Aqueous solution route to high-aspect-ratio zinc oxide nanostructures on indium tin oxide substrates

High-aspect-ratio ZnO nanowires and nanotubes are formed on indium tin oxide (ITO) substrates using a three-step route at low temperatures. The three steps, including successive ionic layer absorption and reaction (SILAR) deposition of the ZnO seed layer, hydrothermal annealing of the seed layer, and chemical bath deposition (CBD) of the one-dimensional (1D) ZnO nanostructures, are all conducted in aqueous solutions at temperatures below 120 degrees C. Both the hydrothermal annealing of the SILAR seed layer and the low-concentration precursor solution employed in the CBD process are crucial in order to synthesize the uniform and high-aspect-ratio ZnO nanostructures on the ITO substrate. TEM analyses reveal that both the nanowire and the nanotube possess the single-crystal structure and are grown along [001] direction. Room-temperature cathodoluminescence spectrum of the 1D ZnO nanostructures shows a sharp ultraviolet emission at 375 nm and a broad green-band emission.     

Systematic investigation on morphologies, forming mechanism, photocatalytic and photoluminescent properties of ZnO nanostructures constructed in ionic liquids

In this contribution, a series of shape-controllable ZnO nanostructures were synthesized in ionic liquids by a simpler, only one-step, low-temperature route, and characterized by XRD, XPS, TEM, HRTEM, SAED, EDXA, SEM, FTIR, surface area measurement and photoluminescence. We mainly investigate the effect of cations of ionic liquids on the shape of ZnO nanostructures and the forming mechanism of ZnO nanostructures in ionic liquids, as well as the luminescent property and photocatalytic activity for the degradation of Rhodamine B. The results show that the longer alkyl chain at position-1 of the imidazole ring of the ionic liquid will hinder the ZnO nanostructures from growing longer, and the hydrogen bonds may play a crucial role for the directional growth of the 1D nanocrystals. The photoluminescent study shows that the as-obtained ZnO nanostructures exhibit a unique green emission, indicating the existence of oxygen vacancies in the ZnO nanostructures. Importantly, the as-obtained ZnO nanostructures prepared in different ionic liquids show strong size/shape-dependent photocatalysis activity for degradation of Rhodamine B, and the well-dispersed homogeneous ZnO nanoparticles and nanowires display high photocatalytic activity. The investigation of photodegradation kinetics of Rhodamine B indicates that the photodegradation process obeys the rule of a first-order kinetic equation ln( C(0)/ C) = kt. This is the first systematic investigation on the relationship between the structure of ionic liquids and the morphology of ZnO nanostructures.     

Selected-control synthesis of ZnO nanowires and nanorods via a PEG-assisted route

Long-chain polymer-assisted growth of one-dimensional (1D) nanostructures has been investigated in previous research. This kind mild method has lots of merits such as not requiring complex procedures, without template supporting etc. Can the short-chain polymer also be used to grow long nanowires? In the present work, a short-chain polymer (PEG400) was found to promote the formation of 1D ZnO nanostructures, which cannot be obtained by long-chain polymers (such as PEG10000). Moreover, nanowires and nanorods can be selectively synthesized by using short-chain polymers. The influence factors for the formation of 1D ZnO nanostructures were also investigated in detail. The XRD, Raman spectrum, XPS, SEM, TEM, ED, HRTEM, EDXA, and PL spectra have been provided for the characterization of the as-obtained nanowires and nanorods.     

Systematic Synthesis of ZnO Nanostructures

In this study, we report a simple solution‐phase method to prepare ZnO nanostructures with controllable morphologies. By using oleylamine (OAm) and dodecanol (DDL) as solvents, zinc oxide nanocrystals with tunable sizes and diverse shapes (hexagonal pyramids, bulletlike, and pencil‐like shapes) have been obtained under mild conditions. At the same time, the introduction of presynthesized gold nanocrystals can also lead to the hybrid nanostructures of gold–zinc oxide hexagonal nanopyramids. In addition, the possible formation mechanism of the as‐prepared ZnO nanostructures has been investigated. Notably, the unique optical properties of the ZnO nanostructures with different sizes and shapes have also been discussed. We hope that this strategy will be a general and effective method for fabricating other metal oxide nanocrystals.     

