The preparation of highly ordered TiO2 nanotube arrays by an anodization method and their applications

The tubular-shaped nanostructure of TiO(2) is very interesting, and highly ordered arrays of TiO(2) nanotubes (TNTs) can be easily fabricated by anodization of the Ti substrate in specific electrolytes. Here in this feature article, we review synthesis methods for various TNTs including normal, alloy, and architectural forms such as bamboos, lace, and flowers. Specific nanosize architectures such as bamboo and lace types can be regulated by alternating voltage and further anodizing. In order to extend light response of TNTs to visible solar spectra, various dopings of specific elements have been discussed. The normal and modified TNTs are suggested for applications such as dye sensitized solar cells, water splitting, photocatalytic degradation of pollutants, CO(2) reduction, sensors, energy storage devices including Li ion batteries and supercapacitors, and other applications such as flexible substrate and biomaterials.     

Flexible fiber-type dye-sensitized solar cells based on highly ordered TiO2 nanotube arrays

A double-sided, transparent conducting and flexible dye-sensitized solar cell (DSSC) was developed. The device comprised two metal electrodes whereby the working electrode consisted of highly ordered titania (TiO₂) nanotube arrays. The maximum conversion efficiency of the DSSC was 5.1% and decreased by 6% under a 90° bending. Surface treatment of the TiO₂ nanotube arrays in niobium isopropoxide solution lifted the conversion efficiency to 6.8%.     

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%.     

Fabrication of multi-sectional TiO 2 nanotube arrays by anodization

We report a facile method to grow multi-sectional TiO₂ nanotube arrays consisting of alternating bamboo-shaped and smooth-walled nanotube sections by anodization. Two key factors are necessary for obtaining these morphologies. First, in order to avoid possible disruptions between the conjoint sections of the nanotube, the distribution of hydrogen ions is suggested not to be fiercely disturbed when switching from the first to the second stage. Second, to avoid the disruption of the nanotube at the joint which results from the disparity in diameters between sections, the direct current voltage is set to be the maximum of the square wave voltage. These newly developed TiO₂ nanotube arrays are expected to have potential applications in solar cells, drug release and delivery systems.     

Fabrication and supercapacitive performance of long anodic TiO2 nanotube arrays using constant current anodization

A galvanostatic anodization is used to prepare long TiO₂ nanotube arrays (TNTAs). TNTAs of over 100 μm in length, with similar nanotube size and structural regularity to the classic TNTAs made from potentiostatic mode, are achieved at 10 mA cm^− 2. After a post-anodization in a H₃PO₄-based electrolyte, the TNTAs with long nanotubes exhibit good adhesion to Ti substrate. The as-prepared long TNTAs yield a larger areal capacitance of 128.4 mF cm^− 2. Further, the long TNTAs possess a higher surface area, making them suitable as support templates for other active materials.     

Fabrication of self-organized TiO2 nanotube arrays for photocatalytic reduction of CO2

The photocatalytic conversion of CO₂ and H₂O to alcohols was achieved using self-organized TiO₂ nanotube arrays (TNAs), which were prepared by electrochemical anodization of Ti foils in 1 M (NH₄)₂SO₄ electrolyte containing 0.5 wt% NH₄F. Experimental results revealed that the morphology and structure of self-organized TNAs could be strongly influenced by the applied voltage and anodization temperature, and the optimized TNAs were prepared by electrochemical anodization of Ti foils under optimal conditions (i.e., at 20 V for 2 h at 30 °C). The as-prepared TNAs were amorphous and could be transformed to anatase phase during the thermal treatment at 450 °C in air for 3 h. By using the annealed TNAs as a photocatalyst, the photocatalytic reduction of CO₂ to alcohol, predominately methanol and ethanol, was demonstrated under Xenon lamp illumination. Based on the photocatalytic measurements, the production rates of methanol and ethanol were calculated to be ～10 and ～9 nmol cm^?2 h^?1, respectively. In addition, the formation mechanism of methanol and ethanol was also tentatively proposed.     

Photocatalytic decompositions of gaseous HCHO and methylene blue with highly ordered TiO_2 nanotube arrays

The highly ordered Ti O_2nanotubes(NTs) were fabricated by the anodic oxidation method.Their morphology,structure and crystalline phase were characterized by scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The effects of morphology,specific surface area,pore structures and photocatalytic activity of the Ti O_2 NTs were investigated.UV–vis spectra analysis showed that its light absorption had been extended to the visible light range.The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic oxidation of gaseous HCHO and MB aqueous solution.The samples had better adhesion strength in the dark and showed a higher photocatalytic activity than nanoparticles.Especially,with ultraviolet light pretreatment,the nanotubes exhibited more stable active for photocatalytic decomposition and the photodecomposition rate remained at high level after 3 cycles of the photocatalysis experiment.Thus,how the number of surface active group ·OH increased and the mechanism for the great improvement for the photocatalytic activity are discussed.     

Optimizing TiO2 nanotube morphology for enhanced photocatalytic H2 evolution using single-walled and highly ordered TiO2 nanotubes decorated with dewetted Au nanoparticles

In the present work we introduce the formation of highly ordered single-walled TiO₂ nanotubes based on anodizing nanoimprinted titanium substrates. In a first step, anodization on nanoimprinted substrates leads to the formation of highly ordered TiO₂ nanotubes. These as-formed TiO₂ nanotubes have a double-walled nature. After an optimized chemical treatment in piranha solution, the inner wall is removed and an array of single-walled TiO₂ nanotubes is obtained that has a high degree of hexagonal ordering. These single walled arrangements show an enhanced photocatalytic activity for H₂ evolution in comparison with classic self-ordered TiO₂ nanotubes.     

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.     

Evaluation of asphaltene degradation on highly ordered TