阳极氧化TiO_2纳米线生长研究

采用NH4F-乙二醇-H2O溶液体系的电化学阳极氧化法,在金属钛基板上形成厚度为0.9~36μm的TiO2纳米管阵列。研究了阳极氧化电压、氧化时间及电解液的组成对TiO2纳米管阵列结构的影响。结果表明,当醇水体积比为39∶1时,60V电压下氧化2h,TiO2纳米管顶部的氧化层在缺陷处发生二次击穿溶解,产生自组装的孔核,场助溶解驱动力使纳米管顶部在孔核处沿管轴向垂直劈裂,形成直径20nm、长度可达几微米的TiO2纳米线。     

From cobalt nitrate carbonate hydroxide hydrate nanowires to porous Co(3)O(4) nanorods for high performance lithium-ion battery electrodes

We have developed a simple approach for the large-scale synthesis of cobalt nitrate carbonate hydroxide hydrate (Co(CO(3))(0.35)(NO(3))(0.2)(OH)(1.1)·1.74H(2)O) nanowires via the hydrothermal process using sodium hydroxide and formaldehyde as mineralizers at 120?°C. The porous Co(3)O(4) nanorods 10-30?nm in diameter and hundreds of nanometres in length have been fabricated from the above-mentioned multicomponent nanowires by calcination at 400?°C. The morphology and structure of cobalt nitrate carbonate hydroxide hydrate nanowires and Co(3)O(4) nanorods have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and x-ray powder diffraction (XRD). Moreover, the porous Co(3)O(4) nanorods have been applied in the negative electrode materials for lithium ion batteries, which exhibit high electrochemical performance.     

Synthesis of gold nanorods and nanowires by a microwave–polyol method

HAuCl₄ was reduced by ethylene glycol, in the presence of polyvinylpyrrolidone (PVP) under microwave (MW) heating in a continuous wave (CW) mode for 2 min. Dominant products were polygonal nanoplates and close-to-spherical nanoparticles of gold. In addition, small amounts of single crystalline gold nanorods and nanowires (0.5–3% of total number of products) with diameters of 20–100 nm and lengths of 0.6–5 μm were produced. The diameter and length of gold nanorods and nanowires could be controlled by changing the HAuCl₄·4H₂O/PVP ratio. The formation mechanism of anisotropic gold nanostructures was discussed.     

Synthesis and field emission characterization of titanium nitride nanowires

Single crystalline titanium nitride nanowires have been successfully synthesized through a chloride-assisted carbon thermal reduction method using the active carbon, TiO2 and NaCl powders as precursors and cobalt nanoparticles as catalyst. The products were characterized by X-ray diffraction, electron microscopy, and energy-dispersive X-ray spectroscopy. The TiN nanowires possess a cubic structure with typical diameter of 20-60 nm and length up to microns. The field emission property of the TiN nanowires has been characterized for the first time, which follows the conventional Fowler-Nordheim behavior and shows the low turn-on field of 7.1 V microm-1 and good emission stability, indicating the potential applications. The formation mechanism of the TiN nanowires has also been discussed.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

Synthesis of neodymium hydroxide nanotubes and nanorods by soft chemical process

A facile soft chemical approach using cetyltrimethylammonium bromide (CTAB) as template is successfully designed for synthesis of neodymium hydroxide nanotubes. These nanotubes have an average outer diameter around 20 nm, inner diameter around 2 nm, and length ranging from 100 to 120 nm, high BET surface area of 495.71 m(2) g(-1). We also find that neodymium hydroxide nanorods would be obtained when CTAB absented in reaction system. The Nd(OH)3 nanorods might act as precursors that are converted into Nd2O3 nanorods through dehydration at 550 degrees C. The nanorods could exhibit upconversion emission characteristic under excitation of 591 nm at room temperature.     

Standing [111] gold nanotube to nanorod arrays via template growth

Standing [111]-oriented crystalline gold nanotube (AuNT) and nanorod (AuNR) arrays using electrochemical deposition through template growth are reported. Segments of single crystal and bamboo-like crystalline AuNR arrays with growing direction of [111], having a diameter of 100-150?nm and a length of 10?μm, standing perpendicular to Ti metal foil substrates, are synthesized. The as-synthesized AuNTs and AuNRs are characterized by powder and five circle x-ray diffractometry, UV-visible molecular absorption spectrometry, field emission scanning electron microscopy, and transmission electron microscopy. AuNRs and AuNTs are formed by starting with a tube and the wall of the tube gets progressively thicker and eventually sealed up to form nanorods. Optical absorption at 548 and 578?nm wavelength for gold nanotubes and nanorods, respectively, caused by the transverse (width) mode is identified.     