Ultrahigh density arrays of toroidal ZnO nanostructures by one-step cooperative self-assembly processes: mechanism of structural evolution and hybridization with Au nanoparticles

A quick protocol for the fabrication of ultrahigh density arrays of toroidal ZnO nanostructures with tailored structures on a substrate surface is presented based on the one-step spin coating of a common solution composed of inverse micelles of polystyrene-block-poly(4-vinyl pyridine) copolymers (PS-b-P4VP) and sol-gel precursors without the need of conventional complex lithographic techniques. ZnO toroids decorated with gold nanoparticles are also obtained by subsequent loading and reduction of metallic precursors. It was elucidated that the diethanolamine moiety in the sol-gel precursors, which induces selective swelling and structural reorganization of the P4VP core blocks, plays a key role in the generation of toroidal nanostructures. Toroidal ZnO nanostructures embedded in a PS-b-P4VP matrix films or arrays of pure wurtzite ZnO nanorings are obtained by calcination under inert atmosphere. The structural parameters of the toroidal nanostructures such as the width, height, diameter of the rims as well as the spacing of their 2D arrays are controlled by employing PS-b-P4VP with different molecular weight and varying the mixing protocols.     

ZnO/ZnSe复合纳米结构的制备及可见光光催化性能

通过热水解法, 以氧化锌为模板, 成功制备出形貌均一的ZnO/ZnSe复合纳米结构. 为了对比不同O/Se比对光催化性能的影响, 保持其它反应参数不变, 调节还原剂水合肼的用量, 得到不同硒化程度的ZnO/ZnSe复合纳米结构. 采用场发射扫描电子显微镜、 X射线衍射仪和透射电子显微镜对样品的形貌及结构进行了表征, 通过测试该复合结构对亚甲基蓝的可见光催化降解评估了其光催化效率. 结果表明, 与纯ZnO比, ZnO/ZnSe复合结构在可见光区域和紫外光区域的光吸收范围变宽, 显示出较高的光催化效率. 原因在于ZnSe导带上的电子在扩散势能的作用下迁移到ZnO的导带上, 而空穴仍保留在ZnSe价带, 这样有助于光生电子和空穴对的分离, 降低其复合机率, 从而提高ZnO的光催化效率.     

From Zn-Al layered double hydroxide to ZnO nanostructure:Gradually etching by sodium hydroxide

Zn-Al layered double hydroxide(LDH) was used as precursor to produce ZnO nanostructures through dissolution of aluminum hydroxide in caustic soda.The Zn-Al LDH could transform into different nanostructures of ZnO on LDH nanosheets and even pure ZnO nanorods under various NaOH concentration.The formed ZnO nanorods vertically aligned on both LDH sides.UV-vis diverse reflectance spectra show that the obtained ZnO nanorods have a band gap of approximately 3.05 eV.Such ZnO/LDH nanostructures might be used as photocatalyst in the organic pollutant decomposition.     

Full Solution‐Processed Synthesis and Mechanisms of a Recyclable and Bifunctional Au/ZnO Plasmonic Platform for Enhanced UV/Vis Photocatalysis and Optical Properties

The synthesis of noble metal/semiconductor hybrid nanostructures for enhanced catalytic or superior optical properties has attracted a lot of attention in recent years. In this study, a facile and all‐solution‐processed synthetic route was employed to demonstrate an Au/ZnO platform with plasmonic‐enhanced UV/Vis catalytic properties while retaining strengthened luminescent properties. The visible‐light response of photocatalysis is supported by localized surface plasmon resonance (LSPR) excitations while the enhanced performance under UV is aided by charge separation and strong absorption. The enhancement in optical properties is mainly due to local field enhancement effect and coupling between exciton and LSPR. Luminescent characteristics are investigated and discussed in detail. Recyclability tests showed that the Au/ZnO substrate is reusable by cleaning and has a long shelf life. Our result suggests that plasmonic enhancement of photocatalytic performance is not necessarily a trade‐off for enhanced near‐band‐edge emission in Au/ZnO. This approach may give rise to a new class of versatile platforms for use in novel multifunctional and integrated devices.     

Solvent-Free Synthesis of ZnO Nanoparticles by a Simple Thermal Decomposition Method

This paper reports on a novel processing route for producing ZnO nanoparticles by solid-state thermal decomposition of zinc(II) acetate nanostructures obtained by the sublimation of zinc(II) acetate powder. The sublimation process of the Zn(OAc)₂ powder was carried out in the temperature 150 °C for 2 h. In addition, nanoparticles of ZnO were obtained by solid-state thermal decomposition of the synthesized Zn(OAc)₂ nanostructures. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. The sublimation process of the Zn(OAc)₂ powder was carried out within the range of 150–180 °C. The XRD studies indicated the production of pure hexagonal ZnO nanoparticles after thermal decomposition.     

Template-free fabrication of hexagonal ZnO microprism with an interior space

Well-faceted hexagonal ZnO microprisms with regular interior space have been successfully prepared by a template-free hydrothermal synthetic route. The morphologies of the products depend on the experimental conditions such as the solvent, the concentration of ammonia aqueous solution, and the reaction temperature. Through manipulation of the aging time, the as-prepared ZnO can be controlled as a monodispersed hexagonal twinning solid or as hollow microprisms. Moreover, the evolution process of the hollow ZnO nanoarchitecture after reaction for 2, 6, 12, and 24 h has been investigated by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). A possible growth mechanism has also been proposed and discussed. Furthermore, the photoluminescence (PL) measurement exhibits the unique emitting characteristic of hollow ZnO nanostructures.     

从Mn3O4前驱体到MnO2纳米结构的形貌和结构变化

锰氧化物是一类重要的且具有广泛应用背景的材料, 控制合成不同形貌和组成的锰氧化物纳米结构将有助于拓宽其应用领域. 本文报道了以Mn3O4为前驱体, 通过水热法控制合成MnO2纳米结构的方法. 用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等手段对产物进行表征. 在硫酸体系中,当反应温度为80 和180 ℃时, 所得产物分别为γ-MnO2海胆结构和β-MnO2单晶纳米棒. 此外, MnOOH纳米线可以在稀酸溶液中合成. 考察了反应温度、溶液酸度、反应时间对产物结构的影响, 并提出了基于γ-MnO2为中间产物的反应机理. 实验结果表明, 水热体系促进了产物的各向异性生长并最终形成不同形貌和结构的锰氧化物.     

Fabrication of 3D rotor-like ZnO nanostructure from 1D ZnO nanorods and their morphology dependent photoluminescence property

A facile and eco-friendly sonochemical route to fabricate well-defined dentritic (rotor-like) ZnO nanostructures from 1D ZnO nanorods without alloying elements, templates and surfactants has been reported. Phase and structural analysis has been carried out by X-ray diffraction (XRD) and Fourier Transform Infra-Red (FTIR) spectroscopy, showed the formation of hexagonal wurtzite structure of ZnO. Scanning electron microscopic (SEM) study showed the formation of rotor-like ZnO nanostructure having a central core which is surrounded by side branches nanocones. Transmission electron microscopic (TEM) study showed that these nanocones grow along [0001] direction on the six {01–10} planes of central core ZnO nanorods. A plausible formation mechanism of rotor-like ZnO nanostructures was studied by SEM which indicates that the size and morphology of side branches can be controlled by adjusting the concentration of OH^? ions and time duration of growth. The photoluminescence (PL) spectrum of the synthesized rotor-like ZnO nanostructures exhibited a weak ultraviolet emission at 400 nm and a strong green emission at 532 nm recorded at room temperature. The influence of morphology on the origin of green emission was discussed in detail. The results suggested a positive relationship among polar plane, oxygen vacancy and green emission.     

ZnO-based hollow microspheres: biopolymer-assisted assemblies from ZnO nanorods

Many efforts have been made in fabricating three-dimensional (3D) ordered zinc oxide (ZnO) nanostructures due to their growing applications in separations, sensors, catalysis, bioscience, and photonics. Here, we developed a new synthetic route to 3D ZnO-based hollow microspheres by a facile solution-based method through a water-soluble biopolymer (sodium alginate) assisted assembly from ZnO nanorods. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman and photoluminescence spectra of the ZnO-based hollow microspheres were obtained at room temperature to investigate their optical properties. The hollow microspheres exhibit exciting emission features with a wide band covering nearly all the visible region. The calculated CIE (Commission Internationale d'Eclairage) coordinates are 0.24 and 0.31, which fall at the edge of the white region (the 1931 CIE diagram). A possible growth mechanism of the 3D ZnO superstructures based on typical biopolymer-crystal interactions in aqueous solution is tentatively proposed, which might be really interesting because of the participation of the biopolymer. The results show that this biopolymer-directed crystal growth and mediated self-assembly of nanocrystals may provide promising routes to rational synthesis of various ordered inorganic and inorganic-organic hybrid materials with complex form and structural specialization.     

