Hierarchically branched titania nanotubes with tailored diameters and branch numbers

Over the past decade, electrochemical anodization of self-organized TiO(2) nanotubes has been studied intensively with the main focus being on uniform diameters along the TiO(2) nanotube depth direction. In the present work, hierarchically branched TiO(2) nanotubes with tailored diameters and branch numbers are successfully achieved by adjusting the anodization voltage. Reducing the applied voltage by a factor of 1/√n causes a one trunk nanotube to diverge into n-branched TiO(2) nanotubes, whose diameters are 1/√n of the trunk nanotube diameter (n is an integer). Multiple layers of branched TiO(2) nanotubes are also obtained by further dividing the branched nanotubes when the applied voltage is further reduced step-by-step with a 1/√n factor. Enlargement and termination of TiO(2) nanotubes occur when the anodization voltage increases by √n times. Alternating increase and decrease in the applied voltage lead to a more sophisticated hierarchical structure of TiO(2) nanotubes. The fundamental understanding of these processes is discussed.     

二氧化钛纳米管的制备与光催化活性

用阳极氧化法,室温条件下在含NH4F和H2O的电解液(丙三醇+NH4F+H2O;乙二醇+NH4F+H2O)中制备了TiO2纳米管阵列。用环境扫描电子显微镜(SEM)、X射线衍射仪(XRD)表征二氧化钛纳米管阵列的微观形貌和物相结构。在丙三醇电解液中,电压为60 V,65 V,70 V,75 V制备的纳米管直径依次为160、170、190、220 nm。对甲基橙(10 mg/L)降解测试TiO2纳米管阵列的光催化性能。研究结果表明:在100 V阳极电压制备经过500℃退火处理后的TiO2纳米管阵列的光催化效果最好,其光催化降解率在光照时间120 min时达到89.2%。     

Anodic growth of highly ordered TiO2 nanotube arrays to 134 microm in length

Described is the fabrication of self-aligned highly ordered TiO(2) nanotube arrays by potentiostatic anodization of Ti foil having lengths up to 134 mum, representing well over an order of magnitude increase in length thus far reported. We have achieved the very long nanotube arrays in fluoride ion containing baths in combination with a variety of nonaqueous organic polar electrolytes including dimethyl sulfoxide, formamide, ethylene glycol, and N-methylformamide. Depending on the anodization voltage, pore diameters of the resulting nanotube arrays range from 20 to 150 nm. Our longest nanotube arrays yield a roughness factor of 4750 and length-to-width (outer diameter) aspect ratio of approximately 835. The as-prepared nanotubes are amorphous but crystallize with annealing at elevated temperatures. In initial measurements, 45 mum long nanotube-array samples, 550 degrees C annealed, under UV illumination show a remarkable water photoelectrolysis photoconversion efficiency of 16.25%.     

Surface-assisted laser desorption-ionization mass spectrometry on titanium dioxide (TiO2) nanotube layers

The paper reports on the use of a titanium oxide (TiO(2)) nanotube layer as a sensitive substrate for surface-assisted laser desorption-ionization mass spectrometry (SALDI-MS) of peptides and small molecules. The nanotube layers were prepared by electrochemical anodization of titanium foil. The optimized TiO(2) nanotubes morphology coupled to a controlled surface chemistry allowed desorption-ionization (D/I) of a peptide mixture (Mix1) with a detection limit of 10 femtomoles for the neurotensin peptide. The performance of the TiO(2) nanotubes for the D/I of small molecules was also tested for the detection of sutent, a small tyrosine kinase inhibitor, and verapamil. A detection limit of 50 fmol was obtained for these molecules, as compared to 500 fmol using classical matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). Both amorphous and anatase TiO(2) layers displayed a comparable performance for D/I of analyte molecules. In a control experiment, we have performed D/I of analyte molecules on a flat TiO(2) layer. The absence of signal emphasizes the role of the nanostructured substrate in the D/I process.     

