聚噻吩敏化TiO_2复合材料的制备和光催化性能

以无水FeCl3为氧化剂,在CHCl3中采用原位氧化聚合法制备了一系列不同噻吩与TiO2摩尔比〔n(Th)/n(TiO2)〕的聚噻吩敏化TiO2(PTh/TiO2)复合材料。用TEM、FTIR、XRD、DRS和PL对复合材料进行了表征。用苯酚的光催化降解反应研究了复合材料在紫外光和太阳光下的光催化活性。结果表明,PTh的修饰减轻了复合纳米粒子之间的团聚,但对TiO2的晶体结构无影响,复合材料粒径25～30nm。PTh的敏化作用可使复合材料吸收200～800nm的光。两种光源下,复合材料的光催化活性均优于纯TiO2,当n(Th)/n(TiO2)=0.04时达最佳。紫外光下,200min时苯酚降解率达76.39%,太阳光下,120min时苯酚降解率达88.27%,较纯TiO2光催化活性分别提高了19.7%和31.53%。     

New aspects of heterogeneous photocatalysts for water decomposition

Several new photocatalysts for overall water splitting are described. Under UV light irradiation (270 nm), La-doped NaTaO₃ modified with NiO decomposed water into H₂ and O₂ with extremely high quantum efficiency. Under an optimized condition, the apparent quantum efficiency, which was estimated with numbers of irradiated photons and evolved H₂ molecules, reached 56%. New stable photocatalytic materials containing elements with d¹⁰ electronic configuration such as In³⁺ Sn⁴⁺ and Sb⁵⁺ were developed for overall water splitting. Some mesoporous oxides were proved to be effective photocatalysts. (Oxy)nitrides of some early transition metals, i.e., Ta, Nb and Ti, were found to be stable materials having potentials for H₂ and O₂ evolutions under visible light irradiation (⪯600 nm). The electronic structures of these photocatalysts are also discussed based on DFT calculation.     

Photocatalytic degradation of Rhodamine B dye under UV/solar light using ZnO nanopowder synthesized by solution combustion route

Nano-sized ZnO powder with crystallite size in the range 12 to 50 nm were prepared by solution combustion route. The product was characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). Photocatalytic degradation of rhodamine B (RB) dye was carried out with ZnO nanopowder. The effect of parameters such as the crystallite size, amount of catalyst, concentration of the dye, pH and irradiation on photocatalytic degradation of RB is studied. The results reveal that the maximum decolorization (more than 95%) of dye occurred with ZnO catalyst in 8 min of stirring at basic pH under solar light irradiation. It was also found that chemical oxygen demand (COD) reduction takes place at a faster rate under solar light as compared to that of UV light. The results suggest that, the ZnO solar photocatalytic irradiation is better than the calcined ZnO/solar and UV light irradiation.     

Rapid assessment of weathering stability from exposure of polymer films. II. The effectiveness of different regions of the solar spectrum in degrading an ABS terpolymer

A simple and rapid method has been developed to determine the relative effectiveness of the different regions of the solar spectrum in weathering a polymer. The method is based on measuring the rate of degradation of the polymer in film form, exposed outdoors under a range of materials which transmit different amounts of solar UV. The stability of an unpigmented ABS terpolymer has been examined using this method. It has been shown that the relatively small amount of solar radiation in the range of 295–340 nm accounts for 41% of the total degradation process. Longer wavelengths are shown to be progressively less effective; wavelengths greater than 450 nm (which account for nearly 90% of the total energy of the solar spectrum) contribute less than 5% to the degradation process.     

Degradation of Atenolol in a Rectangular Staircase Photocatalytic Reactor with Immobilized ZnO

Atenolol (ATL) was removed with a rectangular staircase photocatalytic reactor (RSPR) using immobilized ZnO under solar irradiation. The effects of operational parameters such as flow rate, pH, and initial ATL concentration were examined. The highest degradation was obtained after 240 min photocatalytic reaction. The effects of different scavengers proved that the ATL degradation was mainly due to the direct oxidization with OH^? radicals, whereas, the h⁺ and O₂^?? radicals played a minor role in the degradation process. Five repetitive operations of RSPR allowed for reaching 77 ± 3 % degradation of ATL for each cycle. Kinetic data indicated that the photocatalytic kinetics followed the global matter balance model.     