Co掺杂的钛酸盐和TiO2纳米棒的磁性及光学性能

利用水热合成法,以TiO2(锐钛矿)粉末、钴盐为原料,在NaOH溶液中,180℃水热合成了Co掺杂的钛酸盐纳米棒.将Co掺杂的钛酸盐纳米棒在700℃氩气氛下烧结2 h转化为锐钛矿结构Co掺杂TiO2纳米棒.利用x射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外一可见分光光度计和超导量子干涉磁强计(SQUID)等对Co掺杂的钛酸盐和Ti0,纳米棒的微结构、形貌和性能进行了表征.研究结果表明,Co掺杂的钛酸盐和未掺杂的纯钛酸盐H2Ti3O7具有相同的层状结构,在样品中未监测到Co杂质(如钴的氧化物和氢氧化物)的峰.Co掺杂的钛酸盐纳米棒表面光滑,直径大约为90 nm～120 nm,长度约1 μm,co的掺杂对纳米棒形貌没有明显影响.Co掺杂后的钛酸盐纳米棒与未掺杂的钛酸盐纳米棒相比,其紫外-可见吸收光谱的吸收峰明显红移,带宽变窄.未掺杂的纯钛酸盐纳米棒的带宽为3.2 eV,与TiO2相同;Co掺杂的钛酸盐纳米棒的带宽为2.6 eV,明显变窄.同时,Co掺杂的钛酸盐和TjO2纳米棒在300 K均具有铁磁性,且其磁化强度大小基本一致,矫顽力也相同.     

Nanorods of copper and nickel oxalates synthesized by the reverse micellar route

Nanorods of nickel and copper oxalate have been synthesized by the reverse micellar route. Powder X-ray diffraction studies and thermo gravimetric analysis confirms the formation of monophasic NiC2O4 x 2H2O and CuC2O4 x H2O. Transmission electron microscopy shows that the as prepared nanorods of nickel and copper have diameter of 250 nm and 130 nm while the length is of the order of 2.5 microm and 480 nm respectively. The aspect ratio of the nanorods could be modified by changing the solvent. The nickel oxalate nanorods appear very smooth with uniform length while the copper oxalate nanorods appear to be corrugated. Nickel oxalate dihydrate nanorods show an antiferromagnetic transition at T(N) = 34 K while the copper based nanorods show temperature independent paramagnetism.     

Single‐Crystalline Barium Titanate Nanowires

Single‐crystalline barium titanate nanowires are synthesized using a solution‐based method, and their ferroelectric properties are investigated by scanning probe microscopy. Pristine nanowires have diameters ranging from 5 to 70 nm and lengths exceeding 10 μm, and they possess perovskite structures with a principal axis aligned along the wire axis. Scanning probe microscopy investigations show that local non‐volatile electric polarization can be reproducibly induced and manipulated on nanowires as small as 10 nm in diameter.     

Fabrication of micrometer-scale spherical titanate nanotube assemblies with high specific surface area

Three-dimensional (3D) micrometer-scale spherical titanate nanotube assemblies have been successfully synthesized via hydrothermal synthesis from Ti powders. The obtained titanate nanotube assemblies have a diameter of around 4-7 µm. The titanate nanotubes have an outer diameter of around 9-10 nm, an inner diameter around 3-4 nm and a length of several micrometers. A proposed two-stage growth mechanism was applied to explain the formation process of these titanate nanotube assemblies. We have also demonstrated that these titanate assemblies have higher specific surface area and larger adsorption capacity than that of titanate nanotubes. And they could possibly be further used in photocatalysts, separation technologies, energy-storage technologies and so on.     

Filling double-walled carbon nanotubes with WO3 and W nanowires via confined chemical reactions

Carbon nanotubes filled with metals and semiconductors have been regarded as one of the most promising materials for nanodevices. Here, we demonstrate a simple and effective method to produce tungsten trioxide (WO3) and tungsten (W) nanowires with diameters of below 4 nm inside double-walled carbon nanotubes (DWCNTs). First, the precursors, i.e., phosphotungstic acid (HPW, H3PW12O40) molecules, are successfully introduced into DWCNTs. Subsequent decomposition and reduction lead to the formation of WO3 and W nanowires inside DWCNTs. The products were carefully characterized by high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. FTIR spectra provide a direct proof that the HPW molecules enter the DWCNTs as an ionic state, i.e., PW12O40(3-) and H+, instead of the molecular state. HRTEM analysis shows that the diameter of the WO3 nanowires inside DWCNTs is 1.1-2.4 nm with the average length of 16-18 nm, and that for W nanowires is 1.2-3.4 nm with the average length of 15-17 nm. Meanwhile, DWCNTs are doped by the encapsulated WO3 and W nanowires. Tangential band shift in Raman spectra revealed the charge transfer between the nanowires and carbon nanotubes.     

Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Guided self-assembly of nanostructured titanium oxide

A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO(x) nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO(x) nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO(x) nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO(x) nanorods with rough surfaces are formed by the self-assembly of TiO(x) nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO(x) nanorods shows stronger ER properties than that of the other nanostructured TiO(x) particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.     

