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.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

Inactivation of LPS and RNase A on photocatalytically active surfaces

TiO₂ coated surfaces are able to generate highly reactive oxidizing species under mild UV-A light exposure in the presence of water and oxygen. We have demonstrated that these radicals are sufficient to eliminate different pathogenic bacteria, by breaking their cell walls. The photocatalytic activity of surfaces coated with titanium dioxide offers therefore an alternative possibility of disinfection. However, restriction of bacterial growth does not protect surfaces from bacterial derived contaminations, such as endotoxins. Lipopolysaccharides (LPS) and Ribonuclease A (RNAse A) represent the two most abundant contaminations, causing severe problems in biomedical and immunological research as well as in the pharmaceutical industry. Due to their high stability, complete removal of these contaminants is technically challenging. Using irradiated TiO₂ coated glass plates, RNAse A and LPS containing contaminations could be completely inactivated. By establishing highly sensitive immuno-based assays, destruction of the contaminants was quantified and shown to be independent of the initial concentrations, following a zero-order reaction. Exposure for 96 h resulted in a reduction of 11 ng of LPS and 7 units of RNase A cm⁻² surface. These amounts are comparable to contamination levels found under standard working conditions. Titanium dioxide coatings provide therefore a powerful tool for auto-disinfection and self-cleaning of surfaces.     

The pH and anion effects on the heterogeneous photocatalytic degradation of o-methylbenzoic acid in TiO2 aqueous suspension

This investigation used UV light of 365 nm and titanium dioxide in aqueous suspension to study the photocatalytic reaction of o-methylbenzoic acid under the influence of pH values, anion additives and the varieties of titanium dioxide. From experimental results, under the condition of 5 g/l TiO2, pH 3 and light intensity of 2.45 mW/cm2, 0.1 mM of o-methylbenzoic acid could be completely decomposed in 2 h. The reaction was faster with lowering pH, and was found to be apparent first-order following Langmuir-Hinshelwood model. In the presence of anion additives, the inhibitive effect of chloride ions was larger than that of sulfate ions under acidic condition for Degussa brand titanium dioxide, but without influence using Janssen brand. Both brands, however, promoted the mineralization of o-methylbenzoic acid (o-MBA).     

Artificial intelligence modeling to evaluate field performance of photocatalytic asphalt pavement for ambient air purification

In recent years, the application of titanium dioxide (TiO₂) as a photocatalyst in asphalt pavement has received considerable attention for purifying ambient air from traffic-emitted pollutants via photocatalytic processes. In order to control the increasing deterioration of ambient air quality, urgent and proper risk assessment tools are deemed necessary. However, in practice, monitoring all process parameters for various operating conditions is difficult due to the complex and non-linear nature of air pollution-based problems. Therefore, the development of models to predict air pollutant concentrations is very useful because it can provide early warnings to the population and also reduce the number of measuring sites. This study used artificial neural network (ANN) and neuro-fuzzy (NF) models to predict NO_x concentration in the air as a function of traffic count (T_r) and climatic conditions including humidity (H), temperature (T), solar radiation (S), and wind speed (W) before and after the application of TiO₂ on the pavement surface. These models are useful for modeling because of their ability to be trained using historical data and because of their capability for modeling highly non-linear relationships. To build these models, data were collected from a field study where an aqueous nano TiO₂ solution was sprayed on a 0.2-mile of asphalt pavement in Baton Rouge, LA. Results of this study showed that the NF model provided a better fitting to NO_x measurements than the ANN model in the training, validation, and test steps. Results of a parametric study indicated that traffic level, relative humidity, and solar radiation had the most influence on photocatalytic efficiency.     

纳米TiO2光催化剂负载技术研究

纳米TiO2光催化剂在废水处理、空气净化等环保领域具有诱人的应用前景,将其负载于一定的载体上,并设计出高效的光反应器是其实用化的关键之一.本文对纳米TiO2光催化剂负载所用载体、固定方法及其效果、相关光催化化学反应器作了综合评述.     

