复合Ag/ZnO分级结构微球的制备及其光催化性能研究

采用化学沉淀法制备ZnO微球,利用柠檬酸三钠（TCD）避光还原硝酸银在ZnO表面沉积银粒子制备Ag/ZnO复合材料.利用XRD、SEM、TEM、EDS、FTIR、UV-vis DRS、PL、BET等对Ag/ZnO的结构、组分、形貌及光谱性质进行了表征,通过紫外及可见光照降解甲基橙溶液评价样品的光催化性能.结果表明：ZnO纳米微球是由ZnO纳米片相互交错构筑而成的具有丰富孔道的分级结构,Ag纳米粒子均匀沉积在ZnO纳米片上.Ag的沉积显著增加了ZnO的可见光吸收,猝灭了ZnO荧光,提高了ZnO催化活性.     

Molecular dynamics simulations of inverse sodium dodecyl sulfate (SDS) micelles in a mixed toluene/pentanol solvent in the absence and presence of poly(diallyldimethylammonium chloride) (PDADMAC)

Well-aligned ZnO nanorods (NRs) were grown on indium-tin-oxide (ITO) slide by the hydrothermal method and used as templates for preparing ZnO/Au composite nanoarrays. The optical and morphological properties of ZnO/Au composites under various HAuCl(4) concentrations were explored via UV-vis absorption spectroscopy, photoluminescence (PL) and scanning electron microscopy (SEM). The density and size of gold nanoparticles (Au NPs) on ZnO NRs can be controlled by adjusting the concentration of HAuCl(4). The optimal ZnO/Au composites display complete photocatalytic degradation of methyl blue (MB) within 60 min, which is superior to that with pure ZnO NRs prepared by the same method. The reason of better photocatalytic performance is that Au NPs act as electron traps and it prevents the rapid recombination of electrons and holes, resulting in the improvement of photocatalytic efficiency. The photocatalytic performance of ZnO/Au composites is mainly controlled by the density of Au NPs formed on ZnO NRs. The application in rapid photodegradation of MB shows the potential of ZnO/Au composite as a convenient catalyst for the environmental purification of organic pollutants.     

纳米ZnO薄膜的制备及其可见光催化降解甲基橙

采用溶胶-凝胶方法制备ZnO透明溶胶, 在铝箔上涂膜后经500 ℃处理制得具有可见光响应的纳米ZnO薄膜光催化剂. 以甲基橙模拟有机污染物, 在可见光下研究了薄膜的降解性能, 结果表明, 用一片有效面积为200 cm2的ZnO/Al薄膜作为催化剂, 甲基橙的降解率达到96.3％, 比ZnO负载在玻璃上制得的ZnO/glass薄膜催化剂活性高得多. 采用扫描电镜与原子力显微镜对ZnO/Al薄膜制备条件进行了表征, 结果发现多孔ZnO/Al薄膜比致密ZnO/Al薄膜具有更高的活性, 实验制备的具有高活性的ZnO/Al薄膜颗粒平均直径为52.2 nm. 采用本方法制备的ZnO/Al薄膜是一种具有应用前景的, 能在可见光下降解有机物的有效光催化剂.     

Preparation and characterization of zinc oxide nanoflakes using anodization method and their photodegradation activity on methylene blue

In this work, we report the formation of leaf-like ZnO nanoflakes by anodization of zinc foil in a mixture of ammonium sulfate and sodium hydroxide electrolytes under various applied voltage and concentration of sodium hydroxide. The morphology and structure of ZnO nanoflakes were investigated by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. In addition, the photocatalytic activity of the prepared nanoflakes zinc oxide was evaluated in the photodegradation of organic dye methylene blue (MB) solution under UV irradiation. It was found that zinc oxide prepared under high concentration of sodium hydroxide and high voltage showed better performance in the photodegradation of methylene blue.     

Enhanced photocatalytic activity of Ni doped TiO2 nanowire–nanoparticle hetero–structured films prepared by hydrothermal and sol–gel methods

TiO₂ nanowire-nanoparticle hetero-structured films were prepared via a sol–gel method and coated on glass substrates by dipping method for photocatalytic activity. In this study 0, 1, 3, and 5 mol% of Ni doped were studied. One-dimensional TiO₂ nanowires (NWs) were prepared by hydrothermal treatment with TiO₂ nanoparticles (NPs) which are commercially available. XRD, FESEM, DRS, and XPS were used to characterize the prepared nanowire-nanoparticle hetero-structures films. 3%Ni doped TiO₂ hetero-structured film (TNi3) had the highest photocatalytic activity on the degradation of methylene blue (MB). TNi3 films provided about 4.3 times of degradation rate compared to undoped TiO₂ (T). It revealed that TNi3 film resulted in shifting the absorption wavelength towards narrowing the energy band gap and small crystallite size. Therefore, the TNi3 film exhibited a photocatalytic activity on the degradation of MB under visible light irradiation greater than undoped film.     

Hydrothermal Synthesis of Ce-doped ZnO Heterojunction Supported on Carbon Nanofibers with High Visible Light Photocatalytic Activity

Ce/ZnO decorated carbon nanofibers(CNFs) heteroarchitectures(Ce/ZnO/CNFs) have been synthesized using electrospinning technique followed hydrothermal method, which have a high visible light photocatalytic activity. The samples were characterized by means of SEM, FTIR and XRD. The photocatalytic performance of Ce/ZnO/CNFs was tested with the methylene blue in the presence of visible light irradiation. In this work, we have analyzed the effects of Ce doping amount, initial methylene blue(MB) concentration and dosage of Ce/ZnO/CNFs on photocatalytic efficiency of the composite. The results showed that the photocatalyst containing 1.0% Ce in molarity(CZC1) obtained by autoclaving at 150℃ has the best photocatalytic degradation of MB than other as-synthesized samples. Ce/ZnO/CNFs catalysts exhibit a good stability and reusability, which would be an economical and environmentally friendly photocatalyst for various practical applications.     

Sol–gel synthesis of ZnO–SiO2 thin films: impact of ZnO contents on its photonic efficiency

Highly crystalline ZnO–SiO₂ films obtained by a sol–gel method at different ZnO contents were deposited on silicon substrate (P(100)) using spin coating process. The XRD results revealed that the strong ZnO(100) peak is grown with highly c-axis oriented film and the crystallinity is progressively improved with increasing ZnO contents. SEM micrographs of the films deposited on silicon substrate show a homogeneous and uniformity structure at different ZnO content. The prepared ZnO–SiO₂ films are compared with either a film prepared from a commercial photocatalysts Hombikat UV-100 or Pilkington Glass Activ? by the determination of their photonic efficiencies for degradation of methylene blue. The photocatalytic efficiency of the 10 wt% ZnO–SiO₂ film was found to be about four times higher than film prepared from UV-100 or Pilkington Glass Activ?. The photocatalytic efficiencies of ZnO–SiO₂ films are increased with increasing ZnO content from 1 wt% to 10 wt% ZnO and then decreased at 15 wt% ZnO. The order of photocatalytic efficiencies of ZnO–SiO₂ films at different ZnO content and commercial photocatalysts after 6 h illumination were as following: 10 wt% ZnO > 15 wt% ZnO > 1 wt% ZnO > as-prepared 10 wt% ZnO–SiO₂ film > UV-100 > Pilkington Glass Activ?, which suggested that the ZnO–SiO₂ films are photoactive than commercial photocatalysts. The improved efficiency and potentially the low-cost synthesis suggest that this material might be practically useful as a photocatalyst film.     

基于微通道内表面上垂直生长的ZnO纳米棒阵列的微反应器型光催化装置

通过在微通道内表面上制备均匀的ZnO晶种层薄膜,再在晶种膜的基础上制备出了垂直生长的ZnO纳米棒阵列。将长有ZnO纳米棒的微通道用作微反应器,以光催化降解亚甲基蓝(MB)溶液为例考察了流体停留时间和连续重复使用对光催化性能的影响。结果表明,在停留时间为80 s时MB的光降解率为95%,连续重复使用180 h后,MB的降解率仍在80%以上。     

Photocatalytic activities of multilayered ZnO-based thin films prepared by sol–gel route: effect of SnO2 heterojunction layer

In present study, ZnO/SnO₂/ZnO/SnO₂/ZnO multi–layer, ZnO/SnO₂/ZnO triple layer and ZnO single layer films have been deposited on glass substrate by sol–gel dip–coating technique. The structural and optical properties of thin films have been investigated by X-ray diffractometer, UV–visible, photoluminescence spectroscopies and scanning electron microscopy. The structural analysis reveals structural inhomogeneities and different crystallite growth processes as function of number of deposited layers. A comparison between photocatalytic activity of zinc oxide samples toward photodegradation of phenol, 4-aminophenol and 4-nitrophenol has been performed under UV light irradiation. Experiments were conducted to study the effects of operational parameters on the degradation rate. Pseudo-first-order photodegradation kinetics was observed on all films and the reaction constants were determined. The results showed that the photocatalytic activity of ZnO multi–layer film was superior to that of the ZnO single- and triple-layer films. Differences in film efficiencies can be attributed to differences in crystallinity, surface morphology, defect concentration of oxygen vacancy and to presence of SnO₂ sublayer that may act as trap for electrons generated in the ZnO layer thus preventing electron–hole recombination. The results reveal that SnO₂ hetrojunction layers improve crystalline quality, optical and photocatalytic properties of ZnO multilayered films.     

An effective nanocomposite of polyaniline and ZnO: preparation,characterizations, and its photocatalytic activity

The polyaniline/zinc oxide (PANI/ZnO) nanocomposites were prepared by in situ polymerization of aniline monomer with ZnO nanomaterials and applied as a photocatalyst for the degradation of methylene blue (MB) dye. The morphological observations elicited the agglomerations of PANI sheets which occurred due to the interaction between PANI and ZnO nanomaterials in PANI/ZnO nanocomposites. As compared to pristine PANI, the UV–vis spectra exhibited that the absorption peak of π–π* transitions considerably shifted to higher wavelength at 360 nm from 325 nm in the nanocomposites. The photocatalytic activity results indicated the substantial degradation of MB dye by ~76% over the surface of PANI/ZnO nanocomposite catalyst under light illumination. The PANI/ZnO nanocomposites showed three times higher photocatalytic activity to MB dye degradation compared to pristine PANI might due to high photogenerated electron (ē)–hole (h⁺) pairs charge separation.     

Fabrication of Co + F Doped ZnO Films for Improved Visible Light Responsive Photocatalysis

The aim of this work is to investigate the efficacy of nebulizer sprayed ZnO–Co–F thin films for degrading the methylene blue (MB) aqueous solution under visible light irradiation. The physical properties of the prepared samples like structural, surface morphological and optical properties are studied using X-ray diffractometer (XRD), Scanning Electron Microscope (FESEM), UV-vis NIR spectrometer, spctroflurometer (PL) and Fourier Transform Infrared spectrometer (FTIR). The photocatalytic studies revealed that ZnO–Co–F film exhibited superior degradation efficiency over ZnO–Co and ZnO against MB as evinced by the degradation rate constants, 0.0782, 0.0475 and 0.0289 min^–1, respectively. This study showed that Co + F doping helps to remove the major limitations of ZnO and thereby leads towards better visible light activity. The structural and optical studies revealed the proper incorporation of Co²⁺ and F^– ions into the ZnO lattice and the reduction in band gap. PL emission confirmed that Co + F doping reduces the electronhole recombination rate and increases the availability of free carriers.     

Defect-enhanced Photocatalytic Activity of ZnO Micro/nanostructures

ZnO micro/nanocrystals with controlled oxygen defects are successfully prepared through annealing precursors obtained via a simple solvothermal method. The size and surface defects of the as-synthesized ZnO mi- cro/nanocrystals increase with the solvent volume ratio of water/ethanol increasing; the BET surface areas of the corresponding samples decrease during these processes; photoluminescence reveals that the type and concentration of surface defects （oxygen vacancy and interstitial oxygen） are quite different for the samples prepared via different solvent volume ratio of water/ethanol. In addition, it is found that the photocatalytic activity of the synthesized ZnO nanocrystals is mainly dependent on the concentration of surface defects. The sample with more surface defects ex- hibits higher photocatalytic activity toward the degradation of methylene blue （MB）. The possible photocatalytic mechanism is discussed in detail.     

