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1.
In the present study, photocatalytic reactions of nitrogen oxides (NOx = NO + NO2) were studied on commercial TiO2 doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO2 was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO2 surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO3/NO3?) was observed with near to unity yield. In addition, traces of H2O2 were observed in the gas phase only in the presence of O2. Formation of the greenhouse gas nitrous oxide (N2O) could be excluded. The uptake kinetics of NO, NO2 and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO2) > 10?5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO3/NO3? is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.  相似文献   

2.
The work studies the photocatalytic activity and the antifungal efficiency of the TiO2/Zn-Al coatings placed on the target commercial façade paints. The photocatalytic active nanocomposite based on TiO2 and Zn-Al-layered double hydroxides (ZnAl-LDHs) was synthesized by a wet impregnation technique with 3 % w/w TiO2. The freshly prepared suspension was applied by spray technique on the surfaces of the white façade paints. The goal of the work was to develop a method that quickly quantifies the antifungal activity of the commercial façade paints with and without biocidal components covered with a photocatalytic coating. The essence of the proposed method is the monitoring of the fungal growth (artificial ageing conditions) and the quantification of its development (UV-A 0.13 mWcm?2) on the façade paint surfaces. A special fungus nutrient (potato dextrose agar (PDA)) was inoculated with the spores of the Aspergillus niger ATCC 6275, and the test samples (façade paints with and without photocatalytic coating) were placed on the inoculated nutrient in the petri dishes. The images of the fungal growth on the samples of the facade paints, during a period of 5 days, were imported into Matlab R2012a where they were converted to binary images (BW), based on the adequate threshold. The percentage of the surface coverage was calculated by applying the specifically written program code which determines the ratio of the black and white pixels. The black pixels correspond to the surface covered with hyphae and mycelia of the fungus.  相似文献   

3.
In this study we investigate the release of metallic silver nanoparticles (Ag-NP) from paints used for outdoor applications. A facade panel mounted on a model house was exposed to ambient weather conditions over a period of one year. The runoff volume of individual rain events was determined and the silver and titanium concentrations of 36 out of 65 runoff events were measured. Selected samples were prepared for electron microscopic analysis. A strong leaching of the Ag-NP was observed during the initial runoff events with a maximum concentration of 145 μ Ag/l. After a period of one year, more than 30% of the Ag-NP were released to the environment. Particles were mostly <15 nm and are released as composite colloids attached to the organic binders of the paint. Microscopic results indicate that the Ag-NP are likely transformed to considerably less toxic forms such as Ag2S.  相似文献   

4.
氮掺杂二氧化钛可见光催化降解曙红Y溶液   总被引:2,自引:1,他引:1  
采用溶胶凝胶法制备了氮掺杂二氧化钛光催化剂,用XRD、SEM、FTIR和粒度分析仪对催化剂进行了表征,并且在可见光作用下对曙红Y溶液进行了光催化降解实验。研究了催化剂的投加量、曙红Y的初始浓度、光照时间和pH对曙红Y溶液的光降解效果。结果表明,以可见光作光源,催化剂的投入量为0.4 g,曙红Y溶液的初始浓度为20 mg/L,光照时间为50 min,pH=4条件下,曙红Y溶液的降解率达98.87%。  相似文献   

5.
Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m3/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H2O2 and TiO2 concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O2 is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H2O2 and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H2O2 was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H2O2 concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H2O2 concentration, the concentration of 20.0 mL/L H2O2 appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H2O2 and TiO2 increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min−1) for the UV/TiO2/H2O2 system were higher than that of the corresponding values for the UV/H2O2 system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H2O2 and TiO2 increases at constant pH and UV intensity. It was found that the UV/TiO2/H2O2 system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO2/H2O2 photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.  相似文献   

6.
The photocatalytic degradation of crotamiton in aqueous solution using TiO2 was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO2 particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO2 particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO2 concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO2 concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.  相似文献   

7.

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.  相似文献   

8.

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO2 was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO2 as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO2 was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO2 crystal.  相似文献   

9.
Abstract

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO2 particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. The half-life (DT50) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K = 0.0532 min?1). The half-life time of photomineralization in the concentration range of 7.5–20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).  相似文献   

10.
This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO2) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO2 nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO2 by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO2-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO2?+?monodisperse TiO2 (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO2-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO2-P25. Using NF-TiO2 layer-by-layer with monodisperse TiO2 (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10?3?min?1 for caffeine, 12.5 and 9.0?×?10?3?min?1 for carbamazepine, and 10.9 and 5.8?×?10?3?min?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO2-based films compared to the direct addition of nanoparticles into the sol.  相似文献   

11.
Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO2 materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol–gel method. The precursors were TiOSO4?xH2O and Fe3(NO3)·9H2O. X-ray studies confirmed that the anatase phase of the iron-doped TiO2 resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO2 materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.  相似文献   

12.
采用H2O2、Fe2(SO43和Fenton溶液对失活的TiO2纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明,经H2O2溶液处理后TiO2催化活性能得到有效再生,经Fe2(SO43和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H2O2和Fenton的强氧化作用,及进入TiO2纳米管的Fe3+的阻止电子-空穴对再复合作用有关。  相似文献   

