Sonoprecipitation dispersion of ZnO nanoparticles over graphene oxide used in photocatalytic degradation of methylene blue in aqueous solution: Influence of irradiation time and power

In this paper, ZnO/Graphene Oxide (ZnO/GO) is synthesized via ultrasound assisted precipitation method and the effect of power and ultrasound time irradiation is studied on photocatalyst properties. The synthesized samples are used for methylene blue (MB) degradation as an organic water pollutant. Physicochemical properties of the samples are investigated by XRD, FESEM, EDX, BET-BJH, FTIR and DRS techniques. Moreover, pH_pzc of the sample with the best performance is calculated to study the effect of acidity on the photocatalyst efficiency in photocatalytic process. Ultrasound has a positive effect on photocatalyst performance that is because of its effect on distribution of particles and semiconductor band gap, but it has no effect on photostability of the nanocomposite. Sonication has modified distribution of particles by enhancing the active sites for oxidation process. Making structural gaps by ultrasound irradiation increases available surface area which has a similar effect on photocatalyst performance. Graphene oxide as electron collector and transporter prevents electron-hole recombination and it can be an acceptable reason for enhancement at photocatalyst performance. Finally, some of operational parameters such as pH, photocatalyst loading and dye concentration are investigated.     

Synthesis of Na-doped ZnO nanowires and their photocatalytic properties

Na-doped ZnO nanowires with an average diameter of ∼40 nm have been fabricated by a thermal decomposition route at temperature around 400 °C. Their properties have been investigated using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), UV-visible spectroscopy, Raman spectra, and photoluminescence (PL) spectroscopy. Room temperature photoluminescence (RT-PL) showed that the as-synthesized ZnO samples exhibited strong visible emission with a major peak at 420 nm. Furthermore, intensity of the visible emission increased and then decreased with increase in Na concentration. The improvement of visible emission at 420 nm in the Na-doped ZnO samples should be a result of the surface defects increased by doping of Na in zinc oxide. In addition, photocatalytic studies indicated that these nanomaterials showed good photocatalytic performance for organic pollutants in water.     

Carbon quantum dots supported ZnO sphere based photocatalyst for dye degradation application

A Carbon quantum dots supported ZnO hollow Sphere (ZnO/C-dots) were synthesized through a solvothermal method using polyethylene glycol 400 (PEG 400) as a solvent. The phase and crystal structure of as-prepared ZnO/C-dots photocatalyst were characterized by powder X-ray diffraction (XRD). The surface morphology and size of the composite were analyzed using field emission scanning microscopy (FE-SEM). The optical properties of the as-prepared nanocomposites were examined using UV–visible (UV–Vis) spectrometer. The photocatalytic activity of pure ZnO and ZnO/C-dots nanocomposites were evaluated by the degradation of methylene blue (MB) under UV–Visible light irradiation. The ZnO/C-dots nanocomposites exhibited maximum photocatalytic MB dye degradation efficiency of 96% which is much higher that the pure ZnO (63%). The enhanced photocatalytic activity of ZnO/C-dots is due to the extended light absorption in the visible region and suppressed photoexcited electron-hole pair recombination rate. Moreover, the activity of photocatalyst after five cycles exhibits high stability, which is vital for the sustainable photocatalytic procedures. It is concluded that the prepared ZnO/C-dots composite have low cost, good stability and has a great potential application for Photocatalytic dye degradation.     

Facile,high yield ultrasound mediated protocol for ZnO hierarchical structures synthesis: Formation mechanism,optical and photocatalytic properties

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV–Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.     

