Shape and size control of ZnO nanostructures via a simple solution route

ZnO nanostructures with different morphologies were synthesized by condensing the Zn(OH)4(2-) precursors under hydrothermal conditions in the presence of a surfactant, cetyltrimethylammonium bromide (CTAB). Shape and size control of ZnO nanostructures was achieved by relatively simple variations of molar ratio of CTAB to Zn(OH)4(2-). With a higher molar ratio, ZnO nanotubes were obtained, whereas with a lower molar ratio, ZnO nanorods were formed; furthermore, with a moderate w value, the coexistence of ZnO nanorods and nanotubes was also observed. The photoluminescence of ZnO nanorods and nanotubes was also investigated.     

Controllable synthesis of flower- and rod-like ZnO nanostructures by simply tuning the ratio of sodium hydroxide to zinc acetate

A controlled synthesis of flower-?and rod-like ZnO nanostructures in a hydrothermal phase has been realized in the absence of an additional template. The well-defined morphologies are obtained by simply tuning the ratio of sodium hydroxide to zinc acetate in a narrow range. The products are characterized by powder x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The growth mechanism is suggested to be that the supersaturation of the precursor Zn(OH)(4)(2-) results in various nucleation habits, which induce the ZnO nanostructures with different morphologies.     

化学溶液法外延组装ZnO分级纳米结构

采用气相法、液相法相结合的方法外延组装了一种形貌新颖的复杂ZnO分级纳米结构--"纳米毛刷".首先用热蒸发的方法制备了宽面为极性面的ZnO纳米带,然后采用化学溶液法,在强碱溶液中在ZnO纳米带的极性面上外延生长Zno纳米棒阵列,实现了ZnO分级纳米结构"由下而上"地外延组装.采用负离子配位多面体生长基元模型讨论了ZnO分级纳米结构的外延组装机理.这种ZnO分级结构的实现,可望作为ZnO纳米器件的原型材料构建新型光电器件.     

Enhanced optical properties of heterostructured ZnO/CeO2 nanocomposite fabricated by one-pot hydrothermal method: Fluorescence and ultraviolet absorption and visible light transparency

Many researchers investigated the properties of either discrete metal oxide CeO₂ or ZnO materials. However, less attention has been paid to the various nanostructure and performances of CeO₂ and ZnO nanocomposite up to now. In this paper, a facile and low cost one-pot hydrothermal synthesis method has been adopted to obtained directly precursors of CeCO₃OH and Zn₅(CO₃)₂(OH)₆ with different Ce atom molar ratios to Zn, which are transformed into their corresponding metal oxide to form the ZnO/CeO₂ heterostructure nanocomposites (HSNCs) by pyrolysis. The heterostructure is composed of ZnO and CeO₂ monocrystals, simultaneously, CeO₂ monocrystals are well dispersed on the surface of ZnO monocrystal for cosmetics. Bing dependent on the analysis results of XRD and TEM for the obtained precursors before and after pyrolysis, the formation mechanism of HSNCs was proposed. To the best of our knowledge, the paper first reported heterostructured ZnO/CeO₂ nanocomposite grown in one-pot mixed aqueous solution of cerium nitrate, zinc acetate and urea without other extra surfactant. Additionally, the influence of various Ce/Zn molar ratios on the heterostructure, fluorescence emission and UV–visible absorption properties of HSNCs was investigated in detail. ZnO/CeO₂ HSNCs display higher fluorescence emission with the increasing Ce/Zn molar ratio. Meanwhile, the larger Ce/Zn molar ratio of ZnO/CeO₂ HSNCs, the stronger transparency in the visible light region and the weaker UV absorption. The results are due to the fact that the band gap of ZnO/CeO₂ HSNCs will decrease from 3.25 to 3.08 eV when Ce/Zn atom molar ratio is increased from 0 to 0.08. By the comprehensive analysis on the optical performances of HSNCs with the different Ce/Zn atom molar ratios, ZnO/CeO₂-0.04 HSNCs could become UV absorber materials and transparent material in the visible region. ZnO/CeO₂-0.04 HSNCs with the UV-filtering and Vis-transparent properties is appropriate for personal-care cosmetics.     

