光催化技术及其在室内空气净化方面研究现状

阐述了光催化技术的基本原理、二氧化钛光催化剂的特性,以及光催化技术在环境保护领域的广阔应用。介绍了中国室内空气污染的现状和甲醛、苯系物等主要污染物的性质与来源。简单讨论了物理法,化学法等主要的室内空气污染处理技术,突出表述了光催化技术的优势。从降解机理、降解效果、反应器应用等3个方面介绍了光催化技术在室内空气净化方面的研究现状。指出了单一技术的不足和联合协同作用的必要性。强调了将研究结果投入实际运用的迫切性,希望真正有效的室内空气净化器尽早普及。     

悬浮型和流化床型纳米TiO2光催化反应器研究进展

围绕避免催化剂沉积、提高光透过率和催化剂分离3个方面的问题,综述了国内外在悬浮型和流化床型光催化反应器的工艺设计及改良方面所取得的进展,对当前应发展的悬浮型和流化床型反应体系提出了建议。     

Photocatalytic degradation of bentazone in soil washing wastes containing alkylpolyoxyethylene surfactants

Three alkylpolyoxyethylene surfactants bearing the same hydrophobic chain and a different number of oxyethylene groups were investigated as suitable candidates for the soil washing treatment of contaminated soil samples containing bentazone. Comparable good recoveries of the pesticide were obtained working with these surfactants. The photocatalytic treatment of the collected washing wastes, performed in the presence of suspended TiO₂ particles under irradiation with simulated sunlight, leads to the effective degradation of bentazone residues after a time depending on the nature and concentration of the chosen amphiphile. Brij 35 was found to be the best surfactant candidate, giving the faster abatement of the pesticide in the collected wastes. The overall treatment time depends on the bentazone mineralization kinetics, markedly slow in the presence of surfactants. Useful information about the photocatalytic degradation route was obtained from the HPLC-MS analysis of transient intermediates formed in water.     

Enhanced photocatalytic activities of silicon nanowires/graphene oxide nanocomposite: Effect of etching parameters

Homogeneous and vertically aligned silicon nanowires (SiNWs) were successfully fabricated using silver assisted chemical etching technique. The prepared samples were characterized using scanning electron microscopy, transmission electron microscopy and atomic force microscopy. Photocatalytic degradation properties of graphene oxide (GO) modified SiNWs have been investigated. We found that the SiNWs morphology depends on etching time and etchant composition. The SiNWs length could be tuned from 1 to 42 µm, respectively when varying the etching time from 5 to 30 min. The etchant concentration was found to accelerate the etching process; doubling the concentrations increases the length of the SiNWs by a factor of two for fixed etching time. Changes in bundle morphology were also studied as function of etching parameters. The SiNWs diameter was found to be independent of etching time or etchant composition while the size of the SiNWs bundle increases with increasing etching time and etchant concentration. The addition of GO was found to improve significantly the photocatalytic activity of SiNWs. A strong correlation between etching parameters and photocatalysis efficiency has been observed, mainly for SiNWs prepared at optimum etching time and etchant concentrations of 10 min and 4:1:8. A degradation of 92% was obtained which further improved to 96% by addition of hydrogen peroxide. Only degradation efficiency of 16% and 31% has been observed for bare Si and GO/bare Si samples respectively. The obtained results demonstrate that the developed SiNWs/GO composite exhibits excellent photocatalytic performance and could be used as potential platform for the degradation of organic pollutants.     

