Pattern formation in nanoporous titania templates

We have carried out a systematic investigation into the formation of nanoscaled patterns in titania (TiO2) templates under dc anodization of Ti in HF acid. At lower acid concentrations (around 0.5 wt% HF) either pores or tubes form at the surface of anodized titanium foil. The pores or nanotubes are separated from the bottom Ti layer by a thin barrier layer of TiO2. The critical voltage where the transition from pores to tubes occurs has been determined. It is observed that the transition voltage shift towards higher voltages as acid concentration is increased, with pore formation disappearing altogether at high acid concentrations. We have also carried out a systematic investigation into the dependence of pore and tube parameters on the applied dc anodization voltage. Our results indicate that the barrier layer thickness, pore and tube length increase as a function of applied voltage.     

V掺杂TiO2纳米管阵列的制备及光催化研究

以钒钛合金为原料,应用阳极氧化法制备出高度致密、有序的V掺杂TiO2纳米管阵列。应用扫描电镜(SEM)和粉末X光衍射仪(XRD)表征分析纳米管阵列的形貌和结构,结果表明在浓度不同的HF电解液下制备出径向不同的纳米管阵列,电解液浓度(0.5%～1.5%(质量分数)),管径变化(39.7～72.7nm)。在室温、可见光照射条件下,以10mg/L的亚甲基蓝溶液为模拟污染物进行光催化降解试验,研究了其光催化性能。结果显示V掺杂TiO2纳米管阵列光催化性能优于纯TiO2纳米管,且在HF电解液浓度为1.0%(质量分数)时制备出来的TiO2纳米管光催化降解有机毒物性能最佳。     

Macro,micro and nanostructure of TiO<Subscript>2</Subscript> anodised films prepared in a fluorine-containing electrolyte

The paper presents an electron microscopy study of the macro, micro and nanostructure of titania nano-tubes formed by electrochemical anodisation of titanium in a fluorine containing electrolyte. Scanning electron microscopy (SEM) is used to examine the overall structure of the nano-tubes formed under potentiostatic conditions. Transmission electron microscopy (TEM) has been used to examine the structure of the oxide layer of a sample anodised for a relatively short period (30 min) and provides a new insight into the formation of titania nano-tubes. The fluorine ions are able to nucleate sites on the titanium metal and generate a series of interconnected cavities or pores in the oxide complex formed, allowing current to flow within this film. Under specific conditions the cavities and randomly dispersed pores can align in the direction of the applied electric field and link up to generate an array of tubes, where the passage of ions and water is optimised. We also suggest that oxygen evolution at the anode may play a role in the development of the nano-tubes.     

玻璃基底TiO2纳米管阵列的制备及其光电性能研究

提高二氧化钛纳米管阵列电极的机械稳定性,改善电极的透光性能,有助于提高其光电催化性能,拓展电极的应用范围.通过室温射频溅射方法在玻璃基底上溅射一层金属钛膜,然后在含0.5%HF的电解液,10V阳极氧化电压下进行阳极氧化,得到玻璃基TiO2纳米管阵列电极.扫描电子显微镜和X射线衍射分析表明,玻璃基表面形成了孔径为20～30nm,管长约130nm排列有序的锐钛矿型TiO2纳米管阵列.光电性能测试表明,玻璃基TiO2纳米管阵列与金属钛基TiO2纳米管阵列表现出相似的光电催化性能,明显优于磁控溅射制备的TiO2薄膜.     

自组装高有序氧化钛纳米管束的制备

阳极氧化技术在氟基电解液中，对高有序氧化钛纳米管束的制备、特性及在太阳能方面的应用进行了简要综述。材料的结构证明，该材料在光分解水、光催化、气敏检测、光电转化等方面具有潜在巨大的应用。通过改变电压、电解液浓度、pH值、温度，可获得不同长度、直径、形状、壁厚的氧化钛纳米管束。在电解液中加入有机溶剂、淬火等方式掺杂，可改变氧化钛的禁带宽度，从而有效利用太阳能。     

Facile fabrication of anatase TiO2 nanotube arrays having high photocatalytic and photovoltaic performances by anodization of titanium in mixed viscous solvents

Highly ordered, vertically aligned, one side-opened, and regularly porous anatase TiO₂ nanotube arrays (TNAs) have been facilely grown by anodizing Ti foil in mixed viscous solvents of ethylene glycol (EG) and glycerol. By changing the volume ratio of two solvents, we have controlled the structural properties of TNAs such as tube diameters, wall thicknesses, and tube lengths. Our prepared TNAs have been found to have enhanced (004) planes, which are reactive in catalysis reactions. We have demonstrated that TNAs grown in 2:1 (v/v) EG and glycerol have the lowest band-gap energy and the largest mean crystallite diameter. TNAs grown on Ti foil have been directly employed for photocatalytic materials and the working electrode of photovoltaic dye-sensitized solar cells. Among our prepared samples, TNAs grown in 2:1 (v/v) EG and glycerol have shown the best photocatalytic activity for the degradation of methylene blue and the highest photovoltaic conversion efficiency of 4.08 %.     

