New nanotube synthesis strategy--application of sodium nanotubes formed inside anodic aluminium oxide as a reactive template

Formation of Na nanotubes inside the channels of anodic aluminium oxide (AAO) membranes has been achieved by decomposing NaH thermally on AAO. The as-produced material, Na@AAO, is applied as a reactive template to prepare other tubular materials. Reacting Na@AAO with gaseous C6Cl6 generates carbon nanotubes (ca. 250 nm, wall thickness of 20 nm, tube length of 60 microm) inside the AAO channels. Highly aligned bundles of nearly amorphous carbon nanotubes are isolated after AAO is removed.     

Syntheses of rare-earth metal oxide nanotubes by the sol-gel method assisted with porous anodic aluminum oxide templates

In this paper, we report a versatile synthetic method of ordered rare-earth metal (RE) oxide nanotubes. RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction (XRD) have been employed to characterize the morphology and composition of the as-prepared nanotubes. It is found that as-prepared RE oxides evolve into bamboo-like nanotubes and entirely hollow nanotubes. A new possible formation mechanism of RE oxide nanotubes in the AAO channels is proposed. These high-quantity RE oxide nanotubes are expected to have promising applications in many areas such as luminescent materials, catalysts, magnets, etc.     

Preparation of Polyelectrolyte Nanotubes by a Pressure filter-template Technique Using Microporous Anodic Aluminum Oxide (AAO) as the Template

Polyelectrolyte nanotubes of poly(sodium 4‐styrene‐sulfonate) (PSS) with cationic poly(diallyl dimethyl ammonium chloride) (PDDA) (PSS/PDDA) were fabricated by a pressure‐filter‐template technique using microporous anodic aluminum oxide (AAO) as the template. UV‐Vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and infrared spectroscopy (FT‐IR) were applied to characterize the obtained PSS/PDDA nanotubes. The results have shown that the PSS/PDDA nanotubes exhibit an amorphous structure and have the outer diameter of 200 nm and length of 25 µm respectively, which are in good agreement with the dimensions of the AAO template pores. The wall thickness of the nanotubes may be controlled by the number of the self‐assembled layers. Formation of the nanotubes follows a layer‐by‐layer (LbL) mechanism due to the electrostatic interactions, where the SO^?₃ groups of PSS are first adsorbed on the Lewis acid sites of AAO template pores.     

Nanoporous carbon nanotubes synthesized through confined hydrogen-bonding self-assembly

We report a simple and direct synthetic method for the preparation of nanoporous carbon nanotubes with larger pores (>10 nm) on the tube wall. The method combines the use of anodic aluminum oxide (AAO) as a template for the tube diameter and block copolymer/carbohydrates self-assembly within thin films confined inside AAO pore channels to form nanopores. It involves coating the AAO inner pore channel surface with block copolymer (polystyrene-co-poly(vinylpyridine)) and carbohydrates in dimethylformamide (DMF) solution. Drying of DMF induced microphase separation of PS-PVP and formation of ordered PS and PVP/carbohydrate domains. Within the coating, the carbohydrates stay specifically only in the pyridine domains surrounding PS domains due to the hydrogen bonding between carbohydrates and pyridine blocks. After carbonization at high temperature (>460 degrees C) in argon, PS was removed, forming the nanopores and carbohydrates, and PVP was carbonized, forming the framework of nanoporous carbon tubes within AAO channels. Removal of AAO led to the formation of individual monodisperse nanoporous carbon nanotubes with a tube wall of approximately 16 nm. The ease with which these nanoporous carbon nanotubes can be fabricated, and the ability to tune tube nanostructures and surface chemistry through the choice of block copolymers used and carbonization temperature, should facilitate investigations of their scope for practical applications.     

Wettability transition induced transformation and entrapment of polymer nanostructures in cylindrical nanopores

We apply the concept of wettability transition to manipulate the morphology and entrapment of polymer nanostructures inside cylindrical nanopores of anodic aluminum oxide (AAO) membranes. When AAO/polystyrene (PS) hybrids, i.e., AAO/PS nanorods or AAO/PS nanotubes, are immersed into a polyethylene glycol (PEG) reservoir above the glass transition temperature of PS, a wettability transition from wetting to nonwetting of PS can be triggered due to the invasion of the more wettable PEG melt. The wettability transition enables us to develop a nondestructive method to entrap hemispherically capped nanorods inside nanopores. Moreover, we can obtain single nanorods with the desired aspect ratio by further dissolving the AAO template, in contrast to the drawbacks of nonuniformity or destructiveness from the conventional ultrasonication method. In the case of AAO/PS nanotubes, the wettability transition induced dewetting of PS nanotube walls results in the disconnection and entrapment of nonwetting PS domains (i.e., nanospheres, nanocapsules, or capped nanorods). Moreover, PEG is then washed to recover the pristine wettability of PS on the alumina surface; further annealing of the PS nanospheres inside AAO nanopores under vacuum can generate some unique nanostructures, particularly semicylindrical nanorods.     