Defect-controlled growth of ZnO nanostructures using its different zinc precursors and their application for effective photodegradation

Various zinc precursors, such as zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride, have been used to control the formation of zinc oxide (ZnO) nanostructures onto aluminum substrate by chemical means. FESEM images of the ZnO nanostructures showed the formation of different morphologies, such as flakes, nanowalls, nanopetals, and nanodisks, when the nanostructures were synthesized using zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride precursors, respectively. The TEM image of disk-like ZnO nanostructures formed using zinc chloride as a precursor revealed hexagonally shaped particles with an average diameter of 0.5 μm. Room-temperature photoluminescence (PL) spectra revealed a large quantity of surface oxygen defects in ZnO nanodisks grown from zinc chloride compared with those using other precursors. Furthermore, the ZnO nanostructures were evaluated for photocatalytic activity under ultraviolet (UV) light illumination. Nanostructures having a disk-like shape exhibited the highest photocatalytic performance (k = 0.027 min⁻¹) for all the ZnO nanostructures studied. Improved photocatalytic activity of ZnO nanodisks was attributed to their large specific surface area (4.83 m² g⁻¹), surface oxygen defects, and super-hydrophilic nature of their surface, which is particularly suitable for dye adsorption.     

Photocatalytic,sonocatalytic and sonophotocatalytic degradation of Rhodamine B using ZnO/CNTs composites photocatalysts

A series of ZnO nanoparticles decorated on multi-walled carbon nanotubes (ZnO/CNTs composites) was synthesized using a facile sol method. The intrinsic characteristics of as-prepared nanocomposites were studied using a variety of techniques including powder X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM), transmission electron microscope (TEM), scanning electron microscope (SEM) with energy dispersive X-ray analysis (EDX), Brunauer Emmett Teller (BET) surface area analyzer and X-ray photoelectron spectroscopy (XPS). Optical properties studied using UV–Vis diffuse reflectance spectroscopy confirmed that the absorbance of ZnO increased in the visible-light region with the incorporation of CNTs. In this study, degradation of Rhodamine B (RhB) as a dye pollutant was investigated in the presence of pristine ZnO nanoparticles and ZnO/CNTs composites using photocatalysis and sonocatalysis systems separately and simultaneously. The adsorption was found to be an essential factor in the degradation of the dye. The linear transform of the Langmuir isotherm curve was further used to determine the characteristic parameters for ZnO and ZCC-5 samples which were: maximum absorbable dye quantity and adsorption equilibrium constant. The natural sunlight and low power ultrasound were used as an irradiation source. The experimental kinetic data followed the pseudo-first order model in photocatalytic, sonocatalytic and sonophotocatalytic processes but the rate constant of sonophotocatalysis is higher than the sum of it at photocatalysis and sonocatalysis process. The sonophotocatalysis was always faster than the respective individual processes due to the more formation of reactive radicals as well as the increase of the active surface area of ZnO/CNTs photocatalyst. Chemical oxygen demand (COD) of textile wastewater was measured at regular intervals to evaluate the mineralization of wastewater.     

A comparative evaluation of the photocatalytic and optical properties of nanoparticulate ZnO synthesised by mechanochemical processing

In this study, mechanochemical processing has been used to manufacture a nanoparticulate powder of ZnO with a controlled particle size and minimal hard agglomeration. The suitability of this ZnO powder for use as either a photocatalyst or an optically transparent UV-filter was evaluated by comparing its optical and photocatalytic properties with those of three commercially available powders that were synthesised by chemical precipitation and flame pyrolysis. The ZnO powder synthesised by mechanochemical processing was found to exhibit high optical transparency and low photocatalytic activity per unit of surface area, which indicates that it is suitable for use in optically transparent UV-filters.

     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

Deactivation of photocatalytically active ZnO nanoparticle and enhancement of its compatibility with organic compounds by surface-capping with organically modified silica

Tetraethyl orthosilicate (TEOS) and dimethyldiethoxysilane (DEDMS) were used as co-precursors to prepare organically modified silica (ormosil) via sol-gel process. The resultant ormosil was adopted for surface-capping of ZnO nanoparticle, where methyl (organic functional group) and silica (inorganic component) were simultaneously introduced onto the surface of the nanoparticles for realizing dual surface-modification. The ormosil-capped ZnO nanoparticle showed strong hydrophobicity and good compatibility with organic phases, as well as effectively decreased photocatalytic activity and almost unchanged ultraviolet (UV)-shielding ability. More importantly, the comprehensive properties of ormosil-capped ZnO nanoparticle could be manipulated by adjusting the molar ratio of TEOS to DEDMS during sol-gel process. This should help to open a wider window to better utilizing the unique and highly attractive properties such as high UV-shielding ability and high-visible light transparency of ZnO nanoparticle in sunscreen cosmetics.     