A Highly Efficient and Stable Photocatalyst; N-Doped ZnO/CNT Composite Thin Film Synthesized via Simple Sol-Gel Drop Coating Method

The thin film of N-doped ZnO/CNT nanocomposite was successfully fabricated on soda lime glass substrate by a simple sol-gel drop-coating method. The structural, morphological, chemical, and optical properties of as prepared samples were characterized by a variety of tools such as X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared spectroscopy (FT-IR), and UV-visible spectroscopy. The hexagonal crystalline structure was confirmed from XRD measurement without any other impurity phase detection in samples. The N-doped ZnO/CNT composite showed excellent photo-catalytic activity towards cationic methylene blue (MB) dye degradation with 100% removal rate under UV light irradiation as compared to N-doped ZnO (65%) and pure ZnO (47.36%). The convincing performance has also been observed for the case of visible light irradiation. The enhancement of that photocatalytic activity might be due to narrowing the band gap as well as the reduction of electron–hole pair recombination in ZnO matrix with the incorporation of dopant nitrogen and CNT. It is assumed from the obtained results that N-doped ZnO/CNT nanocomposite thin film can be employed as an economically achievable and ecofriendly method to degrade dye with UV and visible light irradiation. Additionally, density functional theory (DFT) calculations were applied to explore the effect of N-doping on electronic structure of ZnO. The computational study has supported the experimental results of significant band gap contraction, which leads to the maximum absorption towards higher wavelength and no appreciable change of lattice parameters after doping. A conceivable photocatalytic mechanism of N-doped ZnO/CNT nanocomposite has been proposed as well.     

Effect of 3D ZnO:Fe morphology on the photocatalytic activity under solar irradiation

Nanoparticles, microsphere, hedgehog sphere-like and flower-like ZnO:Fe photocatalysts were prepared by the hydrothermal method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet/visible absorption spectra (UV?CVis). The results show that the ZnO:Fe photocatalysts with different 3D morphologies are a hexagonal wurtzite structure with space group of p63mc. The pH value of the precursor has a great influence on various morphologies of ZnO:Fe photocatalysts. The flower-like and hedgehog sphere-like ZnO:Fe photocatalysts exhibit the high solar photocatalytic behavior on methylene blue (MB). The ZnO:Fe order of photocatalytic activity is as follows: flower?>?hedgehog sphere?>?microsphere?>?nanoparticle. The flower-like ZnO:Fe is optimal, which exhibits the highest degradation rate of 98% for light time of 5?h.     

球磨法制备异质结型光催化剂ZnO/Bi_4Ti_3O_(12)及催化性能

本文用水作为分散介质,掺杂一定量的ZnO于Bi_4Ti_3O_(12)中,采用高能球磨法制备了异质结型光催化剂ZnO/Bi_4Ti_3O_(12).利用UV-Vis、XRD、SEM和PL等仪器对样品进行了分析与表征.以375 W中压汞灯为光源,通过对亚甲基蓝的氧化来研究其光催化活性.结果表明,对于光氧化亚甲基蓝(MB),异质结型光催化剂ZnO/Bi_4Ti_3O_(12)光催化活性高于钛酸铋的光催化活性.当ZnO的掺杂量分别是0.0和0.5wt.%,异质结型光催化剂ZnO/Bi_4Ti_3O_(12)对亚甲基蓝光氧化率分别达到50.2和80.3 %.     

Straightforward Synthesis of Mn3O4/ZnO/Eu2O3-Based Ternary Heterostructure Nano-Photocatalyst and Its Application for the Photodegradation of Methyl Orange and Methylene Blue Dyes

Zinc oxide-ternary heterostructure Mn₃O₄/ZnO/Eu₂O₃ nanocomposites were successfully prepared via waste curd as fuel by a facile one-pot combustion procedure. The fabricated heterostructures were characterized utilizing XRD, UV–Visible, FT-IR, FE-SEM, HRTEM and EDX analysis. The photocatalytic degradation efficacy of the synthesized ternary nanocomposite was evaluated utilizing model organic pollutants of methylene blue (MB) and methyl orange (MO) in water as examples of cationic dyes and anionic dyes, respectively, under natural solar irradiation. The effect of various experimental factors, viz. the effect of a light source, catalyst dosage, irradiation time, pH of dye solution and dye concentration on the photodegradation activity, was systematically studied. The ternary Mn₃O₄/ZnO/Eu₂O₃ photocatalyst exhibited excellent MB and MO degradation activity of 98% and 96%, respectively, at 150 min under natural sunlight irradiation. Experiments further conclude that the fabricated nanocomposite exhibits pH-dependent photocatalytic efficacy, and for best results, concentrations of dye and catalysts have to be maintained in a specific range. The prepared photocatalysts are exemplary and could be employed for wastewater handling and several ecological applications.     