Formation and characterization of nanotubes of La(OH)(3) obtained using porous alumina membranes

An electrodeposition process is used to synthesize nanotubes of a lanthanum-containing phase, employing porous alumina membranes as templates. This method should lead to the formation of La(OH)(3) nanowires, according to the previous results presented by Bocchetta et al (2007 Electrochem. Commun. 9 683-8), which can be decomposed to La(2)O(3), as the latter shows more interest for different applications. The results obtained by means of different electron microscopy techniques indicate that this method leads to the formation of nanotubes of about 200?nm in diameter and 30-40?μm in length, instead of the nanowires proposed in the literature. Additionally, the chemical characterization demonstrates that the material synthesized is composed of lanthanum hydroxycarbonate. The presence of carbonates is found to be crucial in determining the conditions for the preparation of La(2)O(3) from the nanotubes here obtained.     

Structural and magnetic properties of Zn1-xcoxO nanorods prepared by microwave irradiation technique

We have successfully synthesized large-scale aggregative flowerlike Zn1-xCo(x)O (0.0 < or = x < or = 0.07) nanostructures, consisting of many branches of nanorods at different orientations with diameter within 100-150 nm (tip diameter approximately 50 nm) and length of approximately 1 microm. The rods were prepared using Zinc nitrate, cobalt nitrate and KOH in 180 Watt microwave radiation for short time interval. The synthesized nanorods were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), field emission transmission electron microscopy (FETEM) and DC magnetization measurements. XRD and TEM results indicate that the novel flowerlike nanostructures are hexagonal with wurtzite structure and Co ions were successfully incorporated into the lattice position of Zn ions in ZnO matrix. The selected area electron diffraction (SAED) pattern reveals that the nanorods are single crystal in nature and preferentially grow along [0 0 1] direction. Magnetic studies show that Zn1-xCo(x)O nanorods exhibit room temperature ferromagnetism. This novel nanostructure could be a promising candidate for a variety of future spintronic applications.     

Effects of sodium content of titanate nanotubes on lithium battery performance

Titanate nanotubes were prepared by hydrothermal process of powder for the application to the anode of lithium batteries. After the synthesis of titanate nanotubes by the chemical treatment with 10 M NaOH solution, the quantity of sodium remnant was controlled by the HCl washing solutions of different pH of 1, 4, 7, 10 and 13. The prepared titanate nanotubes had outer and inner diameter of 9 nm and 6 nm, and the interlayer spacing of about 1 nm. The amount of sodium remnant was investigated using Inductively Coupled Plasma (ICP) Atomic Emission Spectrometer, and the variation of structure and morphology with the contents of the sodium was studied by X-ray diffraction (XRD), Thermogravimetric Analysis (TGA), Field Emission Scanning Electron Microscopy (FE-SEM) and High Resolution Transmission Electron Microscopy (HR-TEM). Coin cells composed of (Titanate nanotubes//1 M LiPF6-EC/DEC//Li metal) were prepared for studying the basic charging-discharging behavior and electrochemical properties of the prepared titanate nanotubes with controlled sodium contents. The effects of the remnant sodium content on the microstructures, morphology and electrochemical properties of titanate nanotubes will be discussed.     

Synthesis and characterization of LnPO4 x nH2O (Ln = La, Ce, Gd, Tb, Dy) nanorods and nanowires

Aqueous precipitation method has been used to synthesize lanthanide orthophosphates LnPO4 x nH2O (Ln = La, Ce, Gd, Tb, Dy) with high purity and yield. It has been shown by XRD, TGA, and FTIR characterization that the as-synthesized samples are the LnPO4 hydrates (LnPO4 x nH2O) with hexagonal rhabdophane-type structure. The X-ray diffraction peaks and absorption of PO4(3-) groups show a systematic shift from LaPO4 x nH2O to DyPO4 x nH2O due to the effect of lanthanide ionic contraction. The value of n in LnPO4 x nH2O depends on the lanthanide element and synthetic condition. Field-emission scanning electron microscopy observations show the morphology of as-synthesized samples, which consist entirely of nanorods/nanowires with diameters of 30-100 nm and lengths ranging from several hundreds of nanometers to several micrometers. The anisotropic growth of crystals should be responsible for the formation of nanorods/nanowires, which is related to the hexagonal crystal structure.     

Thermal Growth and Nanomagnetism of the Quasi-one Dimensional Iron Oxide

Quasi-one dimensional iron oxide nanowires with flat needle shape were synthesized on the iron powders by a rather simple catalyst-free thermal oxidation process in ambient atmosphere. The characterization by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman and high-resolution transmission electron microscopy (HRTEM) revealed that these nanostructures are single crystalline α-Fe2O3. The various dimensions with 40-170 nm in width and 1-8 μm in length were obtained by tuning the growth temperature from 280 to 480℃. A surface diffusion mechanism was proposed to account for the growth of quasi-one dimensional nanostructure. The typical α-Fe2O3 nanowires synthesized at 430℃ had a reduced Morin temperature TM of 131 K in comparison with their bulk counterpart. The coercivitis Hc of these nanowires are 321 and 65 Oe at 5 and 300 K, respectively. The temperature of synthesis also has important effects on the magnetic properties of these nanowires.