Nitrogen-doped TiO2 nanotube array films with enhanced photocatalytic activity under various light sources

Highly ordered nitrogen-doped titanium dioxide (N-doped TiO(2)) nanotube array films with enhanced photocatalytic activity were fabricated by electrochemical anodization, followed by a wet immersion and annealing post-treatment. The morphology, structure and composition of the N-doped TiO(2) nanotube array films were investigated by FESEM, XPS, UV-vis and XRD. The effect of annealing temperature on the morphology, structures, photoelectrochemical property and photo-absorption of the N-doped TiO(2) nanotube array films was investigated. Liquid chromatography and mass spectrometry were applied to the analysis of the intermediates coming from the photocatalytic degradation of MO. The experimental results showed that there were four primary intermediates existing in the photocatalytic reaction. Compared with the pure TiO(2) nanotube array film, the N-doped TiO(2) nanotubes exhibited higher photocatalytic activity in degradating methyl orange into non-toxic inorganic products under both UV and simulated sunlight irradiation.     

Sodium fluoride-assisted modulation of anodized TiO₂ nanotube for dye-sensitized solar cells application

This work reports the use of sodium fluoride (in ethylene glycol electrolyte) as the replacement of hydrofluoric acid and ammonium fluoride to fabricate long and perpendicularly well-aligned TiO? nanotube (TNT) (up to 21 μm) using anodization. Anodizing duration, applied voltage and electrolyte composition influenced the geometry and surface morphologies of TNT. The growth mechanism of TNT is interpreted by analyzing the current transient profile and the total charge density generated during anodization. The system with low water content (2 wt %) yielded a membrane-like mesoporous TiO? film, whereas high anodizing voltage (70 V) resulted in the unstable film of TNT arrays. An optimized condition using 5 wt % water content and 60 V of anodizing voltage gave a stable array of nanotube with controllable length and pore diameter. Upon photoexcitation, TNTs synthesized under this condition exhibited a slower charge recombination rate as nanotube length increased. When made into cis-diisothiocyanato-bis(2,2?-bipyridyl-4,4?-dicarboxylato) ruthenium(II) bis (tetrabutyl-ammonium)(N719) dye-sensitized solar cells, good device efficiency at 3.33 % based on the optimized TNT arrays was achieved with longer electron time compared with most mesoporous TiO? films.     

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation

Copper and titanium remain relatively plentiful in the earth's crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.     

Enhanced photoelectrochemical cell property from alpha-Fe2O3 nanoparticle decoration on vertically grown TiO2 nanotubes arrays

TiO2 nanotube arrays decorated with alpha-Fe2O3 were prepared by forming a nanotube-like TiO2 film on a Ti sheet using an anodization process, followed by electrochemical deposition to decorate hematite (alpha-Fe2O3) nanoparticles on the TiO2 nanotube arrays. The SEM and XRD results revealed that the alpha-Fe2O3 nanoparticles were homogeneously embedded on the surface of the TiO2 nanotube arrays. The photoelectrochemical properties of the alpha-Fe2O3/TiO2 nanotube arrays as photoanode were studied by photocurrent-potential behavior in 1 M NaOH electrolyte under 100 mW/cm2 UV-Visible light irradiation. Also, the length dependence of TiO2 nanotubes and the amount dependence of alpha-Fe2O3 nanoparticles on the photocatalytic ability were studied and thus the optimum conditions were determined.     

Morphology controlled fabrication and ferroelectric properties of vertically aligned one-dimensional lead titanate nanoarrays

Vertically aligned nanowires and highly uniform nanoporous array thin films of PbTiO(3) are synthesized by varying anodic oxidation conditions of Ti foil followed by hydrothermal reaction in an aqueous Pb(II) acetate trihydrate solution. As-synthesized samples have single crystalline nanowire structure and polycrystalline nanoporous structure, although both are pure PbTiO(3) with a tetragonal phase. The structure of intermediate TiO(2) films obtained from different anodic oxidation conditions determines the structure of the product PbTiO(3). The relationships between these morphological structures and ferroelectric properties are investigated. Piezoresponse force microscopy reveals that both these films show ferroelectricity with clear phase contrast and well-defined hysteresis loops. The saturated longitudinal piezoelectric coefficient field (E(c)) of the nanowire sample is smaller than that of nanoporous thin film. Thus, polarization of nanowire thin film is larger in magnitude and easier to flip than that of nanoporous film.     

