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.     

Fabrication of TiO2 nanotube arrays of different dimension for photocatalytic decomposition of IPA in air streams

Abstract

TiO₂ nanotube arrays (TNTs) were fabricated by anodization under various operational conditions. Dimensions of fabricated TNTs were significantly influenced by the temperature and water content of ethylene glycol-based electrolyte prepared for anodization. TNTs of longer length, larger inner diameter, and thinner wall thickness were fabricated in electrolytes of higher temperatures. For TNTs fabricated in electrolyte containing higher water contents, the relatively fast dissolution of TiO₂ led to the formation of TNTs of shorter tube length and larger inner diameter. TNTs were fabricated under different anodization conditions (mainly the water content in ethylene glycol electrolyte and anodization time) to exhibit similar tube length and different inner diameters. Experiments conducted using TNTs of longer tube lengths and smaller inner diameters demonstrated higher photocatalytic decompositions of gaseous isopropyl alcohol (IPA); however, the photocatalytic application of TNTs is limited by the penetration of illumination.     

阳极氧化时间对二氧化钛纳米管阵列形貌的影响

采用电化学阳极氧化法,以乙二醇体系作为电解液,在60V的直流电压下,在纯钛基底表面制备高度有序的TiO2纳米管阵列,通过改变氧化时间来探究其对TiO2纳米管阵列形貌的影响。运用XRD、SEM分别对TiO2纳米管阵列的结构、形貌特征进行表征。结果表明,氧化时间对TiO2纳米管的管壁厚度、管径以及管长均有影响;氧化时间为2～2.5h时,所得到的二氧化钛纳米管管壁约为10nm、管径约为200nm、管长为2～3μm。     

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.     

电解液组分对阳极氧化法制备TiO_2纳米管的影响

在不同电解液组分中采用阳极氧化法制备了不同结构参数的TiO2纳米管,考察了不同电解液组分对TiO2纳米管形貌和尺寸参数的影响.采用场发射扫描电子显微镜(SEM)和X射线衍射仪(XRD)对纳米管的形貌和结构进行了表征,并分析了电解液组分对纳米管生长的影响机制.结果表明,降低电解液中H+浓度以及减少电解液中H2O的含量可有效提高纳米管的长度.     

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.     

高长径比TiO2纳米管阵列的调控制备及其光阳极性能

采用较高粘度的有机溶液作为阳极氧化电解质溶剂制备了TiO₂纳米管阵列. 通过探讨阳极氧化工艺参数对纳米管形貌的影响, 研究出高长径比TiO₂纳米管阵列的制备工艺, 同时对TiO₂纳米管作为染料敏化太阳能电池光阳极的光电性能进行了测试, 并讨论了TiO₂纳米管的形貌对电池性能的影响. 结果表明：提高氧化电压和延长时间有利于获得高长径比纳米管, 在含0.5wt%NH₄F乙二醇电解质中50V氧化17h可制备出长径比为313.6的TiO₂纳米管阵列. TiO₂纳米管(在含0.5wt%NH4F乙二醇电解质中40V氧化13h)作为染料敏化太阳能电池光阳极可得到开路电压为0.723V、短路电流为2.15mA/cm²的光电性能.     

Enhanced photocleavage of water using titania nanotube arrays

In this study highly ordered titania nanotube arrays of variable wall thickness are used to photocleave water under ultraviolet irradiation. We demonstrate that the wall thickness and length of the nanotubes can be controlled via anodization bath temperature. We find that the nanotube wall thickness is a key parameter influencing the magnitude of the photoanodic response and the overall efficiency of the water-splitting reaction. For 22 nm inner pore diameter nanotube arrays, those fabricated in a 5 degrees C anodization bath, 224 nm length and 34 nm wall thickness produced a photoanodic response that was thrice that of a nanotube array fabricated in a 50 degrees C anodization bath, 120 nm length and 9 nm wall-thickness. At high anodic polarization, above 1 V, the quantum efficiency under 337 nm illumination was greater than 90%. For the 5 degrees C anodization bath samples (22 nm pore-diameter, 34 nm wall thickness), upon 320-400 nm illumination at an intensity of 100 mW/cm(2), hydrogen gas was generated at the power-time normalized rate of 960 micromol/h W (24 mL/h W) at an overall conversion efficiency of 6.8%. To the best of our knowledge, this hydrogen generation rate is the highest reported for a titania-based photoelectrochemical cell.     