TiO_2纳米管阵列的制备及其对316不锈钢光生阴极保护作用的研究

应用直接电化学阳极氧化法,于含氟电解液中,在纯钛表面制备一层整齐有序的TiO2纳米管阵列.扫描电子显微镜(SEM),X射线衍射(XRD)表征该纳米管阵列的形貌及晶体结构,光电化学联用系统研究其光电响应特性及对316L的光生阴极保护作用.结果表明:以TiO2纳米管阵列膜作为光生阳极时,在紫外光区(λ<387nm)有显著增强的光生电流响应,并对316不锈钢有较好的光生阴极保护作用.暗态下,光生电极电位仍可维持较长的一段时间,继续起到阴极保护作用.     

Investigation on the dynamics of electron transport and recombination in TiO2 nanotube/nanoparticle composite electrodes for dye-sensitized solar cells

In this work, we report on fabrication and characterization of dye-sensitized solar cells based on TiO(2) nanotube/nanoparticle (NT/NP) composite electrodes. TiO(2) nanotubes were prepared by anodization of Ti foil in an organic electrolyte. The nanotubes were chemically separated from the foil, ground and added to a TiO(2) nanoparticle paste, from which composite NT/NP electrodes were fabricated. In the composite TiO(2) films the nanotubes existed in bundles with a length of a few micrometres. By optimizing the amount of NT in the paste, dye-sensitized solar cells with an efficiency of 5.6% were obtained, a 10% improvement in comparison to solar cells with pure NP electrodes. By increasing the fraction of NT in the electrode the current density increased by 20% (from 11.1 to 13.3 mA cm(-2)), but the open circuit voltage decreased from 0.78 to 0.73 V. Electron transport, lifetime and extraction studies were performed to investigate this behavior. A higher fraction of NT in the paste led to more and deeper traps in the resulting composite electrodes. Nevertheless, faster electron transport under short-circuit conditions was found with increased NT content, but the electron lifetime was not improved. The electron diffusion length calculated for short-circuit conditions was increased 3-fold in composite electrodes with an optimized NT fraction. The charge collection efficiency was more than 90% over a wide range of light intensities, leading to improved solar cell performance.     

铁掺杂TiO2纳米管阵列对不锈钢的光生阴极保护

在含FeSO4的HF、H2SO4/HF、NaF/Na2SO4溶液中,通过电化学阳极氧化直接在纯钛表面制备Fe 掺杂的TiO2(Fe-TiO2)纳米管阵列. 应用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见吸收光谱(UV-Vis)、X 射线光电子能谱(XPS)等手段对纳米管阵列的结构、形貌及化学组成进行表征. 利用光电化学测量研究Fe-TiO2纳米管阵列在不同波长范围内的光电响应特性和光生阴极保护行为. 考察了温度、时间、掺杂含量等参数对TiO2纳米管阵列的几何尺寸、形貌和光电性能的影响. 结果表明, Fe掺杂可有效减缓TiO2纳米管阵列载流子的复合, 窄化TiO2带隙宽度, Fe-TiO2在410-650 nm范围显示强吸收, 并使光谱响应扩展到波长大于400 nm 的可见光区. 实验结果还表明, Fe-TiO2纳米管阵列对316不锈钢(316L)具有良好的光生阴极保护作用, 暗态下阴极保护作用可继续维持.     

TiO2纳米管阳极氧化制备机理及热处理对其影响

采用阳极氧化方法,在NH4F+H2O的乙二醇溶液体系下制备了TiO2纳米管列阵薄膜,建立了TiO2纳米管列阵薄膜的"电场诱导"生长模型。TiO2纳米管的管形结构形成与TiO2的半导体性质相关。纳米管表面吸附的纳米粒子与管壁间空间有关系。经过退火处理的纳米管管口由12~14个直径为25~35 nm的纳米颗粒团聚体组成,600℃时,纳米管结构已被破坏。经过300~600℃之间不同温度处理后的TiO2纳米管呈现锐钛矿晶态,比表面积随温度升高呈下降趋势。     

Nb doping of TiO2 nanotubes for an enhanced efficiency of dye-sensitized solar cells

Nb-doped TiO(2) nanotube (with C(Nb) < 1 wt%) layers were successfully fabricated by self-ordered electrochemical anodization of Ti-Nb alloys. When used in dye-sensitized solar cells the efficiency enhanced by up to 30% compared to non-doped TiO(2) nanotubes. IMVS measurements indicate the beneficial effect to be due to lower recombination losses.     