Shape-controlled synthesis of 3D and 1D structures of CdS in a binary solution with L-cysteine's assistance

A facile L-cysteine-assisted route was designed for the selectively controlled synthesis of 1D and novel, interesting 3D CdS spherical nanostructures constructed from CdS nanorods (or nanopolypods) in a binary solution. By controlling reaction conditions such as the molar ratio between Cd(OAc)2 and L-cysteine and the volume ratio of the mixed solvents, the synthesis of various 3D architectural structures and 1D wirelike structures in large quantities can be controlled. This is the first reported case of the direct growth of novel 3D self-assemblies of CdS nanorods (or nanopolypods). The morphology, structure, and phase composition of the as-prepared CdS products were examined by using various techniques (X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), high-resolution TEM, and Raman spectroscopy). On the basis of the results from TEM studies and our analysis, we speculate that in the present synthesis the L-cysteine dominates nucleation growth and the ethylenediamine (en)-dominated, oriented-assembly process. Interestingly, the products obtained show a gradient evolution in color from light-yellow to dark-yellow, which implies that their intrinsic optical properties change, possibly due to variations in their special morphologies and structures. This facile solution-phase L-cysteine-assisted method could be extended for the controlled preparation of other metal chalcogenides nanostructures with complex morphologies.     

Large-scale fabrication of tower-like, flower-like, and tube-like ZnO arrays by a simple chemical solution route

Large-scale arrayed ZnO crystals with a series of novel morphologies, including tower-like, flower-like, and tube-like samples, have been successfully fabricated by a simple aqueous solution route. The morphology and orientation of the obtained ZnO crystal arrays can be conveniently tailored by changing the reactants and experimental conditions. For example, the tower-like ZnO crystal arrays were obtained in a reaction solution system including zinc salt, ammonia, ammonium salt, and thiourea, and the orientation of these tower-like crystals could be controlled by the contents of these reactants. Flower-like ZnO arrays were obtained at lower temperatures, and tube-like ZnO arrays were obtained by ultrasonic pretreatment of the reaction system. The growth mechanism of the tower-like and tube-like ZnO crystals was investigated by FESEM. The results show that tower-like crystals grow layer by layer, while tube-like crystals grow from active nanowires. Ultrasonic pretreatment is proved to be effective in promoting the formation of active nuclei, which have important effects on the formation of the tube-like ZnO crystals. In addition, large-scale arrays of these ZnO crystals can be successfully synthesized onto various substrates such as amorphous glass, crystalline quartz, and PET. This implies this chemical method has a wide application in the fabrication of nano-/microscale devices.     

Controlled growth of two-dimensional and one-dimensional ZnO nanostructures on indium tin oxide coated glass by direct electrodeposition

A simple electrochemical deposition technique is used to deposit ZnO nanostructures with diverse morphology directly on ITO-coated glass substrates at 70 degrees C. The concentration of the Zn(NO 3) 2.6H 2O electrolyte is important to controlling the dimensionality of the nanostructures, with formation of one-dimensional (1D) nanospikes and nanopillars (with 50-500 nm diameter) below 0.01 M and of two-dimensional (2D) nanowalls and nanodisks (with 50-100 nm wall/disk thickness) above 0.05 M. Glancing-incidence X-ray diffraction study shows their wurtzite structure and confirms the change in the preferred crystal plane orientation with the dimensionality of ZnO nanostructures. UV-vis spectroscopy reveals a higher transmittance from 2D nanostructures than from 1D nanostructures and their optical direct band gaps estimated to be 3.12-3.27 eV. Depth-profiling X-ray photoemission studies show the presence of Zn(OH) 2 outer layers on the ZnO nanostructures, with a higher Zn(OH) 2 moiety for 2D nanostructures relative to 1D nanostructures. Furthermore, a substantial quantity of Cl (provided by the KCl supporting electrolyte) is detected throughout the 2D nanostructures only. The photoemission data therefore affirm our proposed growth mechanism that involves capping of the preferred [0001] growth direction by Cl (-) ions under fast hydroxylation kinetics condition as observed at a higher Zn(NO 3) 2.6H 2O electrolyte concentration.     

表面活性剂种类对纳米氧化锌形貌的影响

利用简单的水热法,以Zn(Ac)2.2H2O为锌源,通过调整表面活性剂的种类及碱源,制备了一系列不同形貌的纳米结构氧化锌;利用场发射扫描电子显微镜和X射线粉末衍射仪分析了产物的形貌和晶体结构,并探讨了多种表面活性剂和醋酸钠碱源对氧化锌纳米结构的影响.结果表明,以NaOH作为碱源时,在不添加任何表面活性剂的情况下,产物的形貌结构与氢氧化钠的加入量有关,当n(Zn2+)∶n(OH-)为1∶2.5、1∶10及1∶20时,分别得到片状、棒状及海胆状纳米结构的氧化锌;产物均为六方相氧化锌.     

Ultrasonic assisted synthesis of ZnO nanoflakes and photocatalytic activity evaluation for the degradation of methyl orange

In the present investigation, ZnO nanoflakes was prepared via sonochemical synthesis route. Effect of ultrasonic treatment time was studied based on structural, morphological and optical properties. X-ray diffraction (XRD) reveals the formation of wurtzite hexagonal crystalline structure of ZnO nanoflakes. Ultrasonic treatments affected the crystallite size and the density of dislocation, which is due to increased nucleation and growth rates of nanoflakes. The samples synthesized at 40–50 min ultrasonic treatment showed a strong absorption band at 605 and 650 (cm^?1) versus other treatments, which is an indication of 2D nanostructure (nanoflakes). FE-SEM analysis further confirms the formation of 2D nanostructures of the ZnO. The composition and purity was confirmed by the energy dispersive X-ray (EDX) analysis, which displays the occurrence of Zn and O elements in the sample. Photocatalytic activity (PCA) of ZnO nanoflakes was studied for methyl orange (MO) dye degradation under UV light exposure and up to 93.13 % dye degradation is achieved within 90 min. Effect of various parameters (dye concentration, mass of photocatalytic material) and kinetic study was also performed. Results revealed that the ultrasonic treatment affected the optical and photocatalytic properties of the of ZnO nanoflakes, which could be employed for the remediation of dyes in textile effluents.     

Formation of amorphous zinc citrate spheres and their conversion to crystalline ZnO nanostructures

We report a method for synthesizing zinc citrate spheres at a low temperature (90 °C) under normal atmospheric pressure. The spherical structures were amorphous and had an average diameter of ～1.7 μm. The amorphous zinc citrate spheres could be converted into crystalline ZnO nanostructures in aqueous solutions by heating at 90 °C for 1 h. By local dissolution of the zinc citrate spheres, nucleation and growth of ZnO occurred on the surfaces of the amorphous zinc citrate spheres. The morphologies and exposed crystal faces of the crystalline ZnO nanostructures (structure I: oblate spheroid; structure II: prolate spheroid; structure III: hexagonal disk; structure IV: sphere) could be controlled simply by varying the solution composition (solutions I, II, III, or IV) in which the as-prepared amorphous zinc citrate spheres were converted. The concentration of citrate anions and solution pH played a decisive role in determining the morphologies and exposed crystal faces of the crystalline ZnO nanostructures. On the basis of experimental results, we propose a plausible mechanism for the conversion of amorphous zinc citrate spheres into the variety of observed ZnO structures.     

Site-specific nucleation and growth kinetics in hierarchical nanosyntheses of branched ZnO crystallites

Here we report a site-specific sequential nucleation and growth route to the systematic building of hierarchical, complex, and oriented ZnO micro/nanostructures in solution nanosynthesis. Structures and morphologies of the products were confirmed by results from X-ray diffraction and scanning electron microscopy studies. The organic structure-directing agents (SDAs), diaminopropane and citrate, are found to play different roles in controlling the evolution of these new morphologies. Through the selective adsorptions of SDAs on different crystal facets of the primary ZnO rods, we have alternated the hierarchical growth of secondary and tertiary new complex nanostructures. Roles of the SDA concentration, nucleation time, and growth kinetics in the solution hierarchical ZnO nanosyntheses have all been systematically investigated.