硅掺杂TiO2纳米管阵列的制备及光电催化活性的研究

通过电化学沉积,在阳极氧化法制备的高度有序TiO2纳米管阵列表面均匀地沉积Si元素.扫描电子显微照片显示Si掺杂的TiO2纳米管垂直于基底定向生长.X射线衍射分析表明,所引入的Si可能掺入到TiO2的晶格中,因而提高了TiO2的热稳定性,抑制了金红石相的生成及晶粒的长大.紫外-可见漫反射分析表明Si掺杂的TiO2纳米管吸收边带发生了明显的蓝移,并且在紫外区的吸收强度明显增强.与未掺杂的TiO2纳米管相比,Si掺杂TiO2纳米管电极的紫外光电化学响应显著提高,其光电流密度是未掺杂的1.48倍.硅掺杂TiO2纳米管阵列光电催化降解五氯酚的动力学常数(1.651h-1)是未掺杂TiO2纳米管电极(0.823h-1)的2.0倍.     

电解液性质对TiO2纳米管阵列形貌及生长机理的影响

采用电化学阳极氧化法在纯钛片表面制备出了结构整齐有序的TiO₂纳米管阵列, 主要研究了电解液的性质、浓度以及氧化时间对TiO₂纳米管阵列形貌的影响, 并对不同电解液中TiO₂纳米管阵列的形成机理进行了初步探讨. 结果表明：在不同浓度的HF酸电解液中均可制备出规则、均匀的TiO₂纳米管阵列, 管径均匀, 表面平整, 但是纳米管的长度均较短, 约为300～350nm. 在高浓度HF电解液中, 同时获得了规则的纳米管阵列和纳米棒阵列. 在0.5wt% NaF和1mol/L Na₂SO₄中性电解液中也可以制备出表面光洁、排列整齐有序的TiO₂纳米管阵列, 纳米管长度明显长于HF酸电解液中获得的纳米管阵列, 达到了700nm, 但是阵列的表面平整度较差. 在乙二醇+0.6wt% NH₄F+2vol% H₂O有机电解液体系中可以制得超长的TiO₂纳米管阵列, 管径在150nm左右, 管长可达6μm.     

HF酸电解液浓度对TiO2纳米阵列结构的影响

TiO2纳米阵列(纳米管、纳米棒)结构具有良好的力学性能、化学稳定性以及抗腐蚀性能,在许多技术领域具有广阔的应用前景。采用阳极氧化法在工业纯钛片表面制备出高度有序的TiO2纳米管阵列和纳米棒阵列,研究了电解液浓度和阳极氧化时间对TiO2纳米阵列结构的影响,并对其形成机理进行了初步探讨。结果表明,低浓度的HF酸电解液有利于制备纳米管阵列,高浓度的HF酸电解液有利于制备纳米棒阵列。     

不同电解液组成对TiO2纳米管形成的影响

电解液在阳极氧化中发挥着重要作用,对TiO2纳米管的形成与否,形成后管的成分、形貌都有着很大的影响.本实验采用了恒压阳极氧化方式,分别以HF(0.5wt%),(NH4)2SO4 HF(0.5wt%),(NH4)H2PO4 HF(0.5wt%),NaNO3 HF(0.5wt%)为电解液,在钛箔表面获得多孔TiO2膜.用FESEM观察了多孔膜的形貌并用EDX和XPS能谱对膜表面成分和构成进行测试分析.实验结果表明:在单一的HF酸电解液中加入(NH4)2SO4或(NH4)H2PO4后,阳极氧化生成的膜孔径明显减小,并且膜表面形态较差.加入NaNO3后,对膜的形貌影响不是很大.由EDX和XPS能谱分析得出,阴离子中的大部分非金属元素较难进入膜表面,而氮元素却很容易掺杂进入膜的表面形成N-Ti-O结构,从而影响膜的成分构成.这表明本实验利用简单电化学方法实现了N的掺杂.通过XRD测试得出,含不同阴离子的电解液对TiO2膜的晶型转变温度影响不大.     