高长径比TiO2纳米管阵列的调控制备及其光阳极性能

采用较高粘度的有机溶液作为阳极氧化电解质溶剂制备了TiO₂纳米管阵列. 通过探讨阳极氧化工艺参数对纳米管形貌的影响, 研究出高长径比TiO₂纳米管阵列的制备工艺, 同时对TiO₂纳米管作为染料敏化太阳能电池光阳极的光电性能进行了测试, 并讨论了TiO₂纳米管的形貌对电池性能的影响. 结果表明：提高氧化电压和延长时间有利于获得高长径比纳米管, 在含0.5wt%NH₄F乙二醇电解质中50V氧化17h可制备出长径比为313.6的TiO₂纳米管阵列. TiO₂纳米管(在含0.5wt%NH4F乙二醇电解质中40V氧化13h)作为染料敏化太阳能电池光阳极可得到开路电压为0.723V、短路电流为2.15mA/cm²的光电性能.     

Fabrication of highly ordered TiO2 nanotube arrays via anodization of Ti-6Al-4V alloy sheet

Uniform and highly ordered TiO2 nanotube arrays were fabricated by the electrochemical anodic oxidation on Ti-6Al-4V surface, using graphite plate as cathode and ethylene glycol (EG) with addition of a certain amount of H2O and NH4F as electrolyte, and the anodization voltage went up to a presetting voltage by stepwise increment. The morphology, structure and composition of TiO2 nanotube arrays were characterized by SEM, EDS, XRD and XPS. The formation process of TiO2 nanotubes was introduced in brief. The experiments were arranged by an orthogonal experiment method and the experimental results showed that the formation of TiO2 nanotube arrays was influenced by not only each factor (F- content, H2O content, external voltage and duration), but also cross correlation among the four factors. The optimal condition was F- content 0.2 wt%, H2O content 4 vol%, external voltage 40 V and duration 1 h in the studied electrochemical system, and the length of obtained nanotubes was 1.5 microm, the outer diameter was approximately 100 nm and the aspect ratio was 15. As-formed nanotube arrays were amorphous and changed to anatase TiO2 after annealed at 500 degrees C for 2 h in air ambience. XPS survey spectra revealed the surface of as-formed nanotube arrays containing Ti, O, C, F and N. The nanotube arrays on Ti-6Al-4V surface with better thermo-stability and crystallinity would have great potential in biomaterials.     

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。     

Self-organized TiO2 nanotubes with controlled dimensions by anodic oxidation

The effect of ammonium fluoride (NH₄F) concentration on the dimensions (length, diameter, and wall thickness) of the self-organized nanotube arrays has been investigated. Results show that varying the concentration of NH₄F exerts a strong effect on changing the dimensions of the as-grown nanotube arrays. The length of the nanotube arrays increases gradually by increasing the concentration up to a maximum length at a concentration of 1.00 wt%, after which the length decreases slightly with the increase in NH₄F concentration. It was also observed that the diameter and wall thickness of the nanotube arrays vary with the change in concentration of NH₄F, where the diameter was found to alter between 80 and 140 nm, and the wall thickness decreases by increasing the NH₄F concentration. These results indicate that it is possible to entirely control the dimensions of the nanotube arrays, by tailoring the concentration of NH₄F besides the anodization time and voltage.     

Efficient growth of aligned SnO2 nanorod arrays on hematite (α-Fe2O3) nanotube arrays for photoelectrochemical and photocatalytic applications

SnO₂ nanorod arrays were fabricated on hematiete nanotube arrays by an efficient hydrothermal method. The hematiete nanotube arrays were prepared by anodization of pure iron foil in an ethylene glycol solution. SnO₂ nanorod arrays grew from the bottom of hematite nanotubes and were firmly combined with the iron foil substrate. The morphology and microstructure of SnO₂ nanorod arrays are investigated by field-emission scanning electron microscopy, grazing incidence X-ray diffraction and UV–Vis absorbance spectra. The sample presented typical SnO₂ nanorod arrays (reacted for 2 h) generally of 400 nm in length and 50 nm in side width showed the best photocatalytic activity and photoelectrochemical response under the UV illumination. It should be attributed to the effective electron–hole separation and the excellent electron transfer pathway along the 1D SnO₂ nanorod arrays and hematiete nanotube arrays.     

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.     

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.     