化学修饰阳极氧化铝模板法合成小尺寸聚苯胺纳米线

利用表面活性剂对阳极氧化铝(AAO)模板进行化学修饰，发展了模板合成法，从而得到更小尺寸的聚苯胺纳米管、线.在表面活性剂十八烷基脂肪酸(R18)修饰下，在14 nm孔径的AAO模板中合成7 nm的纳米线.对不同表面活性剂的比较后发现,通过改变修饰表面活性剂上烷基链长可以对所制备的聚合物纳米管、线的直径进行调控.     

氧化铝模板上定向纳米碳管的快速生长及超声切短

在阳极氧化铝（AAO）模板上电沉积催化剂,快速生长了定向纳米碳管,纳米碳管以顶部生长模式生长.采用了超声的方法来切短露头于AAO模板的纳米碳管,增加纳米碳管膜的定向性.结果显示随着超声时间的增加,纳米碳管的定向性增加.位于纳米碳管膜顶部的催化剂在碳管切短的同时被去除,得到了顶部开口的纳米碳管.解释了纳米碳管被超声切短的机理.     

阳极氧化铝模板上热扩散法制备MoOx纳米阵列

采用简单的热扩散法, MoO3可在模板纳米孔道内有序生长, 经还原后获得MoO2和金属Mo纳米管／线阵列. 运用XRD、SEM、TEM、HRTEM等技术对产物进行了表征. 结果表明: 在70 nm孔径的阳极氧化铝模板上, H2/N2气氛下600 ℃时的还原产物为单晶MoO2; 而在50 nm的模板上, 同样条件的还原产物为MoO2微晶聚合体. 乙醇的加入能够大大改善产物的形貌. H2气氛, 650 ℃以上温度下进一步还原得到了金属Mo纳米管阵列.     

Free-standing, erect ultrahigh-aspect-ratio polymer nanopillar and nanotube ensembles

Free-standing polymer (poly(methyl methacrylate) or cyclic olefin copolymer) nanopillar and nanotube ensembles with previously unreported, ultrahigh aspect ratios (300 to >1600) were fabricated via anodic aluminum oxide (AAO) template-based methods that utilize a dilute, aqueous H3PO4 template etchant followed by freeze drying removal of the aqueous medium. Good replication of the AAO template by either solutions of the polymeric materials or molten polymer was achieved by using ultrasonic degassing and vacuum conditions. Classical surface wetting and viscoelastic fluid rheology theories were applied to explain the formation of polymer nanopillars and nanotubes in the aluminum oxide templates. The utilization of dilute H3PO4 for etching the AAO template and freeze-drying removal of the environmental liquid allows for the preparation of free-standing, erect, and ordered polymeric nanopillars or nanotubes that show much promise for use in biological microelectromechanical systems that target biological analyses.     

A facile synthesis of polypyrrole nanotubes using a template-mediated vapor deposition polymerization and the conversion to carbon nanotubes

Polypyrrole (PPy) nanotubes with highly uniform surface and tunable wall thickness were fabricated by one-step vapor deposition polymerization (VDP) using anodic aluminium oxide (AAO) template membranes, and transformed into carbon nanotubes through a carbonization process.     

Templated nanostructured PS‐b‐PEO nanotubes

With anodic aluminum oxide (AAO) membranes as wetting templates, nanotubes of the cylinder‐forming polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) copolymer were generated. The PS‐b‐PEO solution was introduced into the cylindrical nanopores of an AAO membrane by capillary force and polymeric nanotubes formed after solvent evaporation. Because of the water solubility of the cylindrical PEO microdomains and the orientation of the cylindrical PEO microdomains with respect to the nanotube walls, the nanotubes were permeable to aqueous media. PS‐b‐PEO nanotubes were also prepared on the interior walls of amorphous carbon nanotubes (a‐CNTs). Because of the unique water permeability of the PEO microdomains, an avenue for functionalizing the interior of the a‐CNTs is enabled. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2912–2917, 2007     

Atomic layer deposition of TiO2 nanotubes and its improved electrostatic capacitance

Titanium dioxide (TiO₂) nanotubes are fabricated into anodic aluminum oxide (AAO) membrane via atomic layer deposition (ALD). For the ALD of TiO₂, gaseous precursors, titanium (IV) isopropoxide and water are sequentially applied and chemically reacted with each other. A thickness of nanotubes is precisely controlled by the applied cycle numbers of ALD and the morphology of nanostructures is investigated by SEM and TEM. The amorphous property of TiO₂ nanostructures is revealed by XRD and the composition of nanotubes is measured by TEM–EDX. The impurity contents and binding structure of the nanostructures are analyzed by XPS. The electrostatic capacitance of TiO₂ nanotubes into AAO is 480 μF/cm² and it is about 3 times higher compared with AAO membrane (172 μF/cm²).     