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.     

Visible light photoelectrochemical performance of W-loaded TiO2 nanotube arrays: structural properties

Well aligned TiO2 nanotubes were successfully synthesized by anodization of Ti foil at 60 V in a fluorinated bath comprised of ethylene glycol with 5 wt% of NH4F and 5 wt% of H2O2. In order to enhance the visible light absorption and photoelectrochemical response of pure TiO2 nanotube arrays, a mixed oxide system (W-TiO2) was investigated. W-TiO2 nanotube arrays were prepared using radio-frequency (RF) sputtering to incorporate the W into the lattice of TiO2 nanotube arrays. The W atoms occupy the substitutional position within the vacancies of TiO2 nanotube arrays. The as-anodized TiO2 is amorphous in nature while the annealed TiO2 is anatase phase. The mixed oxide (W-TiO2) system in suitable TiO2 phase plays important roles in efficient electron transfers due to the reduction in electron-hole recombination. In this article, the effect of the sputtered W into the as-anodized/annealed TiO2 nanotube arrays on the photoelectrochemical response was presented.     

CeO2修饰的透明TiO2纳米管电极的电致变色器件

采用电化学沉积法在阳极氧化制备的TiO2纳米管阵列管壁上沉积一层CeO2纳米颗粒,再将CeO2修饰的透明TiO2纳米管阵列薄膜对电极与聚三甲基噻吩变色电极组装成透过型电致变色器件.实验结果表明:CeO2修饰的TiO2纳米管阵列薄膜仍保持良好的光透过性,其电荷存储能力比纯TiO2纳米管电极提高了30%.经CeO2修饰的TiO2纳米管改善了器件的性能,与对电极为单一TiO2纳米管阵列的器件相比,其对比度仍保持在38%左右,其褪色时间由1.3 s缩短为0.8 s.电致变色器件快速响应得益于纳米管与纳米颗粒组成的复合结构的高比表面积和快速的电荷传输过程.     

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.     

In situ growth of single-crystal TiO2 nanorod arrays on Ti substrate: Controllable synthesis and photoelectrochemical water splitting

Despite one-dimensional (1D) semiconductor nanostructure arrays attracting increasing attention due to their many advantages,highly ordered TiO2 nanorod arrays (TiO2 NR) are rarely grown in situ on Ti substrates.Herein,a feasible method to fabricate TiO2 NRs on Ti substrates by using a through-mask anodization process is reported.Self-ordered anodic aluminum oxide (AAO) overlaid on Ti substrate was used as a nanotemplate to induce the growth of TiO2 NRs.The NR length and diameter could be controlled by adjusting anodization parameters such as electrochemical anodization voltage,anodization time and temperature,and electrolyte composition.Furthermore,according to the proposed NR formation mechanism,the anodized Ti ions migrate and deposit in the AAO nanochannels to form Ti(OH)4 or amorphous TiO2 NRs under electric field,owing to the confinement effect of the template.Photoelectrochemical tests indicated that,after hydrogenation,the TiO2 NRs presented higher photocurrent density under simulated sunlight and visible light illuminations,suggesting their potential use in photoelectrochemical water splitting,photocatalysis,solar cells,and sensors.     

Enhanced photoelectrochemical current response of titania nanotube array

Self-organized and highly-ordered TiO₂ nanotube array with disjunctive wall-hole structure has been synthesized from titanium foil by potentiostatic–galvanostatic anodization process. The morphology and microstructure of the TiO₂ layer depend greatly on the electrolyzing parameters and electrolyte components. TiO₂ formation mechanism by anodization oxidation is discussed. The crystallized TiO₂/Ti nanotube electrode exhibited a significant enhancement of photoelectrochemical current response in comparison with micrometer-sized TiO₂/Ti multiporous electrode. Such kind of TiO₂ nanotube will have many potential applications in various areas as an outstanding photoelectrochemical material.     