Screw dislocation-driven growth of two-dimensional nanoplates

We report the dislocation-driven growth of two-dimensional (2D) nanoplates. They are another type of dislocation-driven nanostructure and could find application in energy storage, catalysis, and nanoelectronics. We first focus on nanoplates of zinc hydroxy sulfate (3Zn(OH)(2)·ZnSO(4)·0.5H(2)O) synthesized from aqueous solutions. Both powder X-ray and electron diffraction confirm the zinc hydroxy sulfate (ZHS) crystal structure as well as their conversion to zinc oxide (ZnO). Scanning electron, atomic force, and transmission electron microscopy reveal the presence of screw dislocations in the ZHS nanoplates. We further demonstrate the generality of this mechanism through the growth of 2D nanoplates of α-Co(OH)(2), Ni(OH)(2), and gold that can also follow the dislocation-driven growth mechanism. Finally, we propose a unified scheme general to any crystalline material that explains the growth of nanoplates as well as different dislocation-driven nanomaterial morphologies previously observed through consideration of the relative crystal growth step velocities at the dislocation core versus the outer edges of the growth spiral under various supersaturations.     

Sol–gel assisted hydrothermal synthesis of ZnO microstructures: Morphology control and photocatalytic activity

ZnO microstructures of different morphologies were synthesized by the sol–gel assisted hydrothermal method using Zn(NO₃)₂, citric acid and NaOH as raw materials. Twining-hexagonal prism, twining-hexagonal disk, sphere and flower-like ZnO microstructures could be synthesized only through controlling the pH of the hydrothermal reaction mixture at 11, 12, 13 and 14, respectively. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). Optical properties were examined by UV–Vis absorption/diffuse reflectance spectroscopy and room-temperature photoluminescence measurements (PL). Photocatalytic activities of the samples were evaluated by degradation of Reactive Blue 14 (KGL). The results indicated that the flower-like ZnO composed of nanosheets possessed superior photocatalytic activity to other ZnO microstructures and commercial ZnO, which could be attributed to the morphology, surface defects, band gap and surface area. The formation mechanisms of different ZnO morphologies were also investigated based on the experimental results.     

Morphology-tuned growth of ZnO microstructures

Morphology-tuned ZnO microcrystals can be prepared by oxidizing zinc metal substrates in aqueous solution using hydrothermal technique. Some typical ZnO growth morphologies such as nanorod superstructures, nanorod arrays, microspheres, hierarchical nanostructures, and split crystals have been chemically fabricated. These microscopic shapes can be finely controlled by selecting Zn(NO₃)₂ concentration and solvent. A conceptual model was proposed to explain the formation of the as-prepared ZnO structures by selecting proper kinetic environments. This one-step, wet-chemical approach is controllable and reproducible, which can be conveniently transferred to industrial applications.     

Photo-initiated growth of zinc oxide (ZnO) nanorods

A photo-initiated process via femtosecond pulse-induced heterogeneous nucleation in zinc ammine complex (Zn(NH₃)₄²⁺)-based aqueous solution without catalyst and surfactant, followed by hydrothermal treatments for crystal growth into zinc oxide (ZnO) nanorods, was investigated. Flat-top hexagonal ZnO nanorods with smooth planes of diameter ≥ 100 nm and length ≤ 1 μm were grown with laser irradiation, compared to porous rod-like structures without irradiation. The flat-top planes indicate slow growth rate, due to the intermediate step of Zn(NH₃)₄²⁺ decomposition to Zn(OH)₄²⁻, before dehydration to ZnO. Prolonged hydrothermal treatment produced nanotubes and lateral splits due to OH⁻ erosion of the crystal faces. XRD analysis showed a hexagonal crystal structure while photoluminescence study indicated a peak at about 380 nm.     

