导电玻璃上室温沉积钛膜及TiO2纳米管阵列的制备与表征

在掺氟的杂nO2(FTO)导电玻璃衬底上采用射频磁控溅射的方法室温沉积纯Ti薄膜, 以NH4F/甘油为电解液, 经电化学阳极氧化得到结构有序、微米级的TiO2纳米管阵列/FTO复合结构, 并通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)以及光电化学的方法对纳米管阵列进行了表征. 研究表明, 在氩气气压为0.5 Pa, 功率为150 W, 时间为0.5 h条件下在导电玻璃上室温沉积获得钛膜的结构为晶带T型组织, 表面均匀性好且致密度较高; 在电压为30 V下, 随着阳极氧化时间从1 h延长至3 h, 纳米管的管径从50 nm增加到75 nm, 纳米管的长度从750 nm增至1100 nm后减至800 nm, 管壁由平滑变为波纹状; 随氧化电压的升高, 纳米管管径逐渐增大, 而表面覆盖物逐渐减少, 可通过在稀的HF溶液(0.05%(w, 质量分数))中超声清洗去除; 此外, 瞬态光电流测试表明结晶的电极表现出更好的光电转换性能, 紫外光照射下能促进TiO2光生载流子有效分离, 在热处理温度为450 ℃时, 具有较高的光电化学性能.     

Fabrication of self-organized TiO2 nanotubes from columnar titanium thin films sputtered on semiconductor surfaces

Self-organized nanotube arrays of TiO₂ have been grown from titanium (Ti) thin films deposited on p-type Si(1 0 0) substrates. Structural and morphological characterizations carried out by X-ray diffraction and scanning electron microcopy indicate that the sputtered crystalline Ti thin films used for subsequent anodization are hexagonally closed packed (hcp-Ti) and show a columnar morphology. Electrochemical anodization of the Ti films was carried out by potentiostatic experiments in 1 M H₃PO₄ + 1 M NaOH + 0.5 wt% HF electrolyte at room temperature. The TiO₂ nanotubes on a semiconductor substrate have an average tube length of approximately 560 nm, diameter in the order of 80 nm and wall thickness approximately 20 nm.     

含氯离子电解液中二氧化钛纳米管的阳极氧化形成机理及应用

采用电化学阳极氧化的方法,以氯化铵(NH₄Cl)水溶液为电解液,在纯钛表面制备了二氧化钛(TiO₂)纳米管。考察了制备电压、氧化时间、Cl^-浓度和钛基体的退火处理对阳极氧化过程的影响规律,探讨了在含氯离子电解液中纳米管的形成机理,并基于上述含氯离子电解液中纳米管形成机制,通过两步阳极氧化法得到无支撑纳米管薄膜。     

TiO2 nanorods branched on fast-synthesized large clearance TiO2 nanotube arrays for dye-sensitized solar cells

A large clearance TiO₂ nanotube arrays (LTAs) has been synthesized by a not more than 12 h anodization duration and based on this a branched TiO₂ nanotube arrays (BLTs) has been achieved through TiO₂ nanorods branch-like grown on the LTAs. Some key factors and probable mechanisms of the fabrication processes on two novel nanoarchitectures are discussed. Exhilaratingly, it is found that the obtained LTAs has demonstrated large pore diameter and void spaces (pore diameter ∼350 nm; void spaces ∼160 nm; and tube length ∼3.5 μm), and the synthesized hierarchical BLTs, compared with conventional TiO₂ nanotube arrays, has shown a much stronger dye absorption performance and an approximately double of the solar cell efficiency (in our case from 1.62% to 3.18% under simulated AM 1.5 conditions).     

阳极氧化法制备二氧化钛纳米管及其荧光性质

室温下采用电化学阳极氧化法在NaF、Na₂SO₄和H₂SO₄的混合溶液中用化学处理后的纯Ti片表面组装了一层结构高度有序的高密度TiO₂纳米管阵列。考察了几种主要的实验参数(阳极氧化电压、温度、电解液浓度)对TiO₂纳米管阵列形貌和尺寸的影响，探讨了二次阳极氧化对纳米管形貌的改善。对TiO₂纳米管阵列进行扫描电子显微镜(SEM)和荧光(PL)分析，探讨其生长机理。结果表明，孔径随阳极氧化电压的升高而变大，温度、电解液浓度影响反应过程中电流密度的大小；二次阳极氧化得到的纳米管的有序性有所改善，孔径大小更为均一，并且发现TiO₂纳米管的荧光具有量子效应。     

Highly-ordered dye-sensitized TiO2 nanotube arrays film used for improving photoelectrochemical electrodes

Thin titanium oxide nanotube arrays (TNAs) films were synthesized by anodization of titanium foil in an aqueous dimethyl sulfoxide solution using a platinum foil counter electrode.TNAs up to 6.8 μm in length,120 nm in inner pore diameter,and 20 nm in wall thickness were obtained by 40 V potentials anodization for 24 h.Their microstructures and surface morphologies were characterized by XRD,TEM,SAED and UV-vis spectroscopy.The photoelectrochemical properties of as-prepared unsensitized and dye-sensitized TNAs electrodes were examined under simulated solar light (AM 1.5,100 mW/cm2) illumination.The results showed that the photocurrent of the dye-sensitized TNAs electrodes reached 6.9 mA/cm2,which was 6 times more than that of the dye-sensitized TiO2 nanoparticles (TNPs) electrodes.It implied that the electron transport process and the charge recombination suppression within TNAs electrodes were much more favorable in comparison with that in the TNPs electrodes.Electrodes applying such kind of titania nanotubes will have a potential to further enhance the efficiencies of TNAs-based dye-sensitized solar cells.     

Anodic composite deposition of RuO2·xH2O–TiO2 for electrochemical supercapacitors

This communication demonstrates the first work on anodic composite deposition of oxide nanocomposites. Rutile TiO₂ nanoflowers with an average petal size of ca. 10 nm in diameter and 100 nm in length were synthesized from a TiCl₃ solution purged with air at 25 °C for 12 days prior to the composite deposition. Hydrous ruthenium oxide (RuO₂·xH₂O) and TiO₂ nanoflowers were composite-deposited onto Ti substrates for supercapacitors. In comparing with RuO₂·xH₂O deposits, RuO₂·xH₂O–TiO₂ nanocomposites with a highly porous nature exhibit the weakly mass-dependent specific capacitance and high-power capacitive characteristics.     

A facile one-step preparation of hierarchically-structured TiO2 nanotube array photoanodes with enhanced photocatalytic activity

Hierarchically structured TiO₂ (HST) films composed of top porous nanoparticle layer and underneath nanotube array layer are obtained by an anodization method on fluorine doped tin oxide surfaces. Compared with the TiO₂ nanotube arrays photoanode on Ti substrate, the HST photoanode exhibits a higher photoelectrocatalytic activity towards the oxidation of water and organics (e.g., glucose).     

Effect of electrolysis conditions on photocatalytic activities of the anodized TiO2 films

Photocatalytic activities of anodized TiO₂ films for decomposition of gaseous acetaldehyde were investigated. The anodized TiO₂ films were fabricated by galvanostatic anodization in a mixed electrolyte composed of H₂SO₄, H₃PO₄, and H₂O₂. Pre-nitridation treatment effectively enhanced the photocatalytic activity of the anodized TiO₂ films. The electrolysis parameters such as anodization time, current density, electrolyte temperature, and electrolyte composition significantly affected the photocatalytic activity of the anodized TiO₂ films. The improvement of photocatalytic activity of the anodized films is attributed to increase in surface areas of the anodized specimens.     

Performance of Impedimetric Biosensors Based on Anodically Formed Ti/TiO2 Electrodes

The advantages and limitations of impedimetric sensors based on Ti/TiO₂ architectures are described. Titanium dioxide (titania) was potentiostatically formed onto titanium electrodes of 2 mm diameter, at 10 and 30 V in 1 M H₂SO₄. The thickness of the titania layers was ellipsometrically determined to be 30 and 86 nm respectively and they are highly insulating with charge‐transfer resistances in the MΩ range, as they were measured with electrochemical impedance spectroscopy under specific experimental conditions. Low voltage anodization (<10 V) results to amorphous TiO₂, whereas at higher applied voltages (>25 V), anatase is the predominant form. SEM images are indicative of quite smooth, compact coatings without any severe cracks.     

Sol-Gel Template Synthesis of Highly Ordered LiCo0.5Mn0.5O2 Nanowire Arrays and Their Structural Properties

Highly ordered LiCo_0.5Mn_0.5O₂ nanowire arrays were prepared using porous anodic aluminum oxide (AAO) template from sol-gel solution containing Li(CH₃COO), Co(CH₃COO)₂, and Mn(CH₃COO)₂. Electron microscope results showed that uniform length and diameter of LiCo_0.5Mn_0.5O₂ nanowires were obtained, and the length and diameter of LiCo_0.5Mn_0.5O₂ nanowires are dependent on the pore diameter and the thickness of the applied AAO template. X-ray diffraction and electron diffraction pattern investigations demonstrate that LiCo_0.5Mn_0.5O₂ nanowires are a layered structure of LiCo_0.5Mn_0.5O₂ crystal. X-ray photoelectron spectroscopy analysis indicates that the most closely resembling stoichiometric layered LiCo_0.5Mn_0.5O₂ material has been obtained.     

Influence of surface properties of the titanium dioxide porous films on the characteristics of solar cells

Porous films formed by cylindrical geometrically anisotropic fragments of TiO₂ have been produced by electrochemical anodization of titanium. The specific surface area and pore volume of the samples were determined by the BET method. It is shown that the samples have a bimodal pore-size distribution with maxima depending on the anodization voltage: by increase in voltage the inner diameter of the cylindrical pores grows, which leads to a decrease in the specific surface area. Dye sensitized solar cells were assembled on the basis of the obtained materials to study the effect of certain characteristics on the efficiency of solar energy conversion. The electrical transport properties of the films were studied by impedance spectroscopy.     

Fabrication of Ordered TiO2 Porous Thin Films by Sol-Dipping PS Template Method

Monolayer polystyrene spheres (∼400 nm) array templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS and porous TiO₂ thin films were prepared by using sol-dipping template method to fill TiO₂ sol into the interstices among the close-packed PS templates and then annealing to remove the PS templates. The effects of TiO₂ precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed pore size of the ordered TiO₂ porous thin film depended mainly on PS size and partly on TiO₂ sol concentration. The shrinkage of pore diameter was about 10% for 0.2 M and 20% for 0.4 M TiO₂ sol concentrations. X-ray diffraction (XRD) spectra indicated the porous thin film was anatase structure. The transmittance spectrum showed that optical transmittance of the porous thin film kept above 70% beyond the wavelength of 430 nm. Optical band-gap of the porous TiO₂ thin film (fired at 550^∘;C) was 3.12 eV.     

低温吸附制备Au-TiO2复合薄膜及其光电化学性质

在低温条件下将预先合成的Au溶胶吸附到TiO₂薄膜上以制备纳米Au-TiO₂复合薄膜,以超高分辨率场发射扫描电镜(FESEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)表征Au-TiO₂膜,并在UV辐照下测定了Au-TiO₂薄膜电极的光电化学性质。纳米Au呈金属态,平均粒径为(4.3±1.2) nm,负载量高,均匀地沉积于TiO₂薄膜表面。光电化学测试表明,沉积纳米Au后,TiO₂电极的光生电流提高近5倍,光生电压明显向负值增大,说明纳米Au可增强光生载流子的分离效率,促进电荷在电极与溶液界面间的转移。Au-TiO₂电极的电荷传递法拉第阻抗(R_ct)是TiO₂电极的一半,说明负载的纳米Au粒抑制了光生电子-空穴的复合,提高了电极中载流子浓度。     

Photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant on highly smooth and ordered TiO2 nanotube arrays

The photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant were achieved on TiO₂ nanotube electrodes with double purposes of environmental protection and renewable energy production under illumination of simulated solar light. The TiO₂ nanotube arrays (TiO₂ NTs) were fabricated by a two-step anodization method. The TiO₂ NTs prepared in two-step anodization process (2-step TiO₂ NTs) showed much better surface smoothness and tube orderliness than TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). In the photoelectrochemical water splitting and simultaneous photoelectrocatalytic decomposition process, the 2-step TiO₂ NTs electrode showed both highest photo-conversion efficiency of 1.25% and effective photodecomposition efficiency with existing of methylene blue (MB) as sacrificial agent and as pollutant target. Those results implied that the highly ordered nanostructures provided direct pathway and uniform electric field distribution for effective charges transfer, as well as superior capabilities of light harvesting.     

Hemoglobin adsorption into TiO2 phytate multi-layer films: particle size and conductivity effects

Hemoglobin (molecular weight 64.5 kDa, isoelectric point 7.4) in 0.1 M phosphate buffer solution at pH 5.5 readily adsorbs onto mesoporous TiO₂ phytate films, which have been formed in a layer-by-layer deposition process from TiO₂ nanoparticles (ca. 6–10 nm diameter) and phytic acid at tin-doped indium oxide (ITO) electrodes. Quartz crystal microbalance data, voltammetry, and SEM evidence are consistent with hemoglobin adsorption only into the outer TiO₂ phytate surface layer. The size of the tetrametric hemoglobin protein (ca. 6 nm diameter) appears to be too big for a homogeneous film to form.The modified ITO electrode immersed in 0.1 M phosphate buffer solution at pH 5.5 allows reversible electron transfer for hemoglobin to be observed with a midpoint potential of 0.01 vs. SCE. Characteristic TiO₂ phytate film thickness and pH effects are observed with both thicker films and lower proton activity causing ‘decoupling’ of the protein redox chemistry due to a reduced electrical conductivity of the TiO₂ phytate film connecting hemoglobin with the electrode. This is the first example of a bi-layer nanofilm structure where the underlying TiO₂ phytate film controls the electrochemical properties of the hemoglobin modified top-layer.     

TiO2纳米管阵列光电催化氧化处理氨氮废水

用电化学阳极氧化法制备了高度有序的钛基二氧化钛纳米管阵列薄膜。用场发射扫描电镜(FE-SEM)、X射线衍射(XRD)表征样品的形貌与晶型特征。以二氧化钛纳米管阵列为光阳极,石墨为对电极,测试了不同pH值和外加偏压条件下的光电流响应和光电催化氧化降解NH4Cl水溶液(以N计,100 mg·L-1)的效率。结果表明:所制备的TiO2纳米管阵列具有锐钛矿和金红石的混晶结构,且主要晶型为锐钛矿。光电流响应的强弱与光电催化氧化效率的高低相对应,降解氨氮废水的最佳条件为pH=11,偏压为1.0 V。     

Micro- and nano-scale hollow TiO2 fibers by coaxial electrospinning: Preparation and gas sensing

We report the preparation of micro- and nano-scale hollow TiO₂ fibers using a coaxial electrospinning technique and their gas sensing properties in terms of CO. The diameter of hollow TiO₂ fibers can be controlled from 200 nm to several micrometers by changing the viscosity of electrospinning solutions. Lower viscosities produce slim hollow nanofibers. In contrast, fat hollow microfibers are obtained in the case of higher viscosities. A simple mathematical expression is presented to predict the change in diameter of hollow TiO₂ fibers as a function of viscosity. The successful control over the diameter of hollow TiO₂ fibers is expected to bring extensive applications. To test a potential use of hollow TiO₂ fibers in chemical gas sensors, their sensing properties to CO are investigated at room temperature.     

Fabrication of AAO films with controllable nanopore size by changing electrolytes and electrolytic parameters

In this paper, we fabricate two kinds of anodic aluminum oxide (AAO) films with controllable nanopore size by changing electrolytes and electrolytic parameters. The first AAO film with a four-layer structure was fabricated by sequential anodization of aluminum in aqueous solution of H₂SO₄, H₂C₂O₄, malonic acid, and tartaric acid at different anodic oxidation voltages. The average pore diameter of the as-prepared AAO film is 25 nm in the first layer, 54 nm in the second layer, 68 nm in the third layer, and 88 nm in the fourth layer, respectively. The pore densities of each layer decrease downwards to Al substrate, which are 300?×?10⁸, 100?×?10⁸, 21?×?10⁸, and 6.9?×?10⁸ cm^?2, respectively. Furthermore, another AAO film with periodically changed pore diameter was fabricated by alternating anodization of aluminum in aqueous solution of H₃PO₄ and tartaric acid under galvanostatic mode. The anodization processes present approximately identical best ordering voltage (195 V) in H₃PO₄ and tartaric acid under galvanostatic mode. The pore diameter with periodic change can be enlarged through a pore-widening treatment. Both AAO films with special nanopore structures can be used not only as templates for preparing nano-array materials whose pore diameter presents periodic change or gradual increase, but also as nanofilters to separate materials in some special media.     

Photoelectrochemical oxidation behavior of methanol on highly ordered TiO2 nanotube array electrodes

The highly ordered titanium dioxide nanotube array (HOTDNA) electrodes were prepared in hydrofluoric acid solution by electrochemical anodic oxidation technique on a pure titanium sheet. The HOTDNA electrodes were characterized by X-ray diffraction, SEM microscopy, and UV–vis spectra. It has shown high density, well ordered and uniform titanium dioxide nanotube array film covered on these electrodes and the TiO₂ structure depending on the heating condition, the anatase phase of TiO₂ appeared when heating to 500 °C. The photoelectrochemical characteristics of methanol in 0.5 M Na₂SO₄ on the HOTDNA electrodes were investigated. The cyclic voltammetry, photocurrent-time and open-circuit photopotential response of methanol on the HOTDNA electrode were represented and significant photogenerated current was observed upon illumination in the UV regions with the light of 253.7 nm central wavelength. The effect of variables such as light intensity, applied potential, and methanol concentration on the photoelectrochemical response was investigated. It was found that the photocurrent was greatly influenced by these factors.