Electrochemical corrosion behaviors of titanium covered by various TiO<Subscript>2</Subscript> nanotube films in artificial saliva

TiO₂ nanotube films obtained by anodization have shown great promise as biomaterials. In the present work, we report on the corrosion behaviors of titanium (Ti) with various TiO₂ nanotubes prepared by using controlled anodization procedures. Special emphasis is put on the impact of film morphologies on the corrosion resistance of the Ti substrate. The corrosion behaviors of Ti with different nanotube films were studied in artificial saliva using open-circuit potential measurement, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques. Ti covered by TiO₂ nanotube films showed the markedly enhanced corrosion resistance properties compared to bare Ti. The existence of the compact oxide layer formed in a fluoride-free electrolyte was found to be beneficial for improving corrosion resistance properties. Besides, the TiO₂ nanotube films obtained by two-step anodization had better corrosion resistance than those obtained by single-step anodization, though they used the identical anodization parameters.     

Self-organized TiO2 nanotube arrays: synthesis by anodization in an ionic liquid and assessment of photocatalytic properties

Self-organized TiO(2) nanotube (NT) arrays were produced by anodization in ethylene glycol (EG) electrolytes containing 1-n-butyl-3-methyl-imidazolium tetrafluoroborate (BMI.BF(4)) ionic liquid and water. The morphology of the as-formed NTs was considerably affected by changing the anodization time, voltage, and water and ionic liquid electrolyte concentrations. In general, a nanoporous layer was formed on the top surface of the TiO(2) NTs, except for anodization at 100 V with 1 vol % of BMI.BF(4), where the NT's mouth was revealed. The length and bottom diameter of the NTs as well as the pore diameter of the top layer showed a linear relationship with increased anodization voltage. These TiO(2) NTs were tested as photocatalysts for methyl orange photodegradation and hydrogen evolution from water/methanol solutions by UV light irradiation. The results show that the TiO(2) NTs obtained by anodization in EG/H(2)O/BMI.BF(4) electrolytes are active and efficient for both applications.     

Free-standing TiO(2) nanotube arrays made by anodic oxidation and ultrasonic splitting

A facile and green method was employed to prepare large-scale free-standing TiO(2) nanotube (TNT) arrays, in which as-anodized TiO(2) nanotube films prepared in organic electrolytes with thickness ranging from seven to tens of micrometers were then ultrasonicated in a mix solution of ethanol and water. By controlling the ratio of ethanol to water, the time and the power of ultrasonication, large-scale free-standing TiO(2) nanotube arrays without any crack could be detached from the Ti substrates. Hydrogen sensing results demonstrated that the free-standing TNT film is more sensitive than a film with Ti substrates when exposed to 1000?ppm hydrogen ambient.     

Site-specific and patterned growth of TiO(2) nanotube arrays from e-beam evaporated thin titanium film on Si wafer

Growth of TiO(2) nanotubes on thin Ti film deposited on Si wafers with site-specific and patterned growth using a photolithography technique is demonstrated for the first time. Ti films were deposited via e-beam evaporation to a thickness of 350-1000?nm. The use of a fluorinated organic electrolyte at room temperature produced the growth of nanotubes with varying applied voltages of 10-60?V (DC) which remained stable after annealing at 500?°C. It was found that variation of the thickness of the deposited Ti film could be used to control the length of the nanotubes regardless of longer anodization time/voltage. Growth of the nanotubes on a SiO(2) barrier layer over a Si wafer, along with site-specific and patterned growth, enables potential application of TiO(2) nanotubes in NEMS/MEMS-type devices.     

Enhanced hydrogen production on porous TiO2 nanotube arrays

Well aligned TiO2 nanotube arrays have been synthesized via anodization in an NH4F and ethylene glycol electrolyte; the resulting carbon-entrained films were treated by oxygen and argon microwave plasma. It was found that as-prepared amorphous TiO2 nanotubes can be easily crystallized into anatase at temperature lower than 150 degrees C. Carbon can be effectively eliminated in oxygen plasma and a new secondary porosity was emerged. It was found such a porous film has obvious photovoltaic and hydrogen production enhancement under simulated solar irradiation compared with that crystallized in inert argon plasma. This phenomenon may be attributed to the improvement of light adsorption and its excellent capability of hole-electron separation derives from highly ordered nanoporous configurations.     