A task specific basic ionic liquid for synthesis of flower-like ZnO by hydrothermal method

Flower-like ZnO morphology, with different shapes, have been successfully synthesized via a novel and environment-friendly hydrothermal method using zinc acetate and a task specific dicationic dibasic ionic liquid, [mmpim]₂[OH]₂, which plays an important role in fabrication of ZnO structure. The structure and morphology of the product were characterized by X-ray diffraction and scanning electron microscopy, which show different flower-like morphologies. Photoluminescence spectrum of the product exhibits a strong ultraviolet emission at 391 nm and two weak blue-green emissions at about 450 and 500 nm.     

Analysis of growth parameters for hydrothermal synthesis of ZnO nanoparticles through a statistical experimental design method

Nanocrystalline ZnO particles were synthesized from an aqueous solution composed of zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and urea (H₂NCONH₂). A precipitating precursor, basic zinc carbonate (Zn₅(CO₃)₂(OH)₆), was first formed by hydrothermally treating the solution at 120 °C for 2–4 h. Nanocrystalline ZnO particles were then obtained by calcining the precursors at 350–650 °C for 0.5–2 h. The synthesis products were characterized using thermogravimetry–differential scanning calorimetry–mass spectrometry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. Based on the experimental results, a possible reaction mechanism for the ZnO formation was proposed. The effects of experimental parameters (namely, the hydrothermal treatment time, the calcination time, and the calcination temperature) on the characteristics of the resulting ZnO products (i.e., the crystalline size and the photoluminescence properties) were analyzed by the Taguchi method to attain the optimum synthesis conditions. By using the appropriate parameters derived from this method, we verified that the optimized synthesis provided a yield of ~70% and that the resulting ZnO particles possessed the characteristics of a ~25 nm crystalline size and a satisfactory photoluminescence property.     

Dependence of the textural properties and surface species of ZnO photocatalytic materials on the type of precipitating agent used in the hydrothermal synthesis

Three different precipitating agents (NaOH, \(\hbox {NH}_{4}(\hbox {H})\hbox {CO}_{3}\) and \(\hbox {CO}(\hbox {NH}_{2})_{2}\)) have been applied for the hydrothermal synthesis of ZnO powder materials, aiming at obtaining various types of porosity and surface species on ZnO. The synthesis procedures were carried out in the presence and in the absence of tri-block copolymer Pluronic (P123, EO20PO70EO20). These materials were characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM)–energy-dispersive X-ray spectroscopy (EDX), BET method and TG–differential thermal analysis (DTA) method, and their photocatalytic activities were tested in the removal azo dye Reactive Black 5 (RB5). The urea precipitant yields spongy-like surface forms and the greatest share of mesopores. It has the highest specific surface area, highest degree of crystallinity of wurtzite ZnO phase and largest content of surface OH groups in comparison with the other two precipitants. The zinc hydroxycarbonate intermediate phase is missing in the case of NaOH as precipitating agent; therefore, it manifests poorer textural characteristics. The morphology of P123-modified sample is different and consists of needle-shaped particles. The urea-precipitated samples display superior performance in the photocatalytic oxidation reaction, compared with the other precipitated samples. The other two precipitating agents are inferior in regard to their photocatalytic activity due to greater share of micropores (not well-illuminated inner surface) and different surface morphologies.     

Growth Mechanism of Different Morphologies of ZnO Crystals Prepared by Hydrothermal Method

Different morphologies of zinc oxide(ZnO),including microrods,hexagonal pyramid-like rods and flower-like rod aggregates,had been synthesized,respectively,on glass substrates by controlling the reaction conditions(such as precursor concentration,reaction time and pH value) of hydrothermal method.The morphologies of the as-obtained ZnO were observed with scanning electron microscopy and transmission electron microscopy.Also,the crystalline natures of different ZnO crystals were analyzed with X-ray diffraction.The possible growth mechanism of ZnO crystals with different morphologies was discussed.     