Solar photocatalytic decolorization of dyes in solution with TiO2 film

Application of TiO₂ film to solar photocatalysis of organic dyes, including Methylene Blue (MB) (λ_max, 660 nm), RR195 (λ_max, 540 nm) and RY145 (λ_max, 420 nm), was investigated. It was found that after 6-h solar irradiation, the extent of color degradation of dyes using solar photocatalytic system without TiO₂ film was quite limited. The color removal percentage for MB, RR195, and RY145 was found to be 23.3, −9.3, and −20.7%, respectively, resulting from competitions between the photosensitizing reaction and formation of colored intermediates during solar irradiation. However, as TiO₂ film was applied, the color degradation capability of solar photocatalytic system was significantly improved, in spite of the fact that only approximately 7% of solar irradiation belongs to the UV region. The color removal percentage for MB, RR195, and RY145 was up to 93.6%, 85.3%, and 71.1%, respectively, after 6-h irradiation. We believed that in such a solar photocatalytic system immobilized with TiO₂ film, both the maximum absorbance wavelength of the dye and the adsorbability of the dye on TiO₂ film played significant roles on the rate and efficiency of color removal of the dye solutions. Moreover, the possible reaction mechanism was proposed. The solar photocatalytic process with immobilized TiO₂ film was found to follow the pseudo-first order reaction kinetics. Color removal rate of MB was almost twice of that of RY145. Accordingly, the photocatalytic degradation process using solar light as an irradiation source, and immobilized TiO₂ as a photocatalyst, showed potential application for the decolorization of wastewater.     

Studies on coupled biological and photochemical treatment of soda pulp bleaching effluents from agro residue based pulp and paper mill

BACKGROUND: The effect of coupled biological and photochemical processes for treatment of bio‐recalcitrant effluents from chlorination (C) and first alkaline extraction (E₁) stages of soda pulp bleaching in an agro‐residue based pulp and paper mill has been investigated. RESULTS: The work aims to evaluate the coupled effect on the extent of degradation in terms of chemical oxygen demand (COD) reduction. Biological treatment of C and E₁ effluent resulted in 30% and 57% COD, respectively, after 1 day of treatment with acclimatized activated sludge. However, further increase in retention time did not show any significant change in degradation efficiency. Investigations on photocatalytic treatment (at 365 nm and 0.625 W) of C effluent resulted in 47% degradation under optimized conditions (3 g L^?1 TiO₂, pH 6.0 and 0.01 mol L^?1 NaOCl), and E₁ effluent showed 37% degradation under optimized conditions (2.5 g L^?1, pH 4.0 and 0.03 mol L^?1 NaOCl) after 6 h of UV irradiation. However, photocatalytic treatment of biotreated (1 day) effluents under similar optimized conditions significantly enhanced the degradation to 81% and 93% in C and E₁ effluent, respectively, after 2 h irradiation. CONCLUSION: Coupled biological treatment followed by photocatalysis is an effective method for the reduction of total organic carbon (TOC) of the test effluents and it would facilitate closed circuiting of water used for soda bleaching in an agro pulp and paper mill. Copyright © 2011 Society of Chemical Industry     

Synthesis of novel ZnO/carbon xerogel composites: Effect of carbon content and calcination temperature on their structural and photocatalytic properties