Graphitic carbon nitride/biochar composite synthesized by a facile ball-milling method for the adsorption and photocatalytic degradation of enrofloxacin

In order to enhance the removal performance of graphitic carbon nitride (g-C₃N₄) on organic pollutant, a simultaneous process of adsorption and photocatalysis was achieved via the compounding of biochar and g-C₃N₄. In this study, g-C₃N₄ was obtained by a condensation reaction of melamine at 550°C. Then the g-C₃N₄/biochar composites were synthesized by ball milling biochar and g-C₃N₄ together, which was considered as a simple, economical, and green strategy. The characterization of resulting g-C₃N₄/biochar suggested that biochar and g-C₃N₄ achieved effective linkage. The adsorption and photocatalytic performance of the composites were evaluated with enrofloxacin (EFA) as a model pollutant. The result showed that all the g-C₃N₄/biochar composites displayed higher adsorption and photocatalytic performance to EFA than that of pure g-C₃N₄. The 50% g-C₃N₄/biochar performed best and removed 45.2% and 81.1% of EFA (10 mg/L) under darkness and light with a dosage of 1 mg/mL, while g-C₃N₄ were 19.0% and 27.3%, respectively. Besides, 50% g-C₃N₄/biochar showed the highest total organic carbon (TOC) removal efficiency (65.9%). Radical trapping experiments suggested that superoxide radical (?O₂^?) and hole (h⁺) were the main active species in the photocatalytic process. After 4 cycles, the composite still exhibited activity for catalytic removal of EFA.     

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.     

Photocatalytic Degradation of the Herbicide Erioglaucine in the Presence of Nanosized Titanium Dioxide: Comparison and Modeling of Reaction Kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO₂ nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO₂ system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir–Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm^{? 1} and 0.984 ppm min^{? 1}, respectively. In this work, we also compared the reactivity between the commercial TiO₂ Degussa P-25 and a rutile TiO₂. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO₂ for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO₂ process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO₂.     

Photocatalytic activity of titanium dioxide modified concrete materials – Influence of utilizing recycled glass cullets as aggregates

Combining the use of photocatalysts with cementitious materials is an important development in the field of photocatalytic air pollution mitigation. This paper presents the results of a systematic study on assessing the effectiveness of pollutant degradation by concrete surface layers that incorporate a photocatalytic material – Titanium Dioxide. The photocatalytic activity of the concrete samples was determined by photocatalytic oxidation of nitric oxide (NO) in the laboratory. Recycled glass cullets, derived from crushed waste beverage bottles, were used to replace sand in preparing the concrete surface layers. Factors, which may affect the pollutant removal performance of the concrete layers including glass color, aggregate size and curing age, were investigated. The results show a significant enhancement of the photocatalytic activity due to the use of glass cullets as aggregates in the concrete layers. The samples fabricated with clear glass cullets exhibited threefold NO removal efficiency compared to the samples fabricated with river sand. The light transmittance property of glass was postulated to account for the efficiency improvement, which was confirmed by a separate simulation study. But the influence of the size of glass cullets was not evident. In addition, the photocatalytic activity of concrete surface layers decreased with curing age, showing a loss of 20% photocatalytic activity after 56-day curing.     

A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO₂:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O₂⁻ radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.     

Enhancement of photocatalytic efficiency by in situ fabrication of BiOBr/BiVO4 surface junctions

Surface junctions between Bi OBr and BiVO_4 were synthesized. The BiOBr/BiVO_4 with 1 wt.%of Bi OBr exhibited the highest photocatalytic activity in the degradation of Rh B under visible-light irradiation. It was found that the highly efficient adsorption of Rh B molecules via the electrostatic attraction between Br-and cationic \N(Et)_2 group played a key role for the high photocatalytic activities of BiOBr/BiVO_4. This efficient adsorption promoted the N-deethylation of Rh B and thus accelerated the photocatalytic degradation of Rh B.Moreover, the metal-to-metal charge transfer(MMCT) mechanism was proposed, which revealed the concrete path paved with Bi–O–Bi chains for the carrier migration in BiOBr/BiVO_4. The interaction between photoexcited Rh B* and the Bi~(3+) in BiVO_4 provided the driving force for the migration of photo-generated carriers along the Bi–O–Bi chains. This work has not only demonstrated the important role of efficient adsorption in the photocatalytic degradation of organic contaminants, but also developed a facile strategy to improve the efficiency of photocatalysts.