硫酸铵低温焙烧中低品位氧化锌矿

以中低品位氧化锌矿为原料、硫酸铵为反应介质,通过低温焙烧得到热料,研究了焙烧温度对Zn提取率的影响。结果表明,培烧温度为450℃时锌的提取率最高,为91.8%。焙烧温度低反应不充分;焙烧温度过高H₂SO₄分解挥发,降低反应率。将熟料溶出过滤得到硫酸锌溶液,经净化除杂得到洁净的硫酸锌溶液。以硫酸锌溶液为原料、碳酸铵为沉淀剂,采用沉淀法制备出碱式碳酸锌前驱体,将其煅烧制备了微细氧化锌粉体。采用XRD、SEM及化学成分分析等手段对前驱体和氧化锌粉体进行了表征。结果表明,溶液中OH^-、HCO₃^-与Zn²⁺共同作用得到前驱体,前驱体受热脱水、分解得到ZnO粉体。碱式碳酸锌前驱体为Zn₄（CO₃）（OH）₆·H₂O,呈类球形颗粒团聚体,氧化锌粉体为六方铅锌矿结构,颗粒呈球形,分散性良好。     

蓝光发光性能优异的氧化锌空心微球的制备及表征

本工作采用低温溶剂水浴热法, 以葡萄糖、柠檬酸盐为辅助剂, 首先制备了柠檬酸锌空心微球, 然后在空气气氛中500℃煅烧制得ZnO空心微球。应用XRD、TG-DSC、SEM、TEM、IR对产物的组成、结构以及形貌进行了研究, 研究发现该方法制备的前驱体为直径约为2 μm, 壁厚约为200 nm的空心微球。由前驱体煅烧后得到的ZnO空心微球由粒径为20~30 nm的纳米粒子组装成, 平均直径约为1 μm, 壁厚约为100 nm。此外还采用光致发光光谱仪(PL)对产物的光学性能进行了研究, 结果表明ZnO空心微球在激发波长为325 nm的条件下具有较好的蓝光发光性能, 发光峰位于469 nm处。     

A facile chemical route to synthesize ZnO nanoarrays: one-dimensional nanowire arrays and two-dimensional porous nanosheet arrays

A facile chemical route is presented to synthesize ZnO nanoarrays including one-dimensional nanowire arrays and two-dimensional porous nanosheet arrays. Large-scale ZnO nanowire arrays with the length of 5 microm and aspect ratio of 42 were achieved by cyclic growth in aqueous solution. After being immerged in the zinc acetate solution for 24 h, the ZnO nanowire arrays converted to sheet-like Zn5(OH)8(CH3COO)2 arrays. Subsequently, the sheet-like Zn5(OH)8(CH3COO)2 arrays converted to the porous ZnO nanosheet arrays by annealing treatment. As demonstrated by the performance of dye-sensitized solar cells (DSC), the porous ZnO nanosheet arrays can improve the efficiency of DSC effectively. In addition, the synthesized ZnO nanoarrays have potential applications in solar cells, catalysis, sensors and other nanodevices.     

Growth of zinc oxide nanorod structures: pressure controlled hydrothermal process and growth mechanism

Zinc oxide (ZnO) nanorods of various morphologies are grown on zinc substrate by pressure-assisted hydrothermal process and the growth mechanism is investigated with the help of molecular dynamics (MD) simulation results. Hydrothermally reacted ZnO₂ nanostructure bottom-up formation from Zn substrate is a useful process employed here. A systematic study on the role of process control parameters such as pressure and temperature on nanorod growth has been carried out. Correlation among the process parameters to form ordered nanostructures is established. The effect of pressure on the diameter and length of the grown ZnO nanorod structures is studied, which is precisely tunable. With a decrease in pressure from 500 to 400 kPa, the nanorod diameter is reduced by 22.2 %, while its length is increased by 24.8 %. At lower vapor pressure, the nanorod tips are sharper, whereas at higher vapor pressure they are flat. These variations along with a detailed analysis of MD simulations helps us hypothesize that pressure plays an important role in governing the diffusion of oxygen atom onto zinc surface and generating wurtzite phase. Simulation results clearly show that ZnO nanorods lift off due to their interaction with the Zn atoms on the substrate and the resulting forces.     