阳极氧化法制备TiO_2纳米管阵列膜及其应用

由阳极氧化法制备的TiO2纳米管阵列,因其独特的有序结构而显示出优异的性能,在许多领域有着广泛的应用,成为一种很有发展前景的新型纳米结构材料。本文简要综述了制备TiO2纳米管阵列结构的方法及其应用研究进展。在比较了当前几种制备TiO2纳米管阵列方法的优缺点后,重点讨论了阳极氧化法制备TiO2纳米管阵列结构过程中,如何通过调整工艺参数来实现此类纳米管阵列结构的可控生长。最后评述了TiO2纳米管阵列材料研究的发展趋势和应用前景。     

Preparation of High-Orderly TiO2 Nanotubes in Organic Solution and Characterization of C-doped TiO2

"High-orderly TiO2 nanotube arrays were fabricated by anodic oxidation of pure titanium substrate in organic electrolyte containing fluoride. Different morphological nanotubes of titania were obtained through controlling the different anodization voltages and durations. The length of the longest nanotubes was approximately 60 1m and the length-to-width aspect ratio was about 600. The nanotube layers were then annealed at different temperatures (450, 550, and 650 oC) in air for 2 h. The samples were characterized by scanning electron microscopy, X-ray diffraction (XRD), energy dispersive X-Ray (EDS) and UV-Vis spectrometer. The XRD results demonstrated that the as-anodized samples were amorphous and the structure changed to antanse and rutile when the samples were annealed at higher temperature. The EDS microanalysis indicated the presence of carbon in the TiO2 nanotubes. The result of degradation of methylene blue showed clearly that the photocatalytic activity of C-doped TiO2 nanotubes increased by 10%."     

TiO2 nanotube layers: Flexible and electrically active flow-through membranes

In the present work we demonstrate the fabrication and use of a new generation of TiO₂ nanotube membranes. We show that anodic oxide nanotube growth can be performed through a patterned Ti foil into an underlying Al metal layer. After the selective dissolution of the Al/alumina layer, a very well defined both side open suspended TiO₂ nanotube layer can be obtained. Using lithographic patterning of the anodization area allows to achieve very large scale, flexible and well electrically connected nanotubular flow-through membranes with fast electrical switching features over the entire membrane.     

Effect of supporting surface layers on catalytic activities of gold nanoparticles in CO oxidation

The surfaces of fumed silica materials were modified with a surface sol-gel process for catalysis applications. This surface-modification approach allows not only a monolayer growth of TiO(2) or Al(2)O(3) but also a stepwise double-layer growth of TiO(2)/TiO(2), Al(2)O(3)/Al(2)O(3), TiO(2)/Al(2)O(3), or Al(2)O(3)/TiO(2) on the surfaces of the silica materials with a monolayer precision. XRD analyses revealed that the coated monolayers and double layers of TiO(2) and Al(2)O(3) were amorphous. Gold nanoparticles were successfully deposited on the above six surface-modified silica materials via a deposition-precipitation method. The catalytic activities of these six gold catalysts for CO oxidation are highly dependent on the structures of their surface monolayers or double layers. The gold catalyst supported on the silica material functionalized with a TiO(2) monolayer (Au/TiO(2)) is the most active in both as-synthesized and oxidized forms, while the gold catalyst supported on the silica material functionalized with an Al(2)O(3)/TiO(2) double layer (Au/Al(2)O(3)/TiO(2)/SiO(2)) is the most active in the reduced form among the six catalysts. Surprisingly, the gold catalyst supported on the silica material functionalized with a TiO(2)/Al(2)O(3) double layer (Au/TiO(2)/Al(2)O(3)/SiO(2)) has much less activity than Au/Al(2)O(3)/TiO(2)/SiO(2) under all various treatments, underscoring the sensitivity of the catalytic activity to the structure of the supporting surfaces.     