TiO2 Thin Film with Varied Porous Structure Applied on the Degradation of Methylene Blue

In this study, porous TiO₂ thin films were prepared by the sol‐gel method employing polyethylene glycol 1000 (PEG 1000) as an organic template. Pore sizes were adjusted by varying the concentration of PEG 1000. The optimal PEG concentration range required to form TiO₂ films with a regular porous structure was investigated and was found to be 0.01–0.015 M. As the PEG 1000 concentration increased, the surface of these films became rougher because of larger pores. Degradation of methylene blue (MB) under UV irradiation was used to determine the photocatalytic activity of the films. In addition, the effect of the pH value of the MB solution on the films was evaluated by controlling its pH value at 5, 7, and 9. The results showed that the photocatalytic activity was correlated to the pore size and pore density of the thin films. TiO2 thin films possessing pore sizes in the diameter range of 35–85 nm exhibited the best conversion of 98% after 8 h of UV irradiation when the pH value was 7.     

Transparent conducting Sn:ZnO films deposited from nanoparticles

Homogeneous transparent conducting Sn:ZnO films on fused silica substrates were prepared by dip-coating from nanoparticle dispersions, while the nanocrystalline Sn:ZnO particles with different dopant concentrations were synthesized by microwave-assisted non-aqueous sol–gel process using Sn(IV) tert-butoxide and Zn(II) acetate as precursors and benzyl alcohol as solvent. The dopant concentration had a great impact on the electrical properties of the films. A minimum resistivity of 20.3 Ω cm was obtained for a porous Sn:ZnO film with initial Sn concentration of 7.5 mol% after annealing in air and post-annealing in N₂ at 600 °C. The resistivity of this porous film could further be reduced to 2.6 and 0.6 Ω cm after densified in Sn:ZnO and Al:ZnO reaction solution, respectively. The average optical transmittance of a 400-nm-thick Sn:ZnO film densified with Sn:ZnO after the two annealing steps was 91%.     

ZnO Nanostructures Doped with Various Chloride Ion Concentrations for Efficient Photocatalytic Degradation of Methylene Blue in Alkaline and Acidic Media

In this study, chloride (Cl⁻) ions were successfully doped into ZnO nanostructures by the solvothermal method. The effect of various Cl⁻ concentrations on the photocatalytic activity of ZnO towards the photodegradation of methylene blue (MB) under the illumination of ultraviolet light was studied. The as-prepared Cl⁻-doped ZnO nanostructures were analyzed in terms of morphology, structure, composition and optical properties. XRD data revealed an average crystallite size of 23 nm, and the XRD patterns were assigned to the wurtzite structure of ZnO even after doping with Cl⁻. Importantly, the optical band gap of various Cl ion-doped ZnO nanostructures was successively reduced from 3.42 to 3.16 eV. The photodegradation efficiency of various Cl⁻ ion-doped ZnO nanostructures was studied for MB in aqueous solution, and the relative performance of each Cl ion-doped ZnO sample was as follows: 20% Cl⁻-doped ZnO > 15% Cl⁻-doped ZnO > 10% Cl⁻-doped ZnO > 5% Cl⁻-doped ZnO > pristine ZnO. Furthermore, the correlation of the pH of the MB solution and each Cl ion dopant concentration was also investigated. The combined results of varying dopant levels and the effect of the pH of the MB solution on the photodegradation process verified the crucial role of Cl⁻ ions in activating the degradation kinetics of MB. Therefore, these newly developed photocatalysts could be considered as alternative materials for practical applications such as wastewater treatment.     

铝基板的界面扩散对薄膜型TiO2光催化活性的影响

以钛酸四丁酯为前驱体, 采用溶胶-凝胶法在铝基板表面制备了纳米晶TiO2薄膜. 运用XRD、SEM和XPS对制得的薄膜进行表征, 并测试了薄膜光催化降解亚甲基蓝(MB)的活性. 结果表明, TiO2薄膜样品在450 ℃焙烧30 min后, 晶粒排列比较致密, 粒径为10-20 nm, 并与铝基板紧密结合; 薄膜与铝基板发生了明显的界面扩散, 薄膜中的Al元素来自铝基板的界面扩散, 且界面层很宽, 扩散层厚度约为75 nm; 界面扩散的发生直接导致了TiO2薄膜的光催化活性下降. 但随着薄膜厚度增加, 铝基板对TiO2薄膜降解亚甲基蓝催化活性的影响不断减小.