Photocatalytic activity of TiO2 films grown on different substrates

Titanium dioxide films were prepared on glass, indium-tin oxide (ITO) glass and p-type monocrystalline silicon and studied for the photocatalytic degradation of rhodamine B in an aqueous medium. Raman, AFM, and XPS spectroscopic investigations of these films indicated that microstructure of titanium oxide films were greatly affected by the substrate materials. Rutile was confirmed to be easily formed on the surface of ITO glass, and TiO2 tended to grow as closely packed particles that were elongated strips with an average size of 20 nm, and had lovely contrast with the perfectly round particles grown on p-type monocrystalline silicon. Charge transfer between the film and silicon substrate was verified by surface photovoltage spectra. This may be the real reason why the films grown on ITO glass and silicon substrates exhibit higher photocatalytic reactivity than the film on glass substrate. Moreover, the different surface properties also seem to be responsible for the different activity.     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Utilization of TiO2 deposited on glass plates for removal of metals from aqueous wastes

Glass plates coated with TiO2 were used in a photocatalytic process to collect mercury, lead, copper and cadmium from aqueous solutions containing individual metals and mixtures. Stripping voltammetry, verified to achieve 1-10 ppb detection limits, was used to show that individual metals at concentrations of 1000 to 5200 ppb were reduced to undetectable levels in 3 to 55 min. Capillary electrophoresis (CE) with 8-hydroxyquinoline-5-sulfonic acid as complexing agent was used when appropriate, since it could quantitate all four metals under study in one run although it was less sensitive. It was demonstrated that 100 mL solutions containing 10 ppm of each of the four metals could be treated with a 10 cm2 TiO2-coated plate to leave undetectable metal concentrations in one hour. Stripping voltammetry using carbon electrodes coated with mercury films was estimated to generate daily about 1.1 L of aqueous waste containing 0.1 ppm of each metal. The results indicate the feasibility of assembling an apparatus capable of treating the waste generated by stripping voltammetry to render the latter suitable for routine on-site analyses without environmental concern. Data were also obtained to show the effectiveness in treating silver containing solutions, indicating suitability of the photocatalytic process in treating photographic processing wastes.     

Development and laboratory performance evaluation of a personal cascade impactor

This paper presents the design and laboratory evaluation of a personal cascade impactor. The system is compact, lightweight, and uses a single battery-operated sampling pump. It operates at a flow rate of 5 L/min and consists of four impaction stages, each equipped with slit-shaped acceleration nozzles, and a backup filter. The impactor was calibrated using polydisperse particles. The 50% cut points of the four stages were 9.6, 2.6, 1.0, and 0.5 microm, respectively. The backup filter is placed downstream of the fourth stage and is used to collect the particles with an aerodynamic diameter smaller than 0.5 microm (dp < 0.5 microm). The major feature of this novel sampler is its ability not only to fractionate the particles with an aerodynamic diameter smaller than 10 microm to the various size fractions, but also to collect them onto relatively small polyurethane foam substrates without using adhesives. Although the impaction substrates are not coated with adhesives such as grease or mineral oil, particle bounce and re-entrainment losses were found to be insignificant. Interstage losses of particles smaller than 0.5 microm were less than 10%; for fine particles, less than 5%; and for coarse particles, less than 12%. The pressure drop across the four stages and the backup filter were 0.015 kPa (0.153 cm H2O),0.025 kPa (0.255 cm H2O), 0.274 kPa (2.794 cm H2O), 0.323 kPa (3.294 cm H2O), and 0.370 kPa (3.773 cm H2O), respectively. Particles can be easily recovered from the foam substrates using aqueous extraction.     

Gas phase trichloroethylene (TCE) photooxidation and byproduct formation: photolysis vs. titania/silica based photocatalysis

Photooxidation of trichloroethylene (TCE) was examined in comparative study using photolysis and photocatalysis. Degussa P25 titania coated on reactor wall and deposited on silica based microporous support were used as photocatalyst. The destruction of TCE and formation of potential byproducts were investigated under steady state conditions using annular photoreactors. Experimental work involved passing polluted air containing TCE through the UV photoreactor at varying concentrations and residence times. Ultraviolet illumination was provided by low pressure mercury lamps with outputs at either 254 nm, 365 nm, or 185/254 nm. Silica supported photocatalyst yielded maximum removal capacity of up to about 6 kg TCE per m3 per hour, nearly twice that provided by the coated titania. Direct photolysis with ozone generating UV also provided very high TCE conversion of up to 6kg TCE per m3 per hour. However, major quantities of phosgene and dichloroacetyle chloride (DCAC) were produced as byproducts. TCE removal using silica based photocatalyst did not result in any detectable DCAC. Only phosgene along with trace amounts of chloroform and carbon tetrachloride were identified as oxidation byproducts with silica based photocatalyst.     