Highly efficient solar cells using TiO(2) nanotube arrays sensitized with a donor-antenna dye

Donor antenna dyes provide an exciting route to improving the efficiency of dye sensitized solar cells owing to their high molar extinction coefficients and the effective spatial separation of charges in the charge-separated state, which decelerates the recombination of photogenerated charges. Vertically oriented TiO(2) nanotube arrays provide an optimal material architecture for photoelectrochemical devices because of their large internal surface area, lower recombination losses, and vectorial charge transport along the nanotube axis. In this study, the results obtained by sensitizing TiO(2) nanotube arrays with the donor antenna dye Ru-TPA-NCS are presented. Solar cells fabricated using an antenna dye-sensitized array of 14.4 microm long TiO(2) nanotubes on Ti foil subjected to AM 1.5 one sun illumination in the backside geometry exhibited an overall conversion efficiency of 6.1%. An efficiency of 4.1% was obtained in the frontside illumination geometry using a 1 microm long array of transparent TiO(2) nanotubes subjected to a TiCl(4) treatment and then sensitized with the Ru-TPA-NCS dye. Open circuit voltage decay measurements give insight into the recombination behavior in antenna-dye sensitized nanotube photoelectrodes, demonstrating outstanding properties likely due to a reduction in the influence of the surface traps and reduced electron transfer from TiO(2) to ions in solution.     

The influence of hydroxide on the initial stages of anodic growth of TiO2 nanotubular arrays

Understanding the mechanism for growing TiO(2) nanotubes is important for controlling the nanostructures. The hydroxide nano-islands on the Ti surface play a significant role at the initial stage of anodization by forming the very first nano-pores at the interface between hydroxide islands and substrate and eliminating the H(2)O electrolysis. A quantitative time dependent SEM study has revealed a nanotube growth process with an initial linear increase of pore diameter, film thickness and number of pores. During the anodization of titanium, different current transient curves are observed for Ti samples with or without hydroxide on the surface. The transient current profile has been quantitatively analyzed by fitting several distinctive stages based on a growth mechanism supported by SEM observations. It is found that a saturated cubic dependent equation is appropriate to fit a short current upturn due to the increase of the surface area.     

Preparation of nanoporous titanium oxide films by electrochemical anodic oxidation

We have investigated the conditions of the formation of tubular layers of nanoporous TiO₂ (NPTO) by the anodic oxidation of Ti in a 1% ammonium fluoride solution in ethylene glycol. The results demonstrate that increasing the anode current density and anodization time increases the nanotube diameter. A model has been proposed for the formation of tubular NPTO layers. The model builds on the concept of anisotropic Ti etching. The rate of the formation of the tubular structure of TiO₂ has been shown to be limited by the oxide film growth rate under the conditions of this study.     

Fabrication of TiO2 Nanotube Arrays by Rectified Alternating Current Anodization

Anodization is a popular method of preparing TiO₂ nanotube array films（TiNTs） by using direct current（DC）power as the driving voltage.In this study,three driving voltage modes,namely,the sine alternating current（sine） mode,the full-wave rectification of sine waves via four diodes（sine-4D,where D means diode） mode,and the DC mode,were used to prepare TiNTs by anodization.At 20 V,TiNTs were formed under sine-4D mode but only irregular porous TiO₂ films were formed under DC mode.At 50 V,TiNTs formed under both the sine-4D and DC modes.No TiNTs formed in the sine mode anodization at either 20 or 50 V.Compared with the DC mode,the sine-4D mode required a lower oxidation voltage for TiNT formation,which suggests that sine-4D is an economical,convenient,and efficient driving voltage for TiNT preparation by anodization.The morphologies and structures of TiNT samples anodized at 50 V in the sine-4D and DC modes at different oxidation time（1,5,10,30,60,and 120 min） were analyzed.TiNT growth processes were similar between the studied modes.However,the growth rate of the films was faster under the sine-4D mode than the DC mode during the first 30 min of anodization.