水热法制备In2O3/ZnO异质结及其高的光催化性能

采用简单的两步水热法合成了不同In₂O₃质量比的In₂O₃/ZnO异质结复合材料．通过X射线衍射仪(XRD)、紫外-可见分光光度计(UV-vis)和扫描电子显微镜(SEM)对复合材料的结构、形貌和性能进行了表征．同时还使用UV-vis分光光度计测试了异质结降解罗丹明B(RhB)的光催化活性．实验结果表明,与纯ZnO和In₂O₃相比,In₂O₃的引入将ZnO的吸收光谱扩展到可见光区域,从而提高了其光生电子和空穴的分离．此外,In₂O₃/ZnO异质结在可见光照射对RhB具有较高的光催化活性．5 wt%-In₂O₃/ZnO异质结对RhB的降解率为84.3%,且具有良好的光催化稳定性．In₂O₃/ZnO异质结复合材料在有机染料废水的降解中有更广阔的应用前景．     

Dependences of the surface and the optical properties on the O2/O2 + Ar flow-rate ratios for ZnO thin films grown on ZnO buffer layers

ZnO active layers on ZnO buffer layers were grown at various O₂/O₂ + Ar flow-rate ratios by using radio-frequency magnetron sputtering. Atomic force microscopy images showed that the surface roughnesses of the ZnO active layers grown on ZnO buffer layers decreased with decreasing O₂ atmosphere, indicative of an improvement in the ZnO surfaces. The type of the ZnO active layer was n-type, and the resistivity of the layer increased with increasing O₂ atmosphere. Photoluminescence spectra from the ZnO active layers grown on the ZnO buffer layers showed dominant peaks corresponding to local levels in the ZnO energy gap resulting from oxygen vacancies or interstitial zinc vacancies, and the peak positions changed significantly with the O₂/O₂ + Ar flow rate. These results can help improve understanding of the dependences of the surface and the optical properties on the O₂/O₂ + Ar ratio for ZnO thin films grown on ZnO buffer layers.     

镉掺杂氧化锌纳米花的制备及其光催化活性

以氯化锌、氯化镉、氢氧化钠为原料,采用水热法合成Cd掺杂纳米花状ZnO光催化剂,并通过该样品对罗丹明B水溶液的降解来研究其光催化活性。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线能量色散谱（EDS）、光致发光谱（PL）及紫外-可见分光光度计（UV-Vis）等测试手段对材料物性进行表征。实验结果表明：当掺杂Cd²⁺时,样品形貌发生变化、粒径减小;掺杂Cd²⁺后的ZnO的吸收边和紫外峰对比于纯ZnO均发生红移,禁带宽度由3.24 eV 减小到3.16 eV。通过光催化实验分析可知,掺杂后纳米ZnO光催化剂对罗丹明B 水溶液的降解率有所提高,光照3 h其降解率高达98%,说明与纯ZnO相比,Cd掺杂ZnO纳米花具有更高的光催化活性。     

Origin of Antibacterial Activity of ZnO Nanoparticles: The Roles of Protonic and Electronic Conductions

To elucidate the origin of antibacterial activity of ZnO nanoparticles, a reactive oxygen species (ROS) mechanism is systematically investigated based on electronic and protonic conductions. While the enhancement of antibacterial activity by an increase in electronic conductivity is marginal, an apparent improvement is observed by in the increase of protonic conductivity in terms of the surface basicity. This study first demonstrates that antibacterial activity can be enhanced by controlling the surface basicity of solid particles. The basicity of ZnO can be modulated by doping alkaline‐earth oxides such as MgO and CaO, and it results in the increase of hydroxyl defects on the surface of solid particles. The basicity shows a strong dependency on mobile OH concentrations. The increase of ROS hydroxyl radicals is confirmed by Mg (ZMO) or Ca‐doping (ZCO), which shows high antibacterial activity, and Ca‐doped ZnO exhibits the highest performance. It is clearly observed that the antibacterial activity is proportional to the basicity, which is controlled by the mobile OH formation. While both electrons and hydroxyl species are required for ROS reactions, it is concluded that the formation of hydroxyl species is a key factor in improving the antibacterial activity in ZnO.     