This paper reports the development of new ZnO/carbon xerogel composites (XZn w) for photocatalytic applications. The use of black wattle tannin as a precursor to the carbon xerogel aimed at reducing costs and environmental impacts. The composites were characterized by diffuse reflectance spectroscopy (DRS), BET surface area, scanning electron microscopy (FEG-SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), infrared spectroscopy (IR), and X-ray diffraction (XRD). The photocatalytic performance of the materials was evaluated in the decomposition process of methylene blue, a known toxic pollutant. The impacts of the catalyst dosage and calcination temperature on the photocatalytic process were also examined systematically. The X-ray profiles of the XZn w evidenced the existence of the hexagonal structure of the zinc oxide (wurtzite) in the composites. The XPS and XRD analyses confirmed the incorporation of carbon in the zinc oxide crystalline structure. The higher carbon content resulted in a larger surface area. All composites presented the ability to absorb radiation in less energetic wavelengths, contrary to pure zinc oxide that only absorbs radiation of wavelengths below 420?nm. The optimal dosage and calcination temperature were found to be 0.2?g?L^?1 and 300?°C. All the developed composites displayed significant photocatalytic activities in the decomposition of methylene blue under both visible and solar light. The composites had superior photocatalytic efficiency under visible light when compared to pure zinc oxide. The XZn 0.5 presented the best degradation efficiency under visible radiation. All materials presented similar photocatalytic responses under solar light, evidencing the synergy between the carbon xerogel and the zinc oxide. The photocatalytic mechanism was evaluated by trapping experiments to be mainly controlled by the electron vacancies that are generated during the photoexcitation of the composites.     

Preparation of Ag-sensitized ZnO and its photocatalytic performance under simulated solar light

ZnO was prepared rapidly by microwave heating method. The results of scanning electron microscopy show that the leaflike ZnO is composed of self-assembled ZnO particles of 30–50 nm. Ag-sensitized ZnO composite was prepared by UV-photoreduction and glycol reduction, respectively. The composite was characterized by means of scanning electron microscopy, X-ray diffraction and photoluminescence. The ZnO and Ag/ZnO prepared were applied in photocatalytic degradation of phenol and methyl orange as model of organic pollutant in water under simulated solar light. The results show that Ag doping in both methods of UV-photoreduction and glycol reduction can remarkably improve the photocatalytic activity of ZnO under simulated solar light. The utilization ratio of Ag in glycol reduction is high and the optimum content of Ag in Ag/ZnO composite is only 1.33%. Therefore, the glycol reduction is a novel and excellent method for preparing Ag-sensitized ZnO composite with high photocatalytic activity.     

Effect of modified graphene quantum dots on photocatalytic degradation property

The effective use of solar energy in sewage disposal has been extensively investigated. This work focuses on the photocatalytic property of graphene quantum dots (GQDs) and polymer-modified GQDs under visible light. A hydrothermal synthesis route to GQDs was developed by using citric acid as a carbon precursor. The GQDs were modified with polyethylenimine (PEI) and polyethylene glycol (PEG). The obtained GQDs, GQDs-PEIs, and GQDs-PEGs were characterized and their structural information was determined through Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), photoluminescence spectroscopy, and UV–Vis absorption spectroscopy. Results revealed that the GQDs were uniform in size (2–5 nm) and rich in oxygen-containing groups. The GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. The photocatalytic performance of these samples was demonstrated on the basis of methylene blue (MB) degradation. The photocatalytic rates of GQDs, GQDs-PEIs, and GQDs-PEGs decreased successively. The polymer-modified GQDs could qualitatively control the degradation rate of MB. Free radical species were generated to oxidize MB under light irradiation. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal.Prime noveltyThe main object of this work is to find out a novel property of graphene quantum dots (GQDs) as efficient nanomaterials for degradation of organic pollutant dyes under visible light irradiation. And, the GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. Moreover, the degradation rate could be qualitatively controlled by using different polymer-modified GQDs. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal. Also, the degradation mechanism is discussed.     