基于层层自组装的CuTsPc/DPDCH纳米管的制备

在阳极多孔氧化铝模板中利用层层自组装技术制备出了高度有序的聚电解质磺化酞菁铜(CuTsPc)/4,4′-联吡啶盐酸盐(DPDCH)纳米管, 并对其组装过程用UV-Vis, XRD和FT-IR进行了分析, 纳米管的微观形貌通过SEM和TEM进行表征. 结果表明, 第一层 CuTsPc和第二层DPDCH在AAO模板上的沉积平衡时间均约为60 min, 沉积过程主要有三个阶段: 模板孔外的吸附过程、孔内扩散控制的沉积过程和孔内表面沉积控制过程. CuTsPc主要以磺酸根吸附于AAO模板上. CuTsPc/DPDCH纳米管为非晶态体系. CuTsPc/DPDCH纳米管的外径和壁厚分别为200和20 nm, 外径受控于AAO模板的孔径, 壁厚与组装的层数有关, 利用此方法还可以制备其他带有相反电荷的有机小分子对纳米管或纳米线.     

Nanoparticle films as a conducting layer for anodic aluminum oxide template-assisted nanorod synthesis

A simple, inexpensive, and robust methodology was developed to fabricate conductive film substrates by mechanically packing nanoparticles (NPs) on one side of anodic aluminum oxide (AAO). Gold, silver NPs, and carbon nanotubes were used as building blocks in the synthesis of conductive film substrates, upon which perpendicular nanorod arrays and colloidal free-standing nanorods were easily constructed. Characterizations by field emission scanning electron microscopy (FE-SEM) and optical dark-field microscopy confirmed the validity of the conductive NP film substrates on the AAO template. This contribution could provide a convenient and low-cost means for the fabrication of various conductive substrates on AAO.     

用AFM研究阳极氧化铝的不稳定生长

用原子力显微镜(AFM)研究了多孔阳极氧化铝(AAO)模板的不稳定生长. 结果表明:AAO模板的不稳定生长导致了纳米孔道结构有序度的降低.在H₃PO₄溶液中生长的AAO模板孔道结构稳定性较差;而在H₂C₂O₄溶液中生长的AAO模板稳定性依赖于氧化电压和电流密度,在低电压和电流密度下稳定性较好,高电压和电流密度下稳定性较差. 充分利用这种不稳定生长特性,通过控制AAO模板的阳极氧化条件,可得到具有分枝孔道结构的特殊模板,这为利用模板法制备各种Y形或T形纳米线、管提供了新的发展空间.     

Electroplating of metal nanotubes and nanowires in a high aspect-ratio nanotemplate

Ordered metal (Co, Pt, and CoPt alloy) nanotube and nanowire structures were fabricated by a simple electroplating method in high aspect-ratio anodic aluminum oxide (AAO) membrane. The growth rate in pulse mode is always larger than that in constant-current mode, which represents that diffusion limitation exists in this electroplating condition. It is also found that the sputtered Au layer structure could influence the electroplating. Traditional nanowires could be fabricated in the template with a uniform Au layer as conducting contact. In case of unblocked AAO membrane, metal electroplating begins from the Au particles which were attached inside the holes during the sputtering step and produces metal nanotubes. Pt and CoPt nanotubes could be easily prepared by this method and might be applied as catalyst and magnetic material.     

Synthesis of Various Metal/TiO2 Core/shell Nanorod Arrays

We present a general approach to fabricate metal/TiO₂ core/shell nanorod structures by two-step electrodeposition. Firstly, TiO₂ nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of thenanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO₂ nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.     

A novel carbon nanotube structure formed in ultra-long nanochannels of anodic aluminum oxide templates

We report the fabrication of a novel carbon structure consisting of uniform carbon nanotubes formed in the nanochannels of anodic aluminum oxide (AAO) templates, with the surface side open and connected by a uniform carbon sheet. The uniformity of the fabricated CNT arrays, plus the carbon film on the AAO surface interconnecting the open ends of all CNTs, constitute the major characteristics unique to our carbon structures. Some potential applications of such structures are noted.     

N,N-双(α-萘基-苯基)-4,4′-联苯二胺纳米管的制备及其光谱行为

利用多孔氧化铝作模板采用熔融法成功制备了一种定向有序排列的有机小分子 (NPB)纳米管 ,并用场发射扫描电镜 (FESEM)、X射线能量损失谱 (EDX)、透射电子显微镜 (TEM)和荧光显微镜对其进行了表征 .发现该纳米管具有整齐的形貌和规整的尺寸 .进一步的研究表明 ,多孔氧化铝模板的亲油亲水处理对能否成功地大量获得纳米管起到非常重要的作用 .值得注意的是 ,在对不同尺寸纳米管材荧光光谱的测定中 ,可明确观察到材料光学性质的尺寸依赖性 .     

Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations

In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.