Syntheses of titania and poly(3,4-ethylenedioxythiophene) bilayer nanotubes

Synthesis of bilayer tubes of poly(3,4-ethylenedioxythiophene) (PEDT) and titania by electrochemical polymerization of PEDT and chemical deposition of titania in the pores of anodic alumina was reported. Electron diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and fourier transformed infrared spectroscopy (FTIR) were used to characterize these bilayer tubes. SEM photographs show the tubes of uniform diameters around 200 nm. TEM photographs confirm the formation of titania and PEDT bilayer tubes of 230 nm and 100 nm diameter, the thickness of outside TiO2 layer and inner PEDT layer are around 20 nm under the experimental condition. The XPS spectra of the bilayer tubes show that the Ti2p peak shifts to a lower binding energy and S2p peak shifts to a higher binding energy. Electron diffraction patterns show that TiO2 nanotubes formed was single crystals of anatase phase. I-V characteristic curves were measured for samples prepared under various conditions.     

Spiral growth of one dimensional titania nanostructures using anodic oxidation

One dimensional spiral titania nanostructures were obtained by anodization of pure titanium from fluoride containing solutions of phosphoric acid. The formation of nanotubes was found to be dependant on current density. Field Emission Scanning Electron Microscopy (FESEM) shows the diameter of tubes around 70-100 nm which is consistent with the High Resolution Transmission Electron Micrographs (HRTEM) and Atomic Force Microscopy (AFM) images. HRTEM showed the one dimensional growth as spiral in nature which was also supported by AFM images. This anisotropic growth is compared with the possible growth mechanisms.     

Vertically Oriented Titania Nanotubes Prepared by Anodic Oxidation on Si Substrates

Vertically oriented titania nanotube arrays were fabricated by anodization of titanium film deposited on silicon substrates under different processing conditions. The anodic formation of nanoporous titania on silicon substrate was investigated in aqueous solutions mixed with highly corrosive Na₂SO₄/NaF/citric acid. In the result of the anodization of titanium film deposited at room temperature, a very thin layer of ~70 nm having a worm-like structure was grown on the top of the porous layer. But, in the case of titanium film deposited at 500deg, vertically oriented TiO₂ nanotube arrays were formed. The average tube outer diameter of the nanotube was 74 nm to 100 nm. The longest nanotube of 681 mum was obtained at 15 V and 30 min. The current density transient curve recorded during anodization under a constant voltage showed a typical behavior for self-organized pore formation.     

Cathodoluminescence of TiO2 nanotubes prepared by low-temperature anodization of Ti foils

We show that anodization of Ti sheets in an ethylene glycol and HF containing electrolyte at temperatures under 0 °C results in the formation of a self-arranged ordered porous structure at the top surface of the sample. This perforated surface structure initiates the growth of an ordered array of titania nanotubes. The inner diameter of nanotubes can be modified in a controlled fashion in the range from 10 nm to more than 250 nm through the change of the electrolyte temperature from −20 °C to + 50 °C. The spectral distribution of cathodoluminescence from a cluster of nanotubes clearly demonstrates the formation of resonator modes which are separated from each other by around 200 meV.     

Effect of hot water and heat treatment on the apatite-forming ability of titania films formed on titanium metal via anodic oxidation in acetic acid solutions

Titanium and its alloys have been widely used for orthopedic implants because of their good biocompatibility. We have previously shown that the crystalline titania layers formed on the surface of titanium metal via anodic oxidation can induce apatite formation in simulated body fluid, whereas amorphous titania layers do not possess apatite-forming ability. In this study, hot water and heat treatments were applied to transform the titania layers from an amorphous structure into a crystalline structure after titanium metal had been anodized in acetic acid solution. The apatite-forming ability of titania layers subjected to the above treatments in simulated body fluid was investigated. The XRD and SEM results indicated hot water and/or heat treatment could greatly transform the crystal structure of titania layers from an amorphous structure into anatase, or a mixture of anatase and rutile. The abundance of Ti–OH groups formed by hot water treatment could contribute to apatite formation on the surface of titanium metals, and subsequent heat treatment would enhance the bond strength between the apatite layers and the titanium substrates. Thus, bioactive titanium metals could be prepared via anodic oxidation and subsequent hot water and heat treatment that would be suitable for applications under load-bearing conditions.     

长程有序纳米孔氧化铝模板的制备与研究

以硫酸和草酸溶液为电解液,采用二次阳极氧化法制备出高度长程有序的纳米孔氧化铝(AAO)模板,并结合扫描电子显微镜(SEM)对其微观结构及形貌进行了观察和表征.通过研究不同的氧化电压和电解液浓度对AAO模板纳米孔形貌(孔径、孔间距、面密度和长程有序性)的影响,得到了最佳的氧化电压和电解液浓度.     

Fabrication of hydrogen sensors with transparent titanium oxide nanotube-array thin films as sensing elements

Transparent thin films comprised of highly ordered titania nanotube-arrays were grown from titanium thin films using an anodization technique, from which highly sensitive and selective hydrogen sensors that can operate at room temperature were fabricated. Titanium films sputter deposited on glass at 500 °C were anodized in a fluorine-containing electrolyte to obtain nanotube-array films. Precise monitoring of current during the anodization enabled removal of the samples from the anodization bath at a point where the remaining metal layer became discontinuous, without destroying the nanotube architecture. The samples were then annealed in oxygen at 420 °C to crystallize the nanotube-arrays as well as oxidize any un-anodized metallic regions, yielding transparent films comprised of titanium oxide nanotube-arrays. Herein, we discuss the morphology, structure and optical characterization of these films. When coated with a 10-nm discontinuous palladium layer, the optically transparent nanotube-array films serve as excellent hydrogen sensors, exhibiting a four-order magnitude drop in resistance with exposure to 1000 ppm hydrogen at room temperature.     

不同制备条件对二氧化钛纳米管阵列及其结构的影响

采用阳极氧化法以NH4F/乙二醇为电解液制备高度有序的TiO2纳米管,研究了不同电解液浓度、电解电压、电解时间等参数对TiO2纳米管的影响.在不同温度下对TiO2纳米管进行退火处理.分别利用转靶X射线衍射仪(XRD)和场发射扫描电子显微镜(SEM)对TiO2纳米管阵列的物相结构和形貌变化进行表征.结合氧化过程电流密度变...     

Supercapacitance of ruthenium oxide deposited on titania and titanium substrates

Titanium planar sheet formed by a chemical polishing process and titania nanotube array formed by an electrochemical anodization process are used as electrode substrates, on which electroactive ruthenium oxides are deposited by an electroreduction and electrooxidation process for supercapacitor applications. Morphological characterization and electrochemical properties of the electrode substrates and ruthenium oxide electrodes have been investigated. Crystalline titania nanotube array shows a much higher electric double layer capacitance than titanium planar sheet due to its high surface area of nanotube walls. Additionally, the well-defined ruthenium oxide–titania/titanium nanotube array electrode exhibits a much higher redox supercapacitance and a lower capacitance decay than ruthenium oxide/titanium planar film electrode. Such a superior energy-storage performance of ruthenium oxide–titania/titanium is ascribed to highly accessible nanotube channels for the reversible redox reaction of ruthenium oxide. The modification strategy of ruthenium oxide electrode by introducing highly ordered nanotube array structure instead of planar film structure can significantly improve specific capacitance as well as cyclic charge-discharge stability.     

Controlled release of phenytoin for epilepsy treatment from titania and silica based materials

Template technique was used to obtain well ordered nanostructured materials: mesoporous silica and nanostructured titania tubes. This technique permits the synthesis of solids with controlled mesoporosity, where a large variety of molecules that have therapeutic activity can be hosted and further released to specific sites. In this work phenytoin (PH), a drug used in epilepsy treatment, was loaded in ordered mesoporous silica (SBA 15) and nanostructured titania tubes (TiO₂). The pure materials and those containing PH were characterized by X-ray diffraction, FTIR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N₂ adsorption–desorption at 77 K. In order to determine the loading capacity of the antiepileptic drug on these silica- and titania-based materials, the loading and release of PH was investigated using UV–vis spectroscopy. Tubular structures were found for the titania samples, for which the X-ray diffractograms showed to be formed by anatase and rutile phases. On the other hand, an amorphous phase was found in the silica sample. A highly ordered hexagonal structure of 1D cylindrical channels was also observed for this material. Loaded PH showed a good stability inside the used materials as observed by spectroscopy analysis. The adsorption and desorption of PH are faster in nanostructured TiO₂ tubes than in mesoporous silica matrix.