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.     

Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process

Large area of self-organized, free standing anodic titanium oxide (ATO) nanotube membranes with clean surfaces were facilely prepared to desired lengths via electrochemical anodization of highly pure Ti sheets in an ethylene glycol electrolyte, with a small amount of NH4F and H2O at 50 V, followed by self-detachment of the ATO membrane from the Ti substrate using recycling processes. In the first anodization step, the nanowire oxide layer existed over the well-arranged ATO nanotube. After sufficiently rinsing with water, the whole ATO layer was removed from the Ti sheet by high pressure N2 gas, and a well-patterned dimple layer with a thickness of about 30 nm existed on the Ti substrate. By using these naturally formed nano-scale pits as templates, in the second and third anodization process, highly ordered, vertically aligned, and free standing ATO membranes with the anodic aluminum oxide (AAO)-like clean surface were obtained. The inter-pore distance and diameter was 154 +/- 2 nm and 91+/- 2 nm, the tube arrays lengths for 25 and 46 hours were 44 and 70 microm, respectively. The present study demonstrates a simple approach to producing high quality, length controllable, large area TiO2 membrane.     

自持TiO2纳米管阵列薄膜与TiO2/FTO透明光电极制备工艺的研究

利用电化学阳极氧化法,采用三步氧化工艺,成功制备出大面积高度有序、孔洞分布均匀、孔道垂直取向且与金属钛基相分离的自持TiO2纳米管阵列膜。然后将其转移粘接至FTO导电玻璃上,形成高度有序的TiO2/FTO纳米管阵列透明光电极。利用场发射扫描电镜、X射线衍射仪、紫外-可见-近红外分光光度计分别对样品的形貌、晶相结构以及光学特性做了表征。研究表明,由三步阳极氧化工艺制备的自持TiO2纳米管阵列膜,其结构参数（如管径、管长及管壁厚度）在很大范围内可控,将其转移粘结至FTO导电玻璃上能制成多种用途的高质量透明光电极;另外,阳极氧化电压对TiO2纳米管阵列薄膜的光学能隙（Eg）也有较为明显的调制作用。显然,这项新工艺对基于TiO2纳米有序阵列复合结构的有机-无机光电器件的应用研究将是非常有益的。     

Fast fabrication of long TiO2 nanotube array with high photoelectrochemical property on flexible stainless steel

Oriented highly ordered long TiO2 nanotube array films with nanopore structure and high photoelectrochemical property were fabricated on flexible stainless steel substrate (50 microm) by anodization treatment of titanium thin films in a short time. The samples were characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and photoelectrochemical methods, respectively. The results showed that Ti films deposited at the condition of 0.7 Pa Ar pressure and 96 W sputtering power at room temperature was uniform and dense with good homogeneity and high crystallinity. The voltage and the anodization time both played significant roles in the formation of TiO2 nanopore-nanotube array film. The optimal voltage was 60 V and the anodization time is less than 30 min by anodizing Ti films in ethylene glycerol containing 0.5% (w) NH4F and 3% (w) H2O. The growth rate of TiO2 nanotube array was as high as 340 nm/min. Moreover, the photocurrent-potential curves, photocurrent response curves and electrochemical impedance spectra results indicated that the TiO2 nanotube array film with the nanoporous structure exhibited a better photo-response ability and photoelectrochemical performance than the ordinary TiO2 nanotube array film. The reason is that the nanoporous structure on the surface of the nanotube array can separate the photo electron-hole pairs more efficiently and completely than the tubular structure.     

Self-organized highly ordered TiO2 nanotubes in organic aqueous system

A simple method to achieve self-organized, freestanding TiO₂ nanotube array was constructed, free of corrosive etching process which was traditionally employed to separate TiO₂ nanotubes from the metallic Ti substrate. The TiO₂ nanotube arrays were constructed through potentiostatic anodization of Ti foil in aqueous electrolyte containing NH₄F and ethylene glycol. The nanotubes in the array were of 45 μm lengths and 100 nm average pore diameters. The effect of NH₄F concentration on the length of the self-organized nanotube arrays was investigated. Electrochemical and spectroscopic measurements showed that the as-prepared nanotubes possessed large surface areas, good uniformity, and were ready for enzyme immobilization. The as-prepared nanotube arrays were amorphous, but crystallized with annealing at elevated temperatures, as demonstrated by X-ray diffraction (XRD).