Improved photocatalytic performance of Pd-doped ZnO

ZnO and Pd-doped ZnO photocatalysts with different molar ratio of Pd/Zn (1/100, 2/100, 3/100 and 4/100) were prepared by a sol-gel method. The photocatalysts prepared were characterized by BET surface area, X-ray diffraction (XRD), UV/vis diffuse reflectance (DRS) and surface photovoltage spectroscopy (SPS), respectively. The results show that doping Pd into ZnO decreases the BET surface area. The XRD spectra of the Pd-doped ZnO catalysts calcined at 773 K show only the characteristic peaks of wurtzite-type. Doping Pd into ZnO increases the absorbance of ZnO in visible region and enhances the photoinduced charge separation rate. The photocatalytic activity of Pd-doped ZnO photocatalysts for decolorization of methyl orange (MO) solution was evaluated, of all the photocatalysts prepared, the Pd-doped ZnO with 3/100 possesses the best photocatalytic activity. The results of further experiments show that increased adsorption ability of light and high separation rate of photoinduced charge carriers all play an important role in promotion of photocatalytic activity of Pd-doped ZnO nanostructure.     

Enhanced performances of ZnO-TFT by improving surface properties of channel layer

Top-contact thin film transistors with ZnO as the channel layer and thermally grown SiO₂ as the gate dielectric were fabricated by using rf sputtering. The performances of ZnO-TFTs with different thicknesses of the active layer were investigated and the optimized condition was obtained. With the active layer thickness from 25 to 70 nm, the leakage current of devices increased from 10⁻¹⁰ to 10⁻⁸ A, and the on/off ratio decreased from 1.2×10⁷ to 2×10⁴. Atomic force microscope research indicated that with the thickness increased, the surface morphology of the active layer improved noticeably at first and then deteriorated. The 25-nm-thick ZnO TFT had the best surface morphology, and showed the best performance with a field effect mobility of 5.1 cm²/V S, on/off ratio of 1.2×10⁷ and threshold voltage of 20 V. This indicates that the surface properties of the channel layer have crucial affects on the performances of ZnO-TFTs.     

ZnO纳米晶/巯基乙酸复合膜的荧光特性

用自组装方法将巯基乙酸(MPA)与ZnO纳米晶薄膜(ZDF)通过共价键偶联到一起,形成纳米晶／巯基乙酸复合膜(ZDF／MPA)。采用发光光谱和XPS电子能谱技术,研究了ZDF／MPA的荧光特性以及它们之间的能量传递机制。研究发现ZDF／MPA中ZnO自由激子发光和束缚激子发光强度随着巯基乙酸的浓度增大而分别呈现不同的非线性减弱关系,当巯基乙酸达到一定的浓度量时,ZnO荧光完全消失。研究表明：ZnO纳米薄膜与MPA之间能够发生成键作用,并且在成键之后发生了能量传递。     

ZnO/Cu_2O异质结纳米阵列制备及光催化性能

利用湿化学法在FTO玻璃基底上制备了高度规整的ZnO纳米棒阵列(ZnO NRAs),以此为衬底,采用磁控溅射法在ZnO NRAs表面沉积Cu_2O薄膜。分别用X射线衍射仪、X射线光电子能谱、扫描电镜、光致光谱、紫外可见分光光度计和电化学工作站对样品的物相、形貌、吸收光谱、光电性能进行了表征,用甲基橙(MO)模拟有机物废水研究复合材料的光催化性能。结果表明:ZnO纳米棒为六方纤锌矿结构,其直径约为80~100 nm,长约2~3μm,棒间距约100~120 nm。立方晶系的Cu_2O颗粒直径约为100~300 nm,形成致密膜层并紧密覆盖在ZnO NRAs表面上,构成ZnO/Cu_2O异质结纳米阵列(ZnO/Cu_2O HNRAs)结构。与纯ZnO NRAs和Cu_2O相比,ZnO/Cu_2O HNRAs在可见光范围内的吸收显著增强,吸收波长向可见光方向偏移。ZnO/Cu_2O HNRAs的载流子传递界面的电荷转移速度快,有效促进了光生电子和空穴的分离。在紫外-可见光照射65 min后,ZnO/Cu_2O HNRAs的降解效率为94%,分别是纯ZnO NRAs和Cu_2O的18倍和1.7倍。     

