Comparison of catalytic activity of two platinised TiO2 films towards the oxidation of organic pollutants

Two types of platinised TiO2 films, i.e., Pt-TiO2/ITO and Pt(TiO2)/ITO, were prepared by a procedure of dip-coating and subsequent photo-deposition, and photo-deposition and subsequent dip-coating, respectively. They were well characterized by DRS, XRD spectra, SEM microscopy and photoelectrochemical measurement. Their photocatalytic, dark catalytic and photoelectrocatalytic activities were investigated using formic acid as a model organic pollutants. Compared with pure TiO2/ITO film, the photocatalytic activity of the platinised TiO2 films were apparently improved. However, the improvement was considerably dependent on the preparation method of these films. Pt-TiO2/ITO not only possessed higher photocatalytic activity but also showed a dark catalytic activity towards HCOOH degradation. As a sequence, it was first emphasized that the dark catalytic effect of Pt-TiO2/ITO was partly responsible for degradation of formic acid in the photocatalytic oxidation process. Although the Pt(TiO2)/ITO film does not exhibit the dark catalytic activity, its photocatalytic degradation efficiencies towards HCOOH are higher than that of Pt-TiO2/ITO film. Therefore, in view of enhanced photocatalytic activity, the Pt(TiO2)/ITO was more favored than Pt-TiO2/ITO film.     

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 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.     

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.     

液晶显示器玻璃基板回收工艺

利用无机溶液对废液晶显示屏的玻璃基板回收工艺作了初步的探索,根据回收处理的难易,简单地将废弃液晶显示屏分为3类:含树脂黑色矩阵膜的上层玻璃基板可以采用氢氧化钠直接浸泡处理、含铬黑矩阵膜的上层玻璃基板和下层玻璃基板可以先用氢氧化钠溶液浸泡去除偏光片,再用氢氟酸溶液浸泡处理。结果表明,利用无机溶液处理可以较快得到干净的玻璃基板,而且工艺简单、成本低。     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

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.     

In situ photoelectrochemical/photocatalytic study of a dye discoloration in a microreactor system using TiO2 thin films

Introduction

In this work, we report in situ studies of UV photoelectrocatalytic discoloration of a dye (indigo carmine) by a TiO₂ thin film in a microreactor to demonstrate the driving force of the applied electrode potential and the dye flow rate toward dye discoloration kinetics.

Methods

TiO₂ 65-nm-thick thin films were deposited by PVD magnetron sputtering technique on a conducting glass substrate of fluorinated tin oxide. A microreactor to measure the discoloration rate, the electrode potential, and the photocurrent in situ, was developed. The dye solutions, before and after measurements in the microreactor, were analyzed by Raman spectroscopy.

Results

The annealed TiO₂ thin films had anatase structure with preferential orientation (101). The discoloration rate of the dye increased with the applied potential to TiO₂ electrode. Further, acceleration of the photocatalytic reaction was achieved by utilizing dye flow recirculation to the microreactor. In both cases the photoelectrochemical/photocatalytic discoloration kinetics of the dye follows the Langmuir?CHinshelwood model, with first-order kinetics.

Conclusions

The feasibility of dye discoloration on TiO₂ thin film electrodes, prepared by magnetron sputtering using a flow microreactor system, has been clearly demonstrated. The discoloration rate is enhanced by applying a positive potential (E _AP) and/or increasing the flow rate. The fastest discoloration and shortest irradiation time (50?min) produced 80% discoloration with an external anodic potential of 0.931?V and a flow rate of 12.2?mL?min^?1.     

Preliminary indications from atomic force microscopy of the presence of rapidly-formed nanoscale films on aquifer material surfaces

The objective of this study was to determine if there is a nanoscale surface film on aquifer-like materials exposed to deep groundwaters, as has previously been found on surfaces exposed to surface and soil waters. Such surface films will modify surface properties that are so important in determining the mobility of many groundwater pollutants. Muscovite mica was used because a) it is a good analogue for the main sorbing phases of many clastic aquifers and b) its cleavage planes are atomically flat allowing high resolution imaging. Freshly-cleaved muscovite plates were exposed to groundwater from a sandstone aquifer for 30 min, and surface properties (morphology, coverage, roughness and tip–substrate force interactions) were measured using atomic force microscopy (AFM). A patchy surface film of several nanometres in depth, incorporating larger separate particles, was found on the mica surface. This film was associated with significantly increased roughness values and AFM probe–sample interaction forces compared with pure water and inorganic (synthetic groundwater) solution controls. Although the results reported are preliminary in nature, if confirmed, such films are likely to affect sorption reactions, surface-facilitated redox interactions, non-aqueous phase liquid wetting angles, and colloid–pathogen–rock attachment, and will thus be of importance in understanding natural attenuation and migration of dissolved, non-aqueous and particulate phases in groundwaters.     

钯/铝双金属体系对3-氯酚的脱氯降解

研究了钯/铝双金属体系对水相中3-氯酚的催化脱氯降解效果,通过置换沉积制备了钯/铝双金属颗粒,考察了该双金属颗粒的稳定性以及溶液pH和钯负载量对脱氯效果的影响。结果表明,pH在4.0以下的酸性条件,钯负载量在1.43%时,可实现水相中3-氯酚的有效脱氯,反应30 min后0.389 mmol/L的3-氯酚转化率可达99%以上,产物主要为苯酚,而钯/铝颗粒在重复测试中能保持较好的稳定性,这与铝基材表面自发形成的氧化膜有关。钯/铝材料表征的结果表明,钯颗粒高度分散在铝基材表面,并极大地提高了铝基材的表面积,从而有助于后续的脱氯反应。     

The effect of background irradiation on photocatalytic efficiencies of TiO2 thin films

TiO(2) thin films were prepared on quartz pipe substrates. Effects of the thickness of the films, the wavelength of the UV light and La doping on efficiencies of background irradiated photocatalysis were investigated, and simultaneously was compared with those of foreground irradiated photocatalysis. The results showed that there was an optimal thickness of the film corresponding with each wavelength of the light source limited in the range from 300 nm to 388 nm in the case of background irradiated photocatalysis, which was quite different from that of foreground irradiated one. But in both cases, the film's photocatalytic activities were enhanced by La non-uniformly doping. The results are useful for the design of high-efficiency photocatalytic reactors.     