Investigation of the antibacterial effects of silver-modified TiO2 and ZnO plasmonic photocatalysts embedded in polymer thin films

Nanosilver-modified TiO₂ and ZnO photocatalysts were studied against methicillin-resistant Staphylococcus aureus on the surface and against naturally occurring airborne microorganisms. The photocatalysts/polymer nanohybrid films were prepared by spray coating technique on the surface of glass plates and on the inner surface of the reactive light source. The photoreactive surfaces were activated with visible light emitting LED light at λ?=?405 nm. The optical properties of the prepared photocatalyst/polymer nanohybrid films were characterized by diffuse reflectance measurements. The photocatalytic properties were verified with the degradation of ethanol by gas chromatography measurements. The destruction of the bacterial cell wall component was examined with transmission electron microscope. The antibacterial effect of the photocatalyst/polymer nanohybrid films was tested with different methods and with the associated standard ISO 27447:2009. With the photoreactive coatings, an extensive disinfectant film was developed and successfully prepared. The cell wall component of S. aureus was degraded after 1 h of illumination. The antibacterial effect of the nanohybrid films has been proven by measuring the decrease of the number of methicillin-resistant S. aureus on the surface and in the air as the function of illumination time. The photocatalyst/polymer nanohybrid films could inactivate 99.9 % of the investigated bacteria on different thin films after 2 h of illumination with visible light source. The reactive light source with the inner-coated photocatalyst could kill 96 % of naturally occurring airborne microorganisms after 48 h of visible light illumination in indoor air sample. The TEM results and the microbiological measurements were completed with toxicity tests carried out with Vibrio fischeri bioluminescence bacterium.     

Photosensitised humic-like substances (HULIS) formation processes of atmospheric significance: a review

Photosensitised reactions can produce compounds that closely resemble the humic-like substances (HULIS) occurring in atmospheric aerosols. The relevant processes have been observed in the laboratory, in both gas–solid systems and the aqueous phase. They involve triplet sensitisers (such as benzophenones, anthraquinones and nitroaromatic compounds, which yield reactive triplet states after sunlight absorption) or photogenerated oxidants like ^?OH, in the presence of substrates that undergo oligomerisation reactions upon oxidation. Formation of higher molecular weight compounds, modification of the wettability properties of organic films and photoproduction of substances with humic-like fluorescence properties have been observed as a consequence of the photosensitised reactions. Ozone plays an important but still not completely clear role in gas–solid systems.     

Effects of driving conditions on diesel exhaust particulates

Four driving conditions were examined to characterize how speeds and loads of a medium-duty diesel engine affect resultant diesel exhaust particulates (DEPs) in terms of number concentrations (< or =400 nm), size distribution, persistent free radicals, elemental carbon (EC), and organic carbon (OC). At the medium engine load (60%), DEPs surged in number concentrations at around 40-70 nm, whereas DEPs from the full engine load (100%) showed a distinctive bimodal distribution with a large population of 30-50 nm and 100-400 nm. Under the full engine load, engine speeds insignificantly affected resultant DEP number concentrations. When the engine load decreased from 100% to the medium level (60%), DEPs of ultrafine size and 100-400 nm decreased at least 1.4 times (from 5.6 x 10(8) to 4 x 10(8) #/cm3) and more than 3 times (from 2.7 x 10(8) to 0.8 x 10(8) #/cm3), respectively. The same reduction in the engine load significantly decreased persistent free radicals in DEPs up to approximately 30 times (from 123 x 10(16) to 4 x 10(16) #spin/g). Decreasing the engine load from 100 to 60% also concurrently reduced both EC and OC in total DEPs around 2 times, from 27.3 to 13.9 mg/m3, and from 17.6 to 9.2 mg/m3, respectively. For DEPs smaller than 1 microm, under the full engine load, EC and OC consistently peaked at 170-330 nm under an engine speed of 1800 rpm or 94-170 nm under an engine speed of 3000 rpm, reflecting processes of nucleation, cluster-cluster agglomeration, and condensation. Decreasing the engine load from 100 to 60% reduced EC and OC in DEPs (smaller than 1 microm) at least 3 times (0.6 to 0.2 mg/m3) and 2 times (0.4 to 0.2 mg/m3), respectively. Taken together, decreasing the full engine load to a medium (60%) level effectively reduced the number concentrations (< or =400 nm), persistent free radicals, EC, and OC of total DEPs, as well as the concentration of EC and OC in ultrafine and accumulation-mode DEPs.     

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm(-2) but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving approximately 90% after 35 min irradiation under 19 W m(-2), while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation.     