Surface modification with EDTA molecule: A feasible method to enhance the adsorption property of ZnO

Surface-functionalized zinc oxide (ZnO) nanoparticles were synthesized with ethylene diamine tetraacetic acid (EDTA) as a modification agent, which were used as adsorbents in the adsorption of Cu²⁺ at certain conditions. The transmission electron microscopy (TEM) results show that the average size of ZnO particles is about 45 nm, and it exhibits hexagonal wurtzite structure. Fourier transform infrared (FTIR) spectra reveal that the EDTA species are chemically bonded on the surface of ZnO. Compared with bare ZnO particles, the functionalized ZnO nanoparticles have a better activity in the Cu²⁺ adsorption. The maximum adsorption capacity of functionalized ZnO nanoparticles is 20.97 mg/g, while it is 17.93 mg/g for the bare ZnO. The adsorption isotherm of bare ZnO particles is in accordance with the Freundlich model, and the chemical adsorption is in a dominant position in the adsorption process of Cu²⁺ on functionalized ZnO particles.     

Cu-Ag协同表面改性TiO_2的第一性原理研究

因在温室气体的降解中扮演重要的角色,通过改性来提高二氧化钛的光催化性能的相关研究备受关注.由于催化反应主要发生在材料表面,因此对材料表面的改性研究尤为重要.本文采用第一性原理方法计算了金属Ag,Cu单掺杂及协同掺杂TiO_2(001)和(101)表面不同位置,通过形成能的比较获得了最稳定的晶体结构.通过对能带及态密度的对比得出:离子掺杂(001)表面所形成的活性基团的氧化性较(101)面更强,利于光催化氧化性能的提升;表面协同掺杂较单掺杂具有更强的光响应效率,与前人的实验结果符合较好.     

Fabrication of needle-like ZnO nanorods arrays by a low-temperature seed-layer growth approach in solution

Uniform, large-scale, and well-aligned needle-like ZnO nanorods with good photoluminescence and photocatalysis properties on Zn substrates, have been successfully fabricated using a simple low-temperature seed-layer growth approach in solution (50 °C). The formation of ZnO seed-layer by the anodic oxidation technique (AOT) plays an important role in the subsequent growth of highly oriented ZnO nanorods arrays. Temperature also proved to be a significant factor in the growth of ZnO nanorods and had a great effect on their optical properties. X-ray diffraction (XRD) analysis, selected-area electron diffraction (SAED) pattern and high-resolution TEM (HRTEM) indicated that the needle-like ZnO nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. The well-aligned ZnO nanorods arrays on Zn substrates exhibited strong UV emission at around 380 nm at room temperature. To investigate their potential as photocatalysts, degradation of pentachlorophenol (PCP) in aqueous solution was carried out using photocatalytic processes, with comparison to direct photolysis. After 1 h, the degradation efficiencies of PCP by direct photolysis and photocatalytic processes achieved 57% and 76% under given experimental conditions, respectively. This improved degradation efficiency of PCP illustrates that ZnO nanorods arrays on Zn substrates have good photocatalytic activity. This simple low-temperature seed-layer growth approach in solution resulted in the development of an effective and low-cost fabrication process for high-quality ZnO nanorods arrays with good optical and photocatalytic properties that can be applicable in many fields such as photocatalysis, photovoltaic cells, luminescent sensors, and photoconductive sensors. PACS 81.07.Bc; 81.10.Dn; 81.15.Pq; 82.50.Hp; 85.60.Jb