Fabrication of novel hierarchical ZnO via ultrasonic assisted hydrothermal route and their gas sensing property

Novel hierarchical ZnO nanomaterials with castellated and turriform morphologies were successfully synthesized by ultrasonic assisted hydrothermal route. The morphology and structure of products were characterized by scanning electron microscopy and X-ray diffraction, respectively. The results show that as-prepared castellated ZnO microrods have six-equal axis symmetry features with the length of 2–4 μm and the diameter of about 1 μm, and ZnO with turriform morphology has radical branch structure with the diameter ranging from 500 to 700 nm. It is found that initial alkaline concentration of the solution plays a crucial role in determining two kinds of hierarchical morphologies by etching ZnO crystal during hydrothermal process. A possible formation mechanism of castellated and turriform ZnO microstructures is also proposed. Gas sensing of hierarchical ZnO to different gases was also examined. The result indicates turriform ZnO sensor has fast response properties and excellent selective resolution capability to C₂H₅OH gas.     

Growth and comparison of different morphologic ZnO nanorod arrays by a simple aqueous solution route

A simple aqueous solution route has been successfully employed to prepare large-scale arrays of ZnO nanorods on the zinc foil without the assistance of any template, oxidant or coating of metal oxide layers. It is found that the growth of ZnO nanorod arrays with different densities, diameters and morphologies is dependent on the ammonia concentration and zinc precursor. The different morphologies of the ZnO nanostructures attained with or without adding Zn²⁺-contained salt in the alkaline solution are compared in the paper. The possible growth mechanism concerning the growth of the different ZnO nanocrystal morphologies is also discussed.     

Growth and properties of Zn(1-x)CdxO and Zn(1-x)CdxO/ZnO core/shell nanoparticles

Octylamine capped Zn(1-x)CdxO alloys and Zn(1-x)CdxO/ZnO core/shell nanoparticles have been grown by the thermal decomposing of zinc and cadmium cupferronates in organic solvents. Zn(1-x)CdxO alloys incorprated with different concentration of Cd have been grown by quickly injecting of their precursors at 200 degrees C. Zn(1-x)CdxO/ZnO core/shell nanoparticles are performed by slowly injecting of shell precursors at 180 degrees C. The prepared nanoparticles are characterized by X-ray diffraction, absorption spectrometer, Mirco-Raman spectrometer and transmission electron microscopy. The band gap of ZnCdO alloys shrinks linearly and the crystal lattice expands with an increase of Cd concentration. The growth of ZnO shells on ZnCdO cores enhances the core luminescence dramatically and results in a red shift in the absorption and emission of Zn(1-x)CdxO cores.     

Comparative study of structural and optical properties of ZnO nanostructures prepared by three different aqueous solution methods

In the present work, zinc oxide (ZnO) nanoparticles with different morphologies and sizes were successfully synthesized via three different aqueous solution routes named proteic sol–gel, PVA-assisted sol–gel and microwave-assisted hydrothermal method. Sol–gel samples were crystallized into hexagonal structure after calcination at 350 °C, presenting uniform growth and predominantly spherical particles. On the other hand, the sample produced via hydrothermal method assumed nanorod morphology, probably due to the adsorption of ammonium on the surface of ZnO nuclei, which affect the growth orientation of the crystals. All the samples exhibited a sharp UV emission peak, related to excitonic recombination, and a broad emission band in the visible region, attributed to internal transitions in color centers. Sol–gel samples calcined at the lowest temperatures presented an UV emission intensity that was 44 and 89 times higher than the visible emission, which can be related to the passivation of the defects by hydrogen ions. As-prepared hydrothermal sample presented a broad emission band centered at approximately 596 nm, which is possibly related to OH groups adsorbed on the particle surfaces. Nevertheless, the emission band of samples calcined above 800 °C was shifted to 540 nm, which is probably related to oxygen vacancy according to the results from chemical analysis.