Green Synthesis of Zinc Oxide Nanoparticles (ZnO NPs) for Effective Degradation of Dye,Polyethylene and Antibacterial Performance in Waste Water Treatment

At present, there is a vital need for river water purification by developing new approaches to eliminate bacterial biofilms, textile dyes, and Low-Density Polyethylene (LDPE) plastics that pose severe threats to human and environmental health. The current work put forward the construction of an eco-friendly green strategy to synthesize zinc oxide nanoparticles (ZnO NPs) using areca nut (Areca catechu) extract and their application to tackle the challenges in water purification. Prepared biogenic NPs were characterized by X-ray diffraction analysis (XRD), Fourier Transform Infra-Red (FT-IR), Energy Diffraction Spectroscopy (EDS), Scanning Electronic Microscopy (SEM), Transmission Electron Microscopy (TEM) analysis, confirmed the spherical shape in 20 nm and UV–vis spectroscopy. The characteristic absorption band exhibited at 326 nm confirmed the formation of ZnO NPs using UV–vis spectroscopy. Among all the tested bacterial pathogens, the E. coli at 50 µg/mL concentration showed the highest inhibition of biofilm activity, followed by the highest growth curve, cellular leakage, and potassium ion efflux. The ZnO NPs observed with photo-degradation of Rhodamine-B (Rh-B), Methylene Blue (MB), and Nigrosine dyes under sunlight irradiation at different time intervals. Finally, the photocatalytic activity of LDPE-ZnO NPs nanocomposite film showed the highest degradation under solar light irradiation were confirmed through photo-induced weight loss, SEM, FTIR, and MALDI-TOF analysis. This study demonstrates ZnO NPs exhibit efficacy against biofilm formation, degradation of photocatalytic textile dyes, and low-density LDPE film under solar light irradiation, which can be a step forward in water purification.

     

Various TiO2 microcrystals: Controlled synthesis and enhanced photocatalytic activities

Titania microspheres with higher photocatalytic activity have been synthesized using TiCl₄ and FeCl₃ as the precursor in the presence of Span-80. The products were characterized with XRD, TEM and UV–vis DRS. XRD and TEM indicated that the microsphere was a mixture of rutile, brookite and anatase with a diameter of about 5–7 μm. The photocatalytic experiments revealed that the microspheres exhibited high photocatalytic activities under UV-light and solar irradiation. The degradation rate of methyl orange (MO) was 100% under UV-light irradiation for 3 h and 91% under solar irradiation for 6 h. In particular, the catalysts could be readily separated by sedimentation after the photocatalytic reaction.     

Photodegradation of four fluoroquinolone compounds by titanium dioxide under simulated solar light irradiation

BACKGROUND; In this study, simultaneous photocatalytic degradation of four fluoroquinolone (FQ) compounds (i.e. ofloxacin, norfloxacin, ciprofloxacin and enrofloxacin) was investigated in TiO₂ suspensions under simulated solar light irradiation. Effects of experimental variables including pH, TiO₂ dosage, initial substrate concentration and hydrogen peroxide (H₂O₂) on the degradation processes were also investigated. RESULTS: The antibiotics degradation was pH‐influenced. The photocatalytic reaction followed the pseudo‐first‐order model, with reaction rate constants (k) 0.026, 0.027, 0.022 and 0.026 min^?1 for ofloxacin, norfloxacin, ciprofloxacin and enrofloxacin, respectively. Complete elimination of four FQs was achieved in a reaction system composed of 0.5 g L^?1 of TiO₂ and 82.5 mg L^?1 of H₂O₂ at pH 6 after 90 min irradiation. Mineralization of FQs during TiO₂ photocatalysis was slower than the FQs conversion, and the antibacterial activity of the four FQs was completely removed by TiO₂ under simulated solar light irradiation. CONCLUSION: The four FQs can be simultaneously degraded and mineralized with commercially available TiO₂ under simulated solar light irradiation. Microbiological analysis showed that the antibacterial activity of the four FQs was completely removed. These results are helpful for antibiotics removal in the environment, and for exploring new technology for wastewater treatment. Copyright © 2012 Society of Chemical Industry     

纳米复合光催化剂Ag@TiO2日光辐照下催化性能

对自制Ag@TiO2光催化剂日光下光催化降解甲基橙模拟污染物的可行性进行了研究,探讨了反应时间、pH值、H2O2用量、催化剂浓度和催化剂重复使用对甲基橙光催化降解效果的影响.结果表明,在H2O2协同作用下,Ag@TiO2光催化剂可以快速降解溶液中的甲基橙,晴好天气下20 min溶液可褪至无色.     

