Highly ordered self-organized TiO2 nanotube arrays prepared by a multi-step anodic oxidation process

Highly ordered TiO₂ nanotube arrays were prepared using a self-templating multi-step anodic oxidation process in a fluoride-containing electrolyte. The microstructures, chemical compositions, and phases of the self-organized TiO₂ nanotube arrays were analyzed by FESEM, XPS, and XRD, respectively. Hexagonal packing density in TiO₂ nanotube arrays significantly improved after the the multi-step anodic oxidation. The area densities of the hexagonal TiO₂ nanotube arrays increased approximately 3 times from the first to second step in the anodic oxidation steps process (4.9 μm⁻² to 16.4 μm⁻²), but there was no difference between the second and third step (16.4 μm⁻² to 16.0 μm⁻²). The as-anodized TiO₂ nanotube array had an amorphous structure and it transformed to an anatase phase during the annealing process at 450 °C for 1 h. The as-anodized TiO₂ nanotube arrays adsorbed the fluoride, hydrocarbon groups (CH), hydroxyl groups (OH, C-OH), and carboxyl groups (O = C-OH) on their surfaces.     

Characteristics of N-doped TiO2 nanotube arrays by N2-plasma for visible light-driven photocatalysis

N-doped TiO₂ nanotube arrays were prepared by electrochemical anode oxidation of Ti foil followed by treatment with N₂-plasma and subsequent annealed under Ar atmosphere. The morphologies, composition and optical properties of N-doped TiO₂ nanotube arrays were characterized using field-emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectrometer (XRD), Photoluminescence (PL) and UV-vis diffusion reflection spectroscopy (UV-vis DRS). Methylene blue (MB) solution was utilized as the degradation model to evaluate the photocatalytic activity of the samples under visible light irradiation. The results suggested N₂-plasma treatment created doping of nitrogen onto the surface of photoelectrodes successfully and the N-doped TiO₂ nanotube arrays display a significantly enhancement of the photocatalytic activity comparing with the pure TiO₂ nanotube arrays under the visible light irradiation.     

氧化参数对TiO_2纳米管结构及双室光电化学池产氢性能的影响

采用乙二醇电解液,在不同氧化电压、氧化时间条件下通过阳极氧化纯钛片制备了一系列TiO_2纳米管阵列薄膜。使用场发射扫描电镜(FESEM)表征TiO_2纳米管的表面、断面形貌,探讨氧化时间及氧化电压对纳米管生长速率的影响。同时通过电化学方法测试TiO_2纳米管的光电化学性能,以无外加电压下双室光电化学池中的产氢量考察其光催化活性。结果表明,相比延长氧化时间,提高氧化电压更容易获得高长/径比的TiO_2纳米管阵列,同时可显著提高TiO_2纳米管的光电流、光电转换效率及产氢量。     

Electrochemical stability of TiO2 nanotubes with different diameters in artificial saliva

Recently, titanium and titanium alloys with nanotube layers by anodizing process have gained great interests as surgical implant materials. In this present paper, their electrochemical stability of self-organized TiO₂ nanotubue layers prepared by anodization of pure Ti in 0.5 wt.% hydrofluoric acid has been investigated in simulated biological environment by use of open-circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The electrochemical testing results indicate that the nanotubular Ti with the diameter of TiO₂ nanotube lower than 86 nm shows a better corrosion resistance in artificial saliva than that of the mechanically polished Ti. Moreover, the electrochemical stability of Ti nanotubes 22 to 59 nm in diameter is improved but that of Ti nanotubes larger than 86 nm decreases. Besides, the corrosion attack of the nanotubular Ti is shown by the collapse of TiO₂ nanotubue layer. The results suggest that the electrochemical corrosion behavior of nanotubular Ti in artificial saliva is related to the diameter of the nanotubes and thickness of the barrier layer.     

TiO2纳米阵列超疏水膜的制备及耐腐蚀性能

采用阳极氧化法在纯钛表面制备TiO2纳米管阵列,使用六甲基二硅胺烷对TiO2纳米管阵列进行低表面能处理,得到超疏水表面．用接触角测量仪测定表面疏水性,采用SEM、EDS技术研究改性前后试样表面的形貌和元素组成,并利用极化曲线和电化学阻抗谱法研究了超疏水膜的耐腐蚀性能．结果表明,TiO2纳米管阵列经改性后超疏水效果明显,...     

Characterization of electronic properties of TiO2 nanotube films

By anodization of titanium, TiO₂ nanotube layers were grown that consist of arrays of individual tubes with a length of ≈2.5 μm, a diameter of ≈100 nm and a wall thickness of ≈15 nm. The electronic properties of TiO₂ nanotube layers were characterized using photoelectrochemical and impedance measurements. Photocurrents for as-anodized tubes are dominated by their amorphous state and a high number of defects. Conversion to anatase by annealing decreases the defect density drastically which results in an enhanced photocurrent.     

Rapid anodic oxidation of highly ordered TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays prepared by anodic oxidation have attracted increasing research interests due to their promising applications in many scientific areas. To the best of our knowledge, a factor limiting the application of TiO₂ nanotube arrays was their long sustaining reaction time by anodic oxidation, usually lasting 6-12 h and even longer when synthesizing thicker nanotubular layers. In the present paper, we reported for the first time a facile but effective approach to accelerate the anodic formation of TiO₂ nanotube arrays by proper addition of sodium carbonate (Na₂CO₃) into the anodization electrolyte. We adopted the 0.3 M NH₄F + 0.03 M Na₂CO₃ + EG (ethylene glycol) + 3.0 vol.% H₂O electrolyte and the average growth rate of the nanotubes achieved in our experiments could be accelerated to 1100 nm/min. The possible mechanism of the rapid electrochemical process was also presented.     

TiO2 nanotube-supported amorphous Ni-B electrode for electrocatalytic oxidation of methanol

Amorphous Ni-B/TiO₂ electrodes were successfully prepared by electroless plating. Highly ordered TiO₂ nanotube arrays fabricated by anodic oxidation were employed as substrate and loaded with Ni-B alloy by electroless plating. The phase formation, microstructures and catalytic activity of electrodes were investigated by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and electrochemistry analyzer, respectively. The results show that Ni-B/TiO₂ electrodes with an average particle size of 200 nm present a typical amorphous structure of Ni and B, and have high catalytic activity for methanol electrooxidation in alkaline medium. The peak current density in cyclic voltammetry (CV) curves reaches 360 mA cm⁻² in the solution with 0.5 mol L⁻¹ methanol, much higher than that of Ni-B/Ti electrode. With the methanol concentration increasing to 1.5 mol L⁻¹, the peak current density increases to 488 mA cm⁻², after which it remains almost constant. The Ni-B/TiO₂ electrodes are relatively stable according to catalytic lifetime test; the peak current density remains 72.1% of the original value after 1300 times cycles. The amorphous Ni-B/TiO₂ electrode should be a promising candidate for direct methanol fuel cell.     

Self-aligned TiO2 nanotube arrays produced by air-cathode as electrode

Air-cathodes were used to produce TiO₂ nanotube arrays. The effects of pH, voltage and degradation of air-cathode in tailoring the morphologies of TiO₂ nanotube arrays were investigated. Preliminary results show that TiO₂ nanotubes could be formed and are comparable to those produced by platinum electrodes under similar conditions. The lengths and diameters of TiO₂ nanotube arrays obtained are in the range of 1.0-2.2 μm and 40-150 nm, respectively. It is found that the rate of formation of the nanotubes is closely related to the pH of the solution. Air-cathodes are found to have relative low values of mass loss rates.     

Electrochemical synthesis,studies and modification of TiO<Subscript>2</Subscript> nanotubes

TiO₂ nanotubes (TiO₂ NTs) were synthesized using the electrochemical method in a 1 M H₂SO₄ + 0.15% HF electrolyte. The initial nanotubes have a diameter of 100 ± 10 nm (with the length of up to 150–200 nm) and a wall thickness of 20 ± 5 nm. Nanotube treatment at 400°C results in negligible changes in their structure compared to the initial samples. At 600°C, a change occurs in the nanotube structure and morphology, i.e., the amount decreases drastically; the diameter changes; and, as a consequence, the surface area value decreases. Changes in the structure lead to changes in the electrochemical properties, which is apparently related to a transition from the amorphous structure to anatase and rutile. It is shown that a reversible two-electron reaction, including hydrogen intercalation and Ti⁴⁺/Ti³⁺ oxidation/reduction in the potential range of (−0.6−0.4 V), occurs as a result of moderate thermal treatment. The possibility of the use and promising character of TiO₂ NTs as support for a nonplatinum catalyst based on cobalt tetra(p-methoxyphenyl)porphyrin are brought to light. The electrocatalytic activity of the synthesized catalyst per nominal CoTMPP mass in the reaction of O₂ reduction at E = 0.7 V is ≈25 A/g_CoTMPP, which is comparable to nonplatinum systems on a carbon support.     

Preparation of titanium dioxide nanotube arrays on titanium mesh by anodization in (NH4)2SO4/NH4F electrolyte

The self‐organized titanium dioxide (TiO₂) nanotube arrays on titanium mesh were prepared by electrochemical anodization with the neutral electrolyte containing ammonium sulfate and ammonium fluoride in a two‐electrode electrochemical cell. The effects of the fluoride ion concentration, the anodic potential, and the oxidation time on the formation of the titanium dioxide nanostructures on titanium mesh with complex geometry were investigated. The anodized titanium mesh was characterized by field emission scanning electron microscope and in situ high temperature X‐ray diffraction. The results show that the titanium dioxide nanotube arrays are grown in a radially outward direction around the titanium wire. The optimized anodization condition for preparing titanium dioxide nanotube arrays with superior architecture on the titanium mesh is 0.5 wt% of ammonium fluoride, 20 V of applied potential, and 20 min of oxidation time. The amorphous titanium dioxide nanotubes on titanium mesh turn to anatase phase at 400 °C and further to rutile phase at 650 °C.     

Influence of electrolyte and anodic potentials on morphology of titania nanotubes

The effects of electrolyte and applied potentials on TiO₂ nanotube morphologies were investigated. The specific surface area of the TiO₂ nanotubes was measured to be 57 m²/g for titania nanotubes formed in HF, and 147 m²/g formed in organic electrolyte, respectively. The results of adsorption-desorption isotherms agree with the morphology of TiO₂ nanotubes. The length and average diameter of nanotubes were influenced by electrolyte and anodic potentials. The multilayered TiO₂ nanotube arrays can be fabricated by changing the electrolyte composition during anodization.     

Au负载N掺杂TiO2纳米管阵列的制备及其性能

TiO₂ 纳米管阵列较大的禁带宽度是导致其光催化效率较低的重要原因,采用磁控溅射、阳极氧化以及气氛退火相结合的方法对 TNAs 改性后制备了 Au 负载 N 掺杂 TiO₂ 纳米管阵列(Au@ N-TNAs),然后以甲基橙为目标污染物, 进一步分析了 Au@ N-TNAs 在不同 Au 负载量时光降解效率的变化情况。 采用 SEM、XRD、TEM 和 X 射线光电子能谱 (XPS)等对 Au 和 N 在 Au@ N-TNAs 中的存在形式进行表征和分析,发现 Au 主要是负载在 TiO₂ 纳米管阵列上,而 N 元素则是以掺杂的方式进入 TiO₂ 纳米管阵列的晶格中。 此外,在光降解试验中发现通过 Au 负载与 N 掺杂相结合的方法对 TiO₂ 纳米管阵列进行复合改性后,TiO₂ 纳米管阵列的光催化效率得到显著提升,其中 20s-Au@ N-TNAs 具有最佳的光降解效率。 但 Ti-N 薄膜中间的 Au 层太厚时会影响阳极氧化过程中 TiO₂ 纳米管阵列的生长,而且过量的 Au 在退火处理时很难及时地扩散均匀,进而使得改性后的 TiO₂ 纳米管阵列(40s-Au@ N-TNAs)的光催化效率明显降低。     

Capacitance performance enhancement of TiO<Subscript>2</Subscript> doped with Ni and graphite

Nano-amorphous TiO₂ was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO₂-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO₂. The electrochemical properties of TiO₂-NiO-C, such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO₂-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO₂-NiO-C shows excellent capacity and cycling performance.     

Preparation of anatase TiO<Subscript>2</Subscript> with assistance of surfactant OP-10 and its electrochemical properties as an anode material for lithium ion batteries

With the assistance of nonionic surfactant (OP-10) and surface-selective surfactant (CH₃COOH), anatase TiO₂ was prepared as an anode material for lithium ion batteries. The morphology, the crystal structure, and the electrochemical properties of the prepared anatase TiO₂ were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and galvanostatic charge and discharge test. The result shows that the prepared anatase TiO₂ has high discharge capacity and good cyclic stability. The maximum discharge capacity is 313 mAh·g⁻¹, and there is no significant capacity decay from the second cycle.     

Electrochemical properties of ordered TiO2 nanotube loaded with Ag nano-particles for lithium anode material

Self-organized TiO₂ nanotube array was grown on titanium (Ti) thin film by anodizing in glycerol solution containing low concentration of NH₄F, and Ag/TiO₂ nanotube was then prepared from TiO₂ nanotube array by thermal decomposition. The physical properties of the synthesized TiO₂ and Ag/TiO₂ nanotubes were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The synthesized two samples were used as negative materials for lithium-ion battery, and their charge–discharge property, cyclic voltammetry, electrochemical impedance spectroscopy, and cycle performance were investigated. The results indicated that the addition of Ag to TiO₂ nanotube could significantly improve the electronic conductivity, charge–discharge capacity, and cycle stability of TiO₂ nanotube.     

Effect of different structured TiO2 particle on anticorrosion properties of waterborne epoxy coatings

Anticorrosion properties of waterborne epoxy coatings with three structured nano-particles of TiO₂ were investigated and compared. The surface morphology and structure of TiO₂ have been analysed by XRD, SEM and N₂ adsorption–desorption. Corrosion performance of the nano-composite coating was investigated employing electrochemical impedance spectroscopy and salt spray test. Coatings with mesoporous TiO₂ (meso-TiO₂) possessed the best corrosion performance among the coating specimens. The EIS results show that the resistance value of coating with meso-TiO₂ was above 5.4?×?10⁸?Ω?cm² which was higher than the other nano-composite coatings. Possible strong interactions between polymeric matrix and meso-TiO₂ caused high barrier properties.     

Synthesis and photocatalytic properties of Sn-doped TiO2 nanotube arrays

TiO₂ nanotube arrays doped by Sn up to 12 at% have been prepared using template-based liquid phase deposition method. Their morphologies, structures and optical properties have been investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV–vis absorption spectroscopy and photoluminescence spectroscopy. The photocatalytic properties of the samples were evaluated with the degradation of methylene blue under UV irradiation. The result shows that doping an appropriate amount of Sn can effectively improve the photocatalytic activity of TiO₂ nanotube arrays, and the optimum dopant amount is found to be 5.6 at% in our experiments.     

热喷涂法制备的La3+掺杂纳米TiO2粉末的表征

采用等离子热喷涂法以钛酸四丁酯为主要原料制备出稀土离子掺杂的纳米TiO2光催化剂.通过XRD,XPS,TEM,UV-Vis等检测手段对样品进行表征,同时检测了其光催化性能,并分析了掺杂对TiO2的影响机理.结果表明,所制备的La3 掺杂纳米TiO2是锐钛矿相和金红石相混晶结构,粒径分布在10～50nm之间;La3 掺杂能够促进锐钛矿向金红石的转变,同时抑制TiO2晶粒的长大;La3 掺杂使TiO2紫外-可见吸收光谱发生红移;适量La3 掺杂能显著提高TiO2的光催化活性,最佳掺杂浓度为0.5%(与Ti原子摩尔比),甲基橙降解率在90min内可达到82.4%.比纯TiO2高出13.2%.     

非晶TiO2 纳米管形貌对其作为超级电容器电化学性能的影响

采用改进的两步电化学阳极氧化和电化学氢化法制备了不同管径、长度和壁厚的氢化无定型TiO₂纳米管阵列（H@am-TNAs）。结果表明,电化学氢化对TiO₂纳米管阵列的结构影响不大。经过电化学氢化后,纳米管在100 mV·s^-1时的比电容为4.05 mF·cm^-2,比未氢化的管长和管径相同的TiO₂纳米管的比电容大20倍。纳米管的比电容不仅与管长有关,还受管径的影响。通过指数函数拟合,纳米管的长径比呈线性关系。面积电容/长径比达到0.056,几乎相当于锐钛矿相TiO₂纳米管。阳极化处理后的纳米管具有最小的电荷转移阻力和最佳的离子扩散/输运动力学,具有最高的面积容量。此外,为了研究H@am-TNAs纳米管的电化学性能的润湿性,相同的H@am-TNAs电极在C-V和C-P测试前,在电解液中浸泡不同时间,结果表明,比电容随着浸泡时间的增加而减小。