (approximately 5.6) supports better contact between bacteria and anatase particles resulting in superior inactivation. TiO2 powder suspension was compared with immobilised powder in sol-gel coated glass beads in order to exclude the need for particles separation from the treated water. TiO2 suspension was more effective by 3 orders of magnitude when compared to coated glass beads. An interesting observation was found between the two bacterial strains based on their hydrophobicity/hydrophilicity balance. The more hydrophobic Flavobacterium compared to E. coli was inactivated photocatalytically by >3 logs more then E. coli in the first 30 minutes of irradiation interval. The results indicate the importance of the parameters involved in the contact between TiO2 particles and microorganisms that govern the successful inactivation rate in CSTR.     

Comparative toxicity of nano-scale TiO2, SiO2 and ZnO water suspensions.

TiO2, SiO2 and ZnO are common additives with improved applications at the nanoscale. The antibacterial activity of TiO2, which has important ecosystem health implications, is well understood. However, less attention has been paid to the antibacterial activity of SiO2 and ZnO despite them also producing reactive oxygen species. This paper explores the relative toxicity of TiO2, SiO2 and ZnO water suspensions towards bacteria (B. subtilis, E. coli) and the eukaryotic Daphnia magna. These three photosensitive nanomaterials were hazardous to all test organisms, with toxicity increasing with particle concentration. Toxicity of the three compounds decreased from ZnO to TiO2 to SiO2 and Daphnia were most susceptible to their effects. Nominal particle size did not affect the toxicity of these compounds. Antibacterial activity was noted under both dark and light conditions indicating that mechanisms additional to ROS production were responsible for growth inhibition. These results highlight the need for caution during the use and disposal of such manufactured nanomaterials to prevent unintended environmental impacts, as well as the importance of further research on the mechanisms and factors that increase toxicity to enhance risk management.     

Case study of odor and indoor air quality assessment in the dewatering building at the Stickney Water Reclamation Plant

Indoor air quality (IAQ) and odors were determined using sampling/monitoring, measurement, and modeling methods in a large dewatering building at a very large water reclamation plant. The ultimate goal was to determine control strategies to reduce the sensory impacts on the workforce and achieve odor reduction within the building. Study approaches included: (1) investigation of air mixing by using CO(2) as an indicator, (2) measurement of airflow capacity of ventilation fans, (3) measurement of odors and odorants, (4) development of statistical and IAQ models, and (5) recommendation of control strategies. The results showed that air quality in the building complies with occupational safety and health guidelines; however, nuisance odors that can increase stress and productivity loss still persist. Excess roof fan capacity induced odor dispersion to the upper levels. Lack of a local air exhaust system of sufficient capacity and optimum design was found to be the contributor to occasional less than adequate indoor air quality and odors. Overall, air ventilation rate in the building has less effect on persistence of odors in the building. Odor/odorant emission rates from centrifuge drops were approximately 100 times higher than those from the open conveyors. Based on measurements and modeling, the key control strategies recommended include increasing local air exhaust system capacity and relocation of exhaust hoods closer to the centrifuge drops.     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

Modelling the kinetics of UV/H2O2 oxidation of dichloroacetic acid.

The intrinsic reaction kinetics of the decomposition of dichloroacetic acid (DCA) using UV/H2O2 was studied. A complete mathematical model, including the effect of the absorbed radiation intensities and H2O2 concentration was developed. The results of the kinetic measurements were analysed using a complete mathematical model of the experimental device that was used for the laboratory operation (a differential reactor inside a recycle). In this way it was expected to obtain intrinsic kinetic parameters. Experimental data agree well with theoretical predictions esmploying just two kinetic parameters derived from the proposed reaction mechanism.     

Simultaneous photocatalytic oxidation of pharmaceuticals and inactivation of Escherichia coli in wastewater treatment plant effluents with suspended and immobilised TiO(2)

Simultaneous Escherichia coli inactivation and oxidation of pharmaceuticals in simulated wastewater treatment plant effluents has been investigated using a photocatalytic treatment with TiO(2) in suspension and immobilised onto a fixed-bed reactor. Non-photocatalytic reference experiments of dark adsorption and photolysis showed a higher sensitivity of E. coli towards the chemical composition of water in comparison with the concentration of pharmaceuticals that remains unaffected. Moreover, it must be underlined that the presence of pharmaceuticals (including antibiotics) did not seem to affect the bacterial viability at such low concentrations. Concerning photocatalytic experiments, both suspended and immobilised TiO(2) were able to simultaneously inactivate and oxidise both kinds of pollutants (bacteria and pharmaceuticals). The fixed-bed reactor showed similar activity to that of the slurry without deactivation after several cycles of reuse. That makes TiO(2) photocatalysis a quite interesting technology for the treatment of drinking water supplies or wastewater plant effluents, allowing the removal of emerging contaminants such as pharmaceuticals during the disinfection treatment.     

Evaluation of the combined solar TiO2/photo-Fenton process using multivariate analysis.

The effect of combining the photocatalytic processes using TiO2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 is used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H2O2 and TiO2 in the degradation of DCA.