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.     

The redox combustion of carbon monoxide for recovering pure carbon dioxide by using molten (Na+,K+)2(CO32-,SO42-) mixtures

Large-scale combustion systems, such as thermal power plants, emit large amounts of carbon dioxide, which can increase global warming. A molten salt redox combustion system was proposed to recover pure carbon dioxide exhausted from the combustion of fossil fuels. This system is composed of two successive processes by using reactions occurring in a molten salt. The molten salt is the mixture of the molten alkali metal sulfates and carbonates. The sulfate ions oxidize the fuels in first processes, being changed to reductive species such as sulfide ions. In this process, carbon dioxide and water are exclusively exhausted. The reductive species of sulfur compounds are oxidized to regenerate the sulfate ions by air in the second process. In this study, these above two processes were tried by using molten [(Na(+))(0.5),(K(+))(0.5)](2)[(CO(3)(2-))(0.9),(SO(4)(2-))(0.1)] alternatively. The oxidation of carbon monoxide as fuel by sulfate ions and the regeneration of sulfate ions by air were investigated in the temperature range of 700-950 degrees C, respectively. These reactions were exothermic. The rate of the regeneration of the sulfate ions was extremely high. During the oxidation of carbon monoxide, the reaction was first order in carbon monoxide with an activation energy of 101 kJ mol(-1). The optimum condition to recover pure carbon dioxide on practical operation was discussed.     

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.     

Effect of adsorbents coated with titanium dioxide on the photocatalytic degradation of propoxur

Photocatalytic oxidation of pesticides in aqueous media irradiated by UV light is a rapidly growing field of research. Therefore, the treatment technology for degradation of propoxur (an insecticide) using titanium dioxide coated on the supports such as activated carbon, zeolite, brick, quartz and glass beads, was performed in this research. Results show that GAC/TiO2 is the best complexing agent for oxidizing propoxur because of its adsorption properities. The others follow the sequence: plain TiO2 > glass beads > zeolite > brick > quartz. The degradation rate of propoxur with plain TiO2 is higher than that with TiO2/GAC complexing agent. But the mineralization rate of propoxur with plain TiO2 is lower than that with TiO2/GAC complexing agent. However, it can be concluded that using GAC as the support can improve the photocatalytic efficiency.     

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.     

Removal of methanol from pulp and paper mills using combined activated carbon adsorption and photocatalytic regeneration

Methanol is one of the major hazardous air pollutants emitted from chemical pulp mills. Its collection and treatment is required by the Maximum Achievable Control Technology portion of the 1998 Cluster Rule. The objective of this study is to investigate the technical feasibility of combined adsorption and photocatalytic regeneration for the removal and destruction of methanol. To facilitate the regeneration, activated carbon (AC) was coated with commercially available photocatalyst by a spray desiccation method. Laboratory-scale experiments were conducted in a fixed-bed reactor equipped with an 8 W black light UV lamp (peak wavelength at 365 nm) at the center. The photocatalyst loaded onto AC had no significant impact on the adsorption capacity of the carbon. High humidity was found to greatly reduce the material's capacity in the adsorption and simultaneous adsorption and photocatalytic oxidation of methanol. The photocatalytic regeneration process is limited by the desorption of the adsorbate. Increasing desorption rate by using purge air greatly increased the regeneration capacity. When the desorption rate was greater than the photocatalytic oxidation rate, however, part of the methanol was directly desorbed without degradation.     

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。     

Photodegradation of monochlorobenzene in titanium dioxide aqueous suspensions

The photocatalytic degradation of monochlorobenzene using titanium dioxide aqueous suspensions was performed under solar-simulated irradiation. The effects of concentration of monochlorobenzene, amount of titanium dioxide and pH of solution on the degradation were examined. The intermediates identified were three monochlorophenols, chlorohydroquinone and hydroxy-hydroquinone.     

