模板组装Fe纳米线阵列及其微结构

铝在硫酸溶液中经直流阳极氧化,得到多孔铝阳极氧化膜(AAO). 以AAO膜为模板,通过交流电沉积的方法,在AAO模板孔内成功组装了Fe纳米线.TEM分析表明,Fe纳米线的长度约为2.5 μm,其长度分布十分均匀；粗细均匀,直径约为25 nm. XRD实验分析证实,所制备的Fe纳米线为α-Fe.选区电子衍射（SAED）实验分析表明,α-Fe纳米线具有单晶结构.     

Synthesis of ordered Al nanowire arrays

Ordered Al nanowire arrays with the same nanowire density but the diameters decrease radially embedded in one piece of anodic alumina membranes were successfully fabricated by two-step synthesis: electrodeposition of Zn and replacement in AlCl₃ solution. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected-area electron diffraction techniques were used to characterize the Al nanowires obtained. SEM and TEM images taken from the different areas of Al nanowire arrays show that we can control the growth of aligned Al nanowires with different diameters in a single process at the same time. The investigation results not only have potential applications in photoelectric devices but also open up a new method for fabricating nano-scale materials.     

离子液体中电沉积制备钴纳米线阵列

Porous anodic alumina (PAA) was used as a template to prepare Co nanowires array from 1-ethyl-3-methylimidazolium chloride ionic liquid by direct current method. The surface morphology of porous anodic alumina template was observed by field emission-scanning tunneling microscopy (FE-SEM) before and after the electrodeposition of Co nanowires. The electrodeposition of Co nanowires was characterized by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). TEM results indicate that the Co nanowire surface is coarse and porous when aqueous solution was used as electrolyte， and the Co nanowire deposited from the ionic liquid is uniform and smooth. XRD results show that the electrodeposition of Co is a mixture of crystal and microcrystal phase.     

On-wire conversion chemistry: engineering solid-state complexity into striped metal nanowires using solution chemistry reactions

Multisegment template-grown metal nanowires have become important one-dimensional materials for a variety of applications in chemistry, physics, engineering, biology, and medicine. Segmented nanowires are traditionally fabricated in anodic alumina membranes using electrodeposition, and this technique is applicable to a range of metals, alloys, and semiconductors. Here we report an alternative and simple solution chemistry strategy for incorporating multimetal components of controllable length and composition into template-grown metal nanowires. By reacting membrane-confined nanowires with metal salt solutions under reducing conditions, site-specific diffusion occurs to convert one or both nanowire tips or the entire nanowire into a variety of multimetal phases. Platinum-based intermetallic compounds were chosen as targets for demonstrating the feasibility of the on-wire conversion chemistry.     

Growth of silver nanowires by an unconventional electrodeposition without template

We describe an unconventional electrochemistry approach to the preparation of silver nanowires. By the electrodeposition in the dilute solution without supporting electrolyte, silver nanowires with diameter 10–50 nm and length up to several μm have been synthesized. It was found that the absence of the supporting electrolyte played a key role in the formation of silver nanowires, and the products from the solution without supporting electrolytes were very different from those with supporting electrolytes. A possible mechanism concerning the transportation of silver ions by electro-migration and the diffusion was proposed.     

Band-gap engineering of semiconductor nanowires through composition modulation

Alloyed ternary CdS(1-x)Se(x) nanowires were synthesized by template-assisted electrodeposition, in which the ratio of S to Se in the nanowires was controlled by adjusting the relative amounts of the starting materials. Higher-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) showed that the alloyed ternary CdS(1-x)Se(x) nanowires are highly crystalline, and no phase-separated Cd was observed in these nanowires. Optical measurements indicated that the band-gap engineering can be realized in these CdS(1-x)Se(x) nanowires through modulating the composition of S and Se. With broadly tunable optical and electrical properties, these alloyed nanowires could be used in color-tuned nanolasers, biological labels, and nanoelectronics.     

Generation and growth mechanism of metal (Fe, Co, Ni) nanotube arrays.

Nanotubes composed of layered or nonlayered materials have been synthesized through various methods, among which template-based electrodeposition technology provides a versatile technique for synthesizing one-dimensional nanostructured materials. However, the growth mechanism of nanotubes using the template method is seldom clarified. Herein, we present the systematic preparation of metal nanotube arrays and put forward the growth mechanism, termed current-directed tubular growth (CDTG), for template-based electrodeposition. There are competitive growth rates for metal atoms entering the crystal lattice, that is, v( parallel) (growth rate parallel to current direction) and v( perpendicular) (growth rate perpendicular to current direction). Metal nanotubes can be obtained at v( parallel)>v( perpendicular), while nanowires can be obtained at v( parallel) approximately v( perpendicular). The as-synthesized metal (Fe, Co, Ni) nanotubes are constructed from nonlayered materials, which are of body-centered cubic iron structure, hexagonal close packed cobalt structure, and face-centered cubic nickel structure, respectively. The CDTG mechanism is expected to have applications in designing and synthesizing other metal nanotubes and even compound nanotubes via template-based electrodeposition technology.     

Novel electrodeposition behavior of Ni on porous anodic alumina templates without a conductive interlayer

During template-assisted electrodeposition, single-crystalline metallic nanowires could be obtained only when the overpotential is low. However, an unusual electrodeposition behavior on the PAA/Si substrate without a conductive interlayer between the template and Si is described in the present study. Through the electrical breakdown of the template, Ni nanodots, nanowires and nanotubes could be obtained by only changing the electrodeposition voltage on the same substrate. The mechanisms leading to the formation of various nanostructures are described in detail and compared with those for the conventional template-assisted electrodeposition process. The electrodeposition first occurred on the pore wall instead of from the underlying substrate, leading to the formation of some Ni nanotubes at a more negative voltage. Besides, single-crystalline Ni nanowires could also be formed even when the electrodeposition voltage was as negative as -40 V, indicating that the formation of single-crystalline metallic nanowires under a large overpotential is possible.     

Dielectrophoretic alignment of metal and metal oxide nanowires and nanotubes: a universal set of parameters for bridging prepatterned microelectrodes

Nanowires and nanotubes were synthesized from metals and metal oxides using templated cathodic electrodeposition. With templated electrodeposition, small structures are electrodeposited using a template that is the inverse of the final desired shape. Dielectrophoresis was used for the alignment of the as-formed nanowires and nanotubes between prepatterned electrodes. For reproducible nanowire alignment, a universal set of dielectrophoresis parameters to align any arbitrary nanowire material was determined. The parameters include peak-to-peak potential and frequency, thickness of the silicon oxide layer, grounding of the silicon substrate, and nature of the solvent medium used. It involves applying a field with a frequency >10(5) Hz, an insulating silicon oxide layer with a thickness of 2.5 μm or more, grounding of the underlying silicon substrate, and the use of a solvent medium with a low dielectric constant. In our experiments, we obtained good results by using a peak-to-peak potential of 2.1 V at a frequency of 1.2 × 10(5) Hz. Furthermore, an indirect alignment technique is proposed that prevents short circuiting of nanowires after contacting both electrodes. After alignment, a considerably lower resistivity was found for ZnO nanowires made by templated electrodeposition (2.2-3.4 × 10(-3) Ωm) compared to ZnO nanorods synthesized by electrodeposition (10 Ωm) or molecular beam epitaxy (MBE) (500 Ωm).     

Chitosan-mediated and spatially selective electrodeposition of nanoscale particles

Nanoscale particles offer a variety of interesting properties, and there is growing interest in their assembly into higher ordered structures. We report that the pH-responsive aminopolysaccharide chitosan can mediate the electrodeposition of model nanoparticles. Chitosan is known to electrodeposit at the cathode surface in response to a high localized pH. To demonstrate that chitosan can mediate nanoparticle deposition, we suspended fluorescently labeled latex nanoparticles (100 nm diameter spheres) in a chitosan solution (1%) and performed electrodeposition (0.05 mA/cm2 for several minutes). Results demonstrate that chitosan is required for nanoparticle electrodeposition; chitosan confers spatial selectivity to electrodeposition; and nanoparticles distribute throughout the electrodeposited chitosan film. Additionally, we observed that the deposited films reversibly swell upon rehydration. This work indicates that chitosan provides a simple means to assemble nanoparticles at addressable locations and provides further evidence that stimuli-responsive biological materials may facilitate fabrication at the microscale.     

The effect of dissolved oxygen on the rate of pulsed electrodeposition of copper and bismuth nanowires under the conditions of template synthesis

The effect of dissolved oxygen on the electrodeposition under the conditions of template synthesis (the fabrication of arrays of meso- and nanowires by the electrochemical deposition into the aluminum oxide membranes with pore diameter of 20 to 200 nm, which were coated with a conducting metal on one side) is studied. It is shown that, when the deposition rate is controlled by mass transfer, it can be raised by using the pulsed electrolysis due to additional delivery of electroactive substance during a pause. However, the method is limited by the material corrosion during the pause (this is shown by the examples of copper deposition from the pyrophosphate solution and bismuth deposition from the nitrate solution). By the example of copper deposition from the pyrophosphate electrolyte, it is shown that corrosion proceeds with oxygen depolarization. The electrodeposition in the inert gas atmosphere gives the possibility to raise the deposition rate by several times, and the rate becomes close to the Faradaic one.     

Free-standing aluminium nanowire architectures made in an ionic liquid

We report on the electrochemical synthesis of free‐standing aluminium nanowire architectures through a template‐assisted electrodeposition technique. For this purpose, nuclear track‐etched polycarbonate membranes were employed as templates. One side of the template was sputtered with a thin gold film to serve as a working electrode. Subsequently the nanowires were made in the ionic liquid 1‐ethyl‐3‐methylimidazolium chloride ([EMIm]Cl)/AlCl₃ (40/60 mol %) under potentiostatic conditions. Two different electrodeposition procedures were employed to fabricate strongly adherent Al nanowire structures on an electrodeposited Al layer. In the first procedure, electrodeposition simultaneously occurs along the pores of the template and on the Au‐sputtered side of the template. In the second procedure, electrodeposition takes place in two different steps: first a thick supporting film of Al is deposited on the sputtered side of the membrane and second Al nanowires are grown within the pores. After chemical dissolution of the membrane in dichloromethane, an aluminium foil of a controlled thickness with a three‐dimensional nanowire structure on one side was obtained. Different nanowire architectures, such as free‐standing nanowires, vertically aligned tree‐shaped arrays, and bunched nanowire films, were obtained. Such nanowire architectures are of particular interest for applications in Li‐ion micro‐batteries.     

模板法制备枝状Pt纳米线

一维纳米材料的制备是近年来纳米材料的研究热点. 利用具有纳米尺度的孔洞阵列模板沉积各种材料构筑纳米线的方法具有制备简便和成本较低等优点[1,2]. 常用的模板有多孔阳极氧化铝(AAO)、多孔硅和聚合物等, 其中AAO模板具有耐高温, 绝缘性好, 孔洞分布均匀, 孔径、孔深大小可控等特点, 是模板法研究的热点. 通过模板法电化学沉积制备各种金属纳米线已有很多报道[3～8], 本研究小组也曾报道了模板法电化学沉积Au等纳米线的制备及性质[9～12], 但用该方法制备的金属纳米线都为单一的线状结构. 组成当代大规模集成电路的基本器件一般具有3个或3个以上的电极. 单一的线状结构纳米线, 不能满足纳米电子学对纳米材料和纳米器件性能研究的需要. 在纳米器件的特性研究和探索中, 枝状或Y形纳米结的制备有重要的意义, 它是纳米器件从理论到实用化的必备条件. Sui等[13]用模板法成功制备了枝状碳纳米管, 但用AAO模板制备枝状金属纳米线的研究至今还未见报道. 本文通过控制铝片的阳极氧化条件, 先制备出具有分枝状孔洞结构的AAO模板, 再用电化学法沉积金属Pt, 实现了枝状Pt纳米线的可控生长. 这对其它金属枝状纳米线的制备以及进一步掺杂、构筑纳米原型器件等具有显著的实用价值.     

Preparation of cobalt hexacyanoferrate nanowires using carbon nanotubes as templates

A simple and convenient method for preparation of cobalt hexacyanoferrate (CoHCF) nanowires by electrodeposition was reported. Multiwall carbon nanotubes (MWNTs) were used as templates to fabricate CoHCF nanowires. MWNTs could affect the size of CoHCF nanoparticles and made them grow on the sidewalls of carbon nanotubes during the process of electrodeposition. Thus CoHCF nanowires could be obtained by this method. Field-emission scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize these nanowires. These results showed the CoHCF nanowires could be easily and successfully obtained and it gave a novel approach to prepare inorganic nanowires.     

Magnetic nanowires via template electrodeposition

The magnetic NiFe_x nanowires were prepared via template-guided electrodeposition. Anodized nanoporous aluminum was used as a template. The pore density and dimensions of alumina templates can be controlled by anodization conditions. Magnetic nanorods (or nanowires) with various aspect ratios were prepared by controlling the electrodeposition time. SEM and TEM micrographs revealed the wire and rod shape morphologies with 50 nm in diameter and 1.5 ~ 10 μm in length. Elemental analysis and ESCA studies suggested that NiFe₃ magnetic alloy was formed. The X-ray diffraction pattern indicates that all the nanowires are stabilized in a BCC structure with a [1 1 0] texture oriented along the long axis of the nanowires. The magnetic measurement showed no hysteresis loops for the whole aspect ratios of the nanowires. Nevertheless, the magnetization is more temperature sensitive for nanowires with lower aspect ratio. This is caused by the fact that the easy magnetization axis is always parallel to the long axis of the nanowires.     

Template electrodeposition of metals. Review

The works devoted to the electrodeposition of metals, alloys, and semiconductors onto the substrates through the templates of various non-conducting materials with pores of various shapes and sizes are reviewed. The composite materials, nanowires, metal foams, and the parts with nanostructured surface obtained by this method are promising materials for the electrocatalysis, electroanalysis of media, development of various sensors, modern miniature magnetic memory devices, optoelectronics, power sources, etc.     

Aqueous-solution growth of GaP and InP nanowires: a general route to phosphide, oxide, sulfide, and tungstate nanowires

A general synthetic route has been developed for the growth of metal phosphide, oxide, sulfide, and tungstate nanowires in aqueous solution. In detail, cetyltrimethylammonium cations (CTA(+)) can be combined with anionic inorganic species along a co-condensation mechanism to form lamellar inorganic-surfactant intercalated mesostructures, which serve as both microreactors and reactants for the growth of nanowires. For example, GaP, InP, gamma-MnO(2), ZnO, SnS(2), ZnS, CdWO(4), and ZnWO(4) nanowires have been grown by this route. To the best of our knowledge, this is the first time that the synthesis of GaP and InP nanowires in aqueous solution has been achieved. This strategy is expected to extend to grow nanowires of other materials in solution or by vapor transport routes, since the nanowire growth of any inorganic materials can be realized by selecting an appropriate reaction and its corresponding lamellar inorganic-surfactant precursors.     

Hierarchical Nanowires Synthesized by Supramolecular Stepwise Polymerization

The self‐organization of pre‐assembled aggregates is an efficient stepwise strategy for fabricating nanostructures with a second level of hierarchy. Herein, we report that anisotropic spindle‐like micelles, self‐assembled from polypeptide graft copolymers with rigid backbones, can serve as ideal pre‐assembled subunits for constructing one‐dimensional materials with hierarchical structures. By adding organic solvents and dialyzing against water, reactive points can be generated at the ends of the spindle‐like micelles, which subsequently drive the anisotropic micelles to grow as rods in a chain and eventually self‐assemble into hierarchical nanowires in a stepwise manner. The second self‐assembly step is a hierarchical process that resembles step polymerization. Hierarchical structures can be precisely synthesized by this new type of polymerization. These nanostructures can be tailored by the activity of the reactive points, which depends on the nature of the solvent and the molecular architecture.     

Synthesis of hybrid nanowire arrays and their application as high power supercapacitor electrodes

Arrays of multi-segmented hybrid nanostructures of carbon nanotube and gold nanowires have been synthesized using a combination of chemical vapour deposition and electrodeposition methods and we further demonstrate that ultra-high power electrochemical double layer capacitors can be engineered using these hybrid nanowires, resulting in very high power densities.     

Architectural control syntheses of CdS and CdSe nanoflowers, branched nanowires, and nanotrees via a solvothermal approach in a mixed solution and their photocatalytic property

Wurtzite CdS and CdSe nanostructures with complex morphologies such as urchin-like CdS nanoflowers, branched nanowires, and fractal nanotrees can be produced via a facile solvothermal approach in a mixed solution made of diethylenetriamine (DETA) and deionized water (DIW). The morphologies of CdS and CdSe nanocrystals can be easily controlled via tuning the volume ratio of DETA and DIW. Urchin-like CdS nanoflowers made of CdS nanorods are in a form of highly ordered hierarchical structures, while the nanowires are branched nanowires, and the fractal CdS nanotrees are a buildup of branched nanopines. The results demonstrated that solvothermal reaction in a mixed amine/water can access a variety of complex morphologies of semiconductor materials. The photocatalytic activity of CdS particles with different morphologies has been tested by the degradation of acid fuchsine under both UV and visible light, showing that the as-prepared branched CdS nanowires exhibit high photocatalytic activity for degradation of acid fuchsine.