Diatom Biosilica Doped with Palladium(II) Chloride Nanoparticles as New Efficient Photocatalysts for Methyl Orange Degradation

A new catalyst based on biosilica doped with palladium(II) chloride nanoparticles was prepared and tested for efficient degradation of methyl orange (MO) in water solution under UV light excitation. The obtained photocatalyst was characterized by X-ray diffraction, TEM and N₂ adsorption/desorption isotherms. The photocatalytic degradation process was studied as a function of pH of the solution, temperature, UV irradiation time, and MO initial concentration. The possibilities of recycling and durability of the prepared photocatalysts were also tested. Products of photocatalytic degradation were identified by liquid chromatography–mass spectrometry analyses. The photocatalyst exhibited excellent photodegradation activity toward MO degradation under UV light irradiation. Rapid photocatalytic degradation was found to take place within one minute with an efficiency of 85% reaching over 98% after 75 min. The proposed mechanism of photodegradation is based on the assumption that both HO^• and O₂^•− radicals, as strongly oxidizing species that can participate in the dye degradation reaction, are generated by the attacks of photons emitted from diatom biosilica (photonic scattering effect) under the influence of UV light excitation. The degradation efficiency significantly increases as the intensity of photons emitted from biosilica is enhanced by palladium(II) chloride nanoparticles immobilized on biosilica (synergetic photonic scattering effect).     

A biotemplate synthesized hierarchical Sn-doped TiO2 with superior photocatalytic capacity under simulated solar light

Despite a number of studies have been carried out on TiO₂ based materials as photocatalysts for water pollutant treatment, it still needs sustained effort to extend the optical range of the photocatalysts and inhibit the recombination of photo-induced carriers to improve their catalytic activities under solar light. In this work, a series of Sn-doped TiO₂ with different amounts of Sn doping (1, 5, 10 and 20 mol%) were biomimetically synthesized by a facile sol–gel method using cellulosic cotton as biotemplate. The Sn-doped TiO₂ materials possess a typical three-dimensional hierarchical structure of microtubes consisting of interwoven nanofibers. The photocatalytic performance was evaluated via the degradation of methylene blue (MB) (10.0 mg L^?1) under Xenon lamp simulated solar irradiation. The results show that Sn(5)-TiO₂ (5 mol% Sn doping) sample exhibits an outstanding photocatalytic capacity with a superior degradation rate of higher than 98% within 30 min and a good reusability without significant decrease of activity after reused for four cycles. The most significantly improved photocatalytic capacity of TiO₂ is ascribed to more extra surface hydroxyl groups and accessible active sites provided by the relatively high surface area, and a higher light capturing and utilization efficiency with less recombination of the photogenerated electron-hole pairs endowed by the good synergistic effect of the special hierarchically porous microstructure and the appropriate amount of Sn doping. Whereas, the excessive Sn doping reduces the photocatalytic activity obviously, resulting from the phase transformation of TiO₂ generating more rutile phase with less reactivity, the phase separation with clear grain boundary blocking the active sites, and the extra Sn⁴⁺ acting as the recombination center. This research presents a facile biomimetic synthesis strategy combined with the traditional sol–gel method to develop various ion doped metal oxides as photocatalysts with enhanced activity.     

Construction of BiVO4 microspheres sensitized TiO2 NTAs for the enhanced photocatalytic mineralization of organic dyes

In the present work, BiVO₄ microspheres were deposited on TiO₂ NTAs via the solvothermal method using urea as the mineralizer. The binary heterojunction formation significantly enhanced the solar response region and intensity, and the electron transfer path was built at the interface of two semiconductors, which was the main reason for the enhanced photoelectrochemical and photocatalytic performances. The S-2 electrode prepared with urea concentration of 2 mol/L displayed the high visible light photocurrent of 73.76 μA/cm² and photovoltage of −0.30 V. Furthermore, the S-2 photocatalyst also showed excellent photocatalytic decoloration ability of MO, RhB and MB dyes, and the corresponding decomposition efficiencies were 55.82%, 41.62% and 89.90% under solar irradiation. Except for the organic dyes, Cr(VI) ions also could be reduced into Cr(III), and the photocatalytic efficiency achieved 74.05% after 3 h solar irradiation. The active group and photocatalytic mechanism were proposed to illuminate the essential reason. The experimental results indicated that the novel BiVO₄/TiO₂ NTAs with binary heterojunction are attractive photocatalysts for the dyeing and printing water treatment.     