Wet and dry atmospheric deposition on TiO2 coated glass

To prevent the soiling of glass window used in the built environment, the use TiO₂ coated products appears an important application matter. To test the cleaning efficiency and the sustainability of self-cleaning glass, a field experiment was conducted under real life condition, on a site representative of the background urban pollution. Samples of float glass, used as reference, and commercialized TiO₂ coated glasses were exposed to dry and wet atmospheric deposition during two years. The crossed optical, chemical and microscopic evaluations performed, after withdrawal, allowed highlighting a sensible difference between the reference and the self-cleaning substrate in terms of accumulation, nature, abundance and geometry of the deposit. This experiment conducted in real site emphasized on the efficacy of self-cleaning glass to reduce the maintenance cost.     

TiO2-assisted degradation of a perfluorinated surfactant in aqueous solutions treated by gliding arc discharge

The plasma–chemical degradation of Forafac 1110, a perfluorinated non-ionic surfactant, in aqueous solutions was investigated using TiO₂ catalysts. The considered plasma was the gliding arc in humid air, which results from an electric discharge at atmospheric pressure and quasi-ambient temperature. Two titanium dioxide powders were used and their synergistic effects on the Forafac degradation were compared. The results were discussed through the evolution of the pH, the conductivity, the fluoride ions concentration released in solutions, the surfactant concentration remaining after treatment and the chemical oxygen demand (COD) measurement.

The combination of the plasma–chemical treatment with heterogeneous catalysis through the use of TiO₂ accelerated the Forafac degradation, since only 60 min was sufficient to remove 96% instead of 360 min needed in the absence of TiO₂. The use of anatase and rutile under the trade-name of Rhodia TiO₂ and Merck TiO₂, respectively, led to different results, because Rhodia TiO₂ has proven to be more efficient. It would seem that the crystalline phase as well as the crystallite size, explain the efficiency of anatase. The advantage of the plasma-catalysis is due to the fact that there is a significant production of the OH^• radicals not only generated by the gliding arc discharge but also by TiO₂.     

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。     

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.     

Spectrophotometric determination of sulphur dioxide

Sulphur dioxide, an important industrial gas and air pollutant, is usually estimated using mercury salts. The authors have developed a method in which hazardous mercury salts are avoided. Sulphur dioxide is trapped in aqueous morpholine and mixed with the excess of dichromate solution in acidic medium. The hexavalent chromium in dichromate is reduced to trivalent chromium by sulphur dioxide and the excess of hexavalent chromium is determined with diphenylcarbazide which yields a soluble red-violet complex with an absorption maximum at 540 nm. The decrease in the absorbance values of the red-violet complex formed after reduction, when compared to that of a reagent control, is proportional to the concentration of sulphur dioxide used for reduction. Beer's law operates between 0.4 and 4 microg ml(-1) concentration of sulphur dioxide in solution.     

Dynamics of sulfur dioxide absorption in a raindrop falling at terminal velocity

Sulfur dioxide absorption dynamics in a raindrop are studied numerically by means of a fully numerical simulation method (FNSM) in which a composite orthogonal grid system consisting of both gas- and liquid-phase is adopted. When a raindrop with fixed radius falls in association with terminal velocity, a recirculation bubble always accompanies the gas-phase flow field in the aft region of the drop. With regard to the drop internal flow structure it has a drastic variation with drop size. When the drop radius is small (e.g. r_s=200 μm), only a single vortex motion is seen inside the drop. Under such a situation, sulfur dioxide absorbed from the interface is mainly transported from the area in front of the aft stagnation point. In contrast, as the drop is relatively large, say, r_s=500 μm, it is of interest to find that a double-vortex motion, composed of a primary and a secondary vortexes, is clearly observed. As a result, the onset of SO₂ transport process occurs at the drop’s surface near where the two vortexes meet. By defining a drop mass transport number, it indicates that the mass transported via internal circulation is always much faster than that by mass diffusion and the latter is highly relevant to the drop radius. Accordingly, the SO₂ transport dynamics in a raindrop is essentially determined by drop size.