宽电压范围下阳极氧化制备TiO_2纳米管阵列及其热稳定性

采用电化学阳极氧化技术,以含有NH4F和H2O的甘油溶液为电解液,在宽氧化电压范围(20~100V)下于纯钛表面制备了结构高度有序的TiO2纳米管阵列。利用扫描电子显微镜(SEM)考察了阳极氧化工艺(氧化电压、NH4F浓度、环境温度、水分含量等因素)及退火处理对纳米管形貌的影响;采用X射线衍射分析(XRD)表征了不同氧化电压和退火前后TiO2纳米管阵列的物相;并从电流-时间曲线出发简要地分析了纳米管阵列的形成机理。结果表明,纳米管的内外径和管长随氧化电压的增大而增大;NH4F浓度和环境温度对纳米管形貌有一定的影响;水分含量的多寡决定了能否在高电压下自组装形成纳米管阵列;TiO2纳米管阵列具有良好的热稳定性,管状形貌可以保持到700℃;直接制备的TiO2纳米管阵列均为无定型结构,经450℃退火处理后,无定型的TiO2纳米管转变为锐钛矿相,而600℃退火处理后,部分锐钛矿相转变为金红石相。     

TiO2-MoO3复合纳米管阵列薄膜的制备及其可见光活性

通过阳极氧化的方法制备TiO₂纳米管薄膜, 在MoO₃存在的条件下对该薄膜进行热处理得到TiO₂-MoO₃复合纳米管阵列薄膜. 利用X射线衍射(XRD), 扫描电子显微镜(SEM), X射线光电子能谱(XPS), 电化学阻抗谱(EIS), Mott-Schottky 及光电化学方法对得到的薄膜进行了表征. XRD结果表明, TiO₂-MoO₃复合纳米管薄膜中的TiO₂主要为锐钛矿晶型. SEM实验证实了薄膜纳米管结构的存在, 样品中的MoO₃均匀地分散在TiO₂纳米管表面. 利用XPS方法分析了TiO₂-MoO₃复合纳米管薄膜元素的组成, 结果表明, MoO₃在TiO₂表面形成TiO₂-MoO₃复合纳米管薄膜. 研究了热处理温度以及热处理时间对样品的光电化学性能的影响, 相对于单纯TiO₂纳米管薄膜, 适量引入MoO₃提高了样品在可见光区的光电响应能力, 样品的平带电位负移. 在450 °C热处理60 min制得的TiO₂-MoO₃复合半导体纳米管阵列薄膜光电响应活性最高.     

甘油基电解液中阴离子对阳极氧化TiO2纳米管生长的影响

在NH4F-甘油-水电解液中, 采用阳极氧化法, 在纯Ti基底上制备了高度取向的TiO2纳米管阵列, 考察了阴离子种类、阳极氧化时间及NaAc浓度对纳米管阵列生长的影响. 结果表明, TiO2纳米管的生长速率和长度强烈依赖于阴离子的种类和浓度. NaNO3和NaCl的加入能增大阳极氧化时的电流密度, 提高TiO2纳米管底部的腐蚀速率, 提高管的生长速率及增加管的长度; 而NaAc的加入更大程度上抑制了已生成的TiO2纳米管顶部的溶解, 提高了纳米管的净生长速率, 得到较长的纳米管阵列.     

High carrier density and capacitance in TiO2 nanotube arrays induced by electrochemical doping

The paper describes the electronic charging and conducting properties of vertically oriented TiO 2 nanotube arrays formed by anodization of Ti foil samples. The resulting films, composed of vertically oriented nanotubes approximately 10 mum long, wall thickness 22 nm, and pore diameter 56 nm, are analyzed using impedance spectroscopy and cyclic voltammetry. Depending on the electrochemical conditions two rather different electronic behaviors are observed. Nanotube array samples in basic medium show behavior analogous to that of nanoparticulate TiO 2 films used in dye-sensitized solar cells: a chemical capacitance and electronic conductivity that increase exponentially with bias potential indicating a displacement of the Fermi level. Nanotube array samples in acidic medium, or samples in a basic medium submitted to a strong negative bias, exhibit a large increase in capacitance and conductivity indicating Fermi level pinning. The contrasting behaviors are ascribed to proton intercalation of the TiO 2. Our results suggest a route for controlling the electronic properties of the ordered metal-oxide nanostructures for their use in applications including supercapacitors, dye-sensitized solar cells, and gas sensing.     

SiW12、PbS对提高TiO2纳米管光电转换效率的协同效应研究

复合薄膜可以改善TiO2纳米管在光电转换时电子-空穴易复合和吸收光谱范围窄的缺陷。用电沉积法将多酸H4SiW12O40（SiW12）沉积在TiO2纳米管表面形成SiW12/TiO2纳米管复合薄膜,再用连续离子层吸附反应法（SILAR）将PbS吸附到SiW12 /TiO2纳米管复合薄膜表面,形成PbS/ SiW12/TiO2纳米管复合薄膜,所得薄膜的光电转换效率相较于TiO2纳米管提高了57倍。X射线衍射（XRD）和扫描电子显微镜（SEM）表征结果表明,用电沉积法和连续离子层吸附反应法实现了PbS/SiW12/TiO2纳米管复合薄膜的制备;紫外可见（UV-vis）吸收光谱测试表明,复合薄膜的光吸收带边扩展到了可见光区域,电化学阻抗测试（EIS）表明,复合薄膜具有更高的电子转移速率;荧光光谱（PL）测试表明,复合薄膜拥有更小的电子-空穴复合率。以上结果说明,SiW12、PbS与TiO2纳米管复合,很好地抑制了TiO2纳米管电子-空穴的复合,并拓宽了吸收光谱范围,能显著地提高TiO2纳米管的光电性能。本文探索了一种有效提高TiO2纳米管光电转换效率的方法,对TiO2纳米管复合薄膜的制备具有一定的参考意义。     

Highly ordered titania nanotube arrays with square, triangular, and sunflower structures

Focused ion beam guided anodization enables the fabrication of TiO(2) nanotubes in a square arrangement with square cell shapes and in a graphite lattice arrangement with triangular cell shapes, which is impossible through self-organized anodization. TiO(2) nanotubes in sunflower patterns are also obtained, which demonstrates the great potential of guided anodization in fabricating asymmetrical nanotubes.     

Elevation of melting temperature for confined palmitic acid inside cylindrical nanopores

High resolution 13C nuclear magnetic resonance was employed to study the phase behavior of the amphiphilic long-chain palmitic acid (PA) confined inside the cylindrical nanopores in the matrix of titanate nanotubes. For a series of mixtures of titanate nanotubes and palmitic acid at various mass ratios, it was shown that annealing at the bulk melting temperature (approximately 335.5 K) of PA induced fast chemisorption of PA on the nanotube surface followed by slow physical trapping of PA into the cylindrical nanopore. It was found that the trapped PA remained solidlike substantially above the bulk melting temperature. Contrary to the bulk neat PA, for the trapped PA, the isotropic molecular-chain reorientation was shown to remain arrested even above the bulk melting temperature. When destabilized at approximately 349 K, the trapped PA deserted the nanopore and formed bulk PA, which could be retrapped into the nanopore upon annealing at the bulk melting temperature. The entire process was shown as reversible.