Highly active photocatalytic coatings prepared by a low-temperature method

Photocatalytic properties of titanium (IV) oxide (TiO₂) in anatase form can be used for various purposes, including photocatalytic purification of water. For such an application, suspended or fixed photocatalytic reactors are used. Those with fixed phase seem to be preferred due to some advantages, one of which is the avoidance of photocatalyst filtration. To avoid leaching and exfoliation of the fixed phase, an immobilization procedure leading to a good adhesion of a catalyst to a substrate is crucial. Within this work, we present physical and photocatalytic characterization results of five commercially available TiO₂ photocatalysts (P25, P90, PC500, KRONOClean 7000, VPC-10) and one pigment (Hombitan LO-CR-S-M), which were successfully immobilized on glass slides by a “sol suspension” procedure. Different mechanical tests and characterization methods were used to evaluate the stability and morphology of the layers. Evaluation of photocatalytic activity was done by tests under UVA and UV–vis irradiation, using a method based on the detection of the fluorescent oxidation product of terephthalic acid (TPA), i.e., hydroxyterephthalic acid (HTPA). Aeroxide® P90 incorporated into the silica-titania binder was the most photocatalytically active layer and, unlike the others, showed significant increase of photocatalytic activity through the entire range of tested UVA irradiation intensities (2.3 mW/cm²–6.1 mW/cm²). The high mechanical stability of some photocatalytic layers allows using them in water photocatalytic purification reactions.     

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%.     

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.     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

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.     

Photocatalytic oxidation of nitrogen oxides using TiO2 loading on woven glass fabric

TiO2 loading on woven glass fabric is applied to treat nitrogen oxides (NOx) by photocatalytic oxidation (PCO). In this paper, the PCO behavior of NO at high concentrations was studied by PCO of NOx at source levels (20-168 ppm). The PCO efficiency reached 27% in this experiment, while the inlet NOx concentration was 168 ppm (147 ppm NO). The dependency of the reaction rate on several key influencing factors (relative humidity, space time, inlet concentration, oxygen percentage) was also studied. The results illustrate that the resulting hydroxyl radical and active oxide play an important role in the oxidation of NOx. The reactions are limited by the thermodynamic equilibrium after ca. 15s space time. A possible explanation for the catalyst deactivation is the accumulation of nitric acid and nitrous acid on the TiO2 surface during the PCO of NOx. However, the photocatalytic activity can be recovered with a simple heat treatment. The results from the study of the effect of the inlet concentration were described with the Langmuir-Hinshelwood model.     

纳米复合ZnO-TiO2晶体的制备及其光电催化性能研究

采用溶胶-凝胶法制备了纳米复合半导体ZnO-TiO2薄膜,并进行了结构和光电催化性能的测试.TiO2薄膜对五氯酚溶液的光电催化降解结果表明当输入正向偏压后,其光催化性能有较大提高.由于ZnO的掺入,半导体薄膜电极的光吸收能力增强;同时,Zn2+可能作为光生载流子的浅俘获中心,导致表面界面电荷转移加速,从而延长光生电子/空穴对的寿命并抑制其复合,有效地提高了TiO2薄膜光电催化活性.     

Experimental studies on particle impaction and bounce: effects of substrate design and material

This paper presents an experimental investigation of the effects of impaction substrate designs and material in reducing particle bounce and reentrainment. Particle collection without coating by using combinations of different impaction substrate designs and surface materials was conducted using a personal particle sampler (PPS) developed by the University of Southern California. The PPS operates at flow rate of 4 l min^-1 with a 50% cutpoint of approximately 0.9 μm in aerodynamic diameter. The laboratory results showed that the PPS collection efficiency for particles larger than 50% cutpoint is strikingly low (e.g., less than 50%) when an uncoated open cavity made of aluminum was used as an impaction substrate. The collection efficiency gradually increased when Teflon tape, Nuclepore, and glass fiber filters were used as impaction surfaces, respectively. Conical or partially enclosed cavity substrate designs increased collection efficiency of particles of 9 μm up to 80–90%. A conical cavity with glass fiber filter used as impaction surface was identified as the optimum configuration, resulting in a collection efficiency of 92% at Stokes numbers as high as 15.4 (corresponding to 9 μm in aerodynamic diameter). Particle losses were low (less than 10%) and relatively independent of particle size in any design with glass fiber filter. Losses seemed to increase slightly with particle size in all other configurations. Finally, outdoor PM₁ concentrations obtained with the PPS (in its optimum configuration) and a modified micro-orifice uniform deposit impactor (MOUDI) with coated impaction stages were in excellent agreement. The mean ratio of the PPS-to-MOUDI concentration was 1.13(±0.17) with a correlation coefficient R²=0.95. Results from this investigation can be readily applied to design particle bounce-free impaction substrates without the use of coating. This is a very important feature of impactors, especially when chemical analysis of the collected particulate matter is desirable.     

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.