纳米TiO2薄膜在不同陶瓷表面的负载及其光催化性能研究

利用2种不同表面处理的陶瓷作为载体,用溶胶凝胶法在其表面进行了纳米TiO2光催化薄膜的负载.采用X射线衍射法(XRD)、X射线光电子能谱仪(XPS)和扫描电镜(SEM)对薄膜的粒径、横断面及表面组成进行了表征和分析,结果表明,TiO2的平均粒径约为15 nm,釉面陶瓷TiO2薄膜分布均匀,膜厚约为300 nm;无釉陶瓷TiO2薄膜分布不均,膜层不明显;2种载体中的一些基质离子在TiO2薄膜有渗透.苯酚的降解实验表明,以2种不同表面处理的陶瓷为载体的TiO2薄膜对苯酚的降解均符合一级反应动力学,就催化活性而言,TiO2/釉面陶瓷＞TiO2/无釉陶瓷,分析认为基质渗透的Ca2 有降低TiO2光催化活性的作用;该薄膜对实际生产多菌灵废水具有催化降解作用.重复降解实验20次,TiO2/釉面陶瓷和TiO2/无釉陶瓷对苯酚的去除率仅分别降低9%和6%.     

Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: an experimental and theoretical examination of hydrazine derivatives

The photocatalytic oxidation of oxalyldihydrazide, N,N'-bis(hydrazocarbonyl)hydrazide, N,N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N2 gas, NH4+ (and/or NO3-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrazo group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrazo groups were photoconverted mainly into N2 gas (in mineralization yields above 70%) and partially to NH4 ions (below 10%). The formation of NO3- ions was scarcely recognized.     

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.     

Toxicity and biodegradability of sulfonamides and products of their photocatalytic degradation in aqueous solutions

The photocatalytic degradation of sulfacetamide, sulfathiazole, sulfamethoxazole and sulfadiazine in water solutions during their illumination of UV radiation (lambda(max) 366 nm) with TiO2 catalyst was examined. The growth-inhibition effect of sulfonamides and intermediate products theirs photodegradation was investigated in aqueous solution with the green alga Chlorella vulgaris. The biodegradability of the investigated compounds was determined in the illuminated solutions and is expressed as Biochemical Oxygen Demand. It was found that all of the investigated sulfonamides in the initial solutions were resistant to biodegradation and were toxic relative to C. vulgaris. The toxicity (EC50 values) relative to C. vulgaris increased in the following order sulfacetamide, sulfathiazole, sulfamethoxazole, sulfadiazine. All of the investigated sulfonamides undergo photocatalytic degradation. The toxicity of intermediate products of the sulfonamides degradation was significantly lower than the toxicity of sulfonamides in the initial solutions and was dependent on illumination time and degradation rate. The intermediate products of photocatalysis in contrast to the initial sulfonamides, might be mineralized using biological methods.     

Enhanced photoelectrocatalytic performance of Zn-doped WO(3) photocatalysts for nitrite ions degradation under visible light

WO(3) and Zn-doped WO(3) thin films were prepared on indium-tin oxide glass by a dip-coating. The composite films were characterized by UV-Vis absorption spectra, X-ray diffraction and scanning electron microscope. The effect of preparation conditions (concentration of Zn, annealing temperature, number of layers) on the photocurrent was studied. It was found that the photocurrent under visible light displayed the highest value for 2% Zn-WO(3) films annealed at 400 degrees C. The photocatalytic activity of the Zn-doped WO(3) was evaluated in terms of decay rate of nitrite ions under visible light. The influence of applied potential, initial pH and nitrite concentration on the reaction rate was studied. The experiments demonstrated that NO(2)(-) could be efficiently degraded on the doped photoanode that showed a higher activity than the undoped WO(3) especially under high anodic potential (>0.7 V). The rate of degradation was enhanced in aqueous NaCl solutions. Furthermore, it was demonstrated that the photodegradation mechanism of NO(2)(-) proceeded mainly indirectly via OH radicals. The possible reason of enhancement of reaction rate was also discussed.     

The enhanced PC and PEC oxidation of formic acid in aqueous solution using a Cu-TiO2/ITO film

The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of Cu-TiO2/ITO films for degrading formic acid in aqueous solution was investigated in this study. Compared with a TiO2/ITO film, the degradation efficiency of formic acid on the Cu-TiO2 films increased markedly in both the PC and PEC oxidation processes. However, it was found that the photodeposited Cu metal on the Cu-TiO2 films could electrochemically dissolute during the PEC reaction, while an electrical bias with the voltage higher than 1.48 V was applied. It is believed this is a common problem occurred for several metals deposition on the TiO2 films, which results in a poor stability of the metal-deposited TiO2 electrode in PEC processes. To improve the stability of the Cu-TiO2 electrode, an alternative process between PC and PEC reactions was investigated. It was found that the dissolute Cu metal during the PEC process was re-deposited on the Cu-TiO2 film again during the PC process. The experiments with repeated runs demonstrated that this alternative process could not only overcome the loss of Cu, but also enhance the PEC oxidation efficiency of the Cu-TiO2 films.     

真空紫外光降解五氯酚钠以及过硫酸盐对反应的促进作用

研究了真空紫外光(VUV,185 am)对于水溶液中五氯酚钠的降解,反应2 h后,初始浓度为10 mg/L的五氯酚钠的去除率达到99%以上,有机氯的脱除率达到70%以上,有效地实现了五氯酚钠的脱毒.溶液初始pH值对五氯酚钠的真空紫外光解有很大影响,pH=10.9时的降解速率常数是pH=3.1时的3倍.表观一级反应速率常数随初始浓度的增加而线性下降.在反应溶液中加入过硫酸盐,可有效提高五氯酚钠的真空紫外光降解速率和矿化速率,过硫酸盐和五氯酚钠摩尔比为24时,降解速率提高3倍,反应4 h后TOC去除率达到95%.     

Systematic biases in measured PM10 values with U.S. Environmental Protection Agency-approved samplers at Owens Lake, California

From 1993 through 1998, Wedding or Graseby high-volume PM10 samplers were collocated with tapered element oscillating microbalance (TEOM) samplers at three sites at Owens Lake, CA. The study area is heavily impacted by windblown dust from the dry Owens Lake bed, which was exposed as a result of water diversions to the city of Los Angeles. A dichotomous (dichot) sampler and three collocated Partisol samplers were added in 1995 and 1999, respectively. U.S. Environmental Protection Agency (EPA) operating procedures were followed for all samplers, except for a Wedding sampler that was not cleaned for the purpose of this study. On average, the TEOM and Partisol samplers agreed to within 6%, and the dichot, Graseby, and Wedding samplers measured lower PM10 concentrations by about 10, 25, and 35%, respectively. Surprisingly, the "clean" Wedding sampler consistently measured the same concentration as the "dirty" Wedding sampler through 85 runs without cleaning. The finding that the Graseby and Wedding high-volume PM10 samplers read consistently lower than the TEOM, Partisol, and dichot samplers at Owens Lake is consistent with PM10 sampler comparisons done in other fugitive dust areas, and with wind tunnel tests showing that sampler cut points can be significantly lower than 10 microns under certain conditions. However, these results are opposite of the bias found for TEOM samplers in areas that have significant amounts of volatile particles, where the TEOM reads low due to the vaporization of particles on the TEOM's heated filter. Coarse particles like fugitive dust are relatively unaffected by the filter temperature. This study shows that in the absence of volatile particles and in the presence of fugitive dust, a different systematic bias of up to 35% exists between samplers using dichot inlets and high-volume samplers, which may cause the Graseby and Wedding PM10 samplers to undermeasure PM10 by up to 35% when the PM10 is predominantly from coarse particulate sources.     

光纤ZnO薄膜的制备及光催化性能研究

实验利用射频磁控溅射镀膜工艺,分别在光纤和石英玻璃上成功制备了ZnO薄膜。采用X射线衍射仪、原子力显微镜和荧光分光光度计对薄膜进行了测试分析,并对其光催化降解苯酚的性能进行了对比测试。结果表明,该薄膜具有良好的C轴取向性,光致发光峰分别位于362nm、421nm和486nm附近,且随着薄膜样品晶粒的减小而出现蓝移,光纤上ZnO薄膜的光催化能力是以石英玻璃为基底的ZnO薄膜的193倍,光催化效果显著。     

The photocatalytic degradation of methylene blue by green semiconductor films that is induced by irradiation by a light-emitting diode and visible light

This study develops a low-energy rotating photocatalytic contactor (LE-RPC) that has Cu-doped TiO₂ films coated on stainless-steel rotating disks, to experimentally evaluate the efficiency of the degradation and decolorization of methylene blue (MB) under irradiation from different light sources (visible 430 nm, light-emitting diode [LED] 460 nm, and LED 525 nm). The production of hydroxyl radicals is also examined. The experimental results show that the photocatalytic activity of TiO₂ that is doped with Cu²⁺ is induced by illumination with visible light and an LED. More than 90% of methylene blue at a 10 mg/L concentration is degraded after illumination by visible light (430 nm) for 4 hr at 20 rpm. This study also demonstrates that the quantity of hydroxyl radicals produced is directly proportional to the light energy intensity. The greater the light energy intensity, the greater is the number of hydroxyl radicals produced.

Implications: The CuO-doped anatase TiO₂ powder was successfully synthesized in this study by a sol–gel method. The catalytic abilities of the stainless-steel film were enhanced in the visible light regions. This study has successfully modified the nano-photocatalytic materials to drop band gap and has also successfully fixed the nano-photocatalytic materials on a substratum to effectively treat dye wastewater in the range of visible light. The results can be useful to the development of a low-energy rotating photocatalytic contactor for decontamination purposes.     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.