13.
This work explores the competitive removal of pharmaceuticals from synthetic and environmental waters by combined adsorption-photolysis treatment. Five drugs usually present in waterways have been used as target compounds, some are pseudo-persistent pollutants (carbamazepine, clofibric acid, and sulfamethoxazole) and others are largely consumed (diclofenac and ibuprofen). The effect of the light source on adsorption of drugs onto activated carbons followed by photolysis with TiO2 was assessed, being UV-C light the most effective for drug removal in both deionized water and river water. Different composites prepared from titania nanoparticles and powdered activated carbons were tested in several combined adsorption-photocatalysis assays. The composites prepared by calcination at 400 °C exhibited much better performance than those synthesized at 500 °C, being the C400 composite the most effective one. Furthermore, some synthetic waters containing dissolved species and environmental waters were used to investigate the effect of the aqueous matrix on each drug removal. In general, photocatalyst deactivation was found in synthetic and environmental waters. This was particularly evident in the experiments performed with bicarbonate ions as well as with wastewater effluent. In contrast, tests conducted in seawater showed adsorption and photocatalytic degradation yields comparable to those obtained in deionized water. Considering the peculiarities of substrate competition in each aqueous matrix, the combined adsorption-photolysis treatment generally increased the overall elimination of drugs in water.  相似文献   

14.
The increasing production of nanomaterials will in turn increase the release of nanosized byproducts to the environment. The aim of this study was to evaluate the behaviour, uptake and ecotoxicity of TiO2 byproducts in the earthworm Eisenia fetida. Worms were exposed to suspensions containing 0.1, 1 and 10 mg/L of byproducts for 24 h. Size of TiO2 byproducts showed aggregation of particles up to 700 μm with laser diffraction. Only worms exposed at 10 mg/L showed bioaccumulation of titanium (ICP-AES), increasing expression of metallothionein and superoxide dismutase mRNA (Real-time PCR) and induction of apoptotic activity (Apostain and TUNEL). TiO2 byproducts did not induce cytotoxicity on cœlomocytes, but a significant decrease of phagocytosis was observed starting from 0.1 mg/L. In conclusion, bioaccumulation of byproducts and their production of reactive oxygen species could be responsible for the alteration of the antioxidant system in worms.  相似文献   

15.
The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO2) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO2 and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO2(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO2 synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.  相似文献   

16.
采用溶剂热合成法制备了一种新型的汉沙黄/TiO2复合物光催化剂,利用多种手段SEM、XRD、FT-IR对催化剂的样品形貌、结构进行表征。分别以罗丹明B、亚甲基蓝、中性红为目标降解物,考察了可见光下溶液pH值对催化剂的吸附性能和催化活性的影响。结果表明,敏化后的TiO2对光的响应由紫外区扩展到可见区,催化活性优于纯TiO2,对上述3种染料的吸附率分别为19.2%、29.2%和43.2%,降解率分别为98.6%、92.5%和97.8%。制备的汉沙黄/TiO2光催化剂稳定性好,重复使用率高,在印染废水处理中具有很好的应用前景。  相似文献   

17.
Kumar A  Pandey AK  Singh SS  Shanker R  Dhawan A 《Chemosphere》2011,83(8):1124-1132
Extensive production and consumption of nanomaterials such as ZnO and TiO2 has increased their release and disposal into the environment. The accumulation of nanoparticles (NPs) in ecosystem is likely to pose threat to non-specific targets such as bacteria. The present study explored the effect of ZnO and TiO2 NPs in a model bacterium, Salmonella typhimurium. The uptake of ZnO and TiO2 bare NPs in nano range without agglomeration was observed in S. typhimurium. TEM analysis demonstrated the internalization and uniform distribution of NPs inside the cells. Flow cytometry data also demonstrates that both ZnO and TiO2 NPs were significantly internalized in the S. typhimurium cells in a concentration dependent manner. A significant increase in uptake was observed in the S. typhimurium treated even with 8 and 80 ng mL−1 of ZnO and TiO2 NPs with S9 after 60 min, possibly the formation of micelles or protein coat facilitated entry of NPs. These NPs exhibited weak mutagenic potential in S. typhimurium strains TA98, TA1537 and Escherichia coli (WP2uvrA) of Ames test underscoring the possible carcinogenic potential similar to certain mutagenic chemicals. Our study reiterates the need for re-evaluating environmental toxicity of ZnO and TiO2 NPs presumably considered safe in environment.  相似文献   

18.

Purpose  

Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO2 nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion.  相似文献   

19.
Li X  Zou X  Qu Z  Zhao Q  Wang L 《Chemosphere》2011,83(5):674-679
In this work, Ag-doping TiO2 nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO2 nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N2 adsorption. The nanotubular TiO2 photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO2 nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO2 nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO2 nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO2 and H2O.  相似文献   

20.

In this paper, a crosslinked carboxymethyl starch (CCMS) was prepared with corn starch as the raw material, epichlorohydrin as the crosslinking agent, and chloroacetic acid as the etherifying agent through a series of crosslinking, alkalization, and etherification reactions, respectively. Nano-TiO2 was loaded onto the surface of the CCMS by the sol-gel method to obtain a TiO2/CCMS composite. The TiO2/CCMS composite was characterized by XPS, XRD, SEM, and BET. XPS showed that the surface chemical composition of the TiO2/CCMS composite material contained titanium; XRD diffraction patterns indicated that the crystal form of the TiO2/CCMS composite was a combination of the CCMS and anatase TiO2. The surface morphology obtained by SEM showed that there were nano-TiO2 particles on the surface of the CCMS. The specific surface area of the TiO2/CCMS composite was larger than that of CCMS. The adsorption-photodegradation performance of the TiO2/CCMS composite was also studied under UV irradiation, and the results showed that significant adsorption-photodegradation synergies occurred.

  相似文献   

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