Ag-doped nickel ferrites and their composite with rGO: Synthesis,characterization, and solar light induced degradation of coloured and colourless effluents

Nickel ferrites (NF), silver doped nickel ferrites (AgNF), and a composite of silver doped nickel ferrites with reduced graphene oxide (AgNF@rGO) were prepared through the co-precipitation method. The X-ray diffraction analysis was carried out to confirm the structure of prepared materials, and the crystallite size of prepared ferrites was less than 10 nm. FT-IR spectroscopy was performed for the confirmation of functional groups present in the synthesized materials. The surface morphology of prepared samples was investigated via scanning electron microscopy. Optical analysis was carried out with the help of UV–Visible spectroscopy. Thermogravimetric analysis was performed to check the thermal stability. The photocatalytic degradation of methylene blue under solar light irradiation was studied. The AgNF@rGO composite showed 76% degradation of coloured compound (methylene blue) and 50% degradation of colourless compound (benzimidazole). The enhanced photocatalytic degradation efficacy of AgNF@rGO was ascribed to the reduced graphene oxide sheets, which provided a large surface area and the ability to trap electrons from the conduction band. As a result, the decreased recombination rate of electrons and holes enhanced the degradation ability of the composite based photocatalyst. A scavenging experiment was also performed to determine the most photoactive species taking part in the degradation process. In comparison among all prepared samples, AgNF@rGO showed the maximum photocatalytic activity. It was because of the large surface area of the AgNF@rGO. It was investigated that AgNF@rGO is the most effective catalyst for the degradation of coloured and colourless organic pollutants.     

杂多酸/Fe3O4磁性催化剂的制备及其对次甲基蓝溶液的降解

采用浸渍法将磷钨酸、磷钼酸和硅钨酸等杂多酸负载在Fe3O4磁性材料上,并将杂多酸/Fe3O4磁性材料作为光催化剂用于降解次甲基蓝溶液,考察了光源类型（紫外光与太阳光）、杂多酸种类及催化剂用量等对光催化降解效果的影响。结果表明,在250 W汞灯照射、次甲基蓝溶液浓度20 mg·L-1、降解体系pH=5.5、光催化剂用量30 mg和光催化120 min条件下,次甲基蓝降解率达85%,负载型杂多酸/Fe3O4磁性催化剂对次甲基蓝的降解效果明显优于相应单一的Fe3O4或杂多酸催化剂。     

Microwave-hydrothermal synthesis of extremely high specific surface area anatase for decomposing NOx

Apparently C-doped and undoped or pure nanoparticles of anatase were synthesized using a microwave hydrothermal process in the temperature range of 140–180 °C for 1 h from several Ti precursors, such as Ti ethoxide, Ti isopropoxide and Ti oxysulfate. Nanoparticles of anatase samples were characterized by powder X-ray diffraction, transmission electron microscopy (TEM) and photocatalytic activity measurements. Results showed that nanoparticles in the size range of 4–17 nm of anatase were obtained in all cases with surface areas in the range of 151–267 m²/g. The photocatalytic activity of the prepared titanias was measured using methylene blue (MB) and NO_x molecules. Because MB has very strong adsorption on the samples, photocatalytic degradation under either solar light or black light irradiation was found to be very limited. However, the DeNO_x abilities of carbon-doped titanias were higher than those of Degussa P25 commercial titania sample and undoped or pure titanias especially under irradiation by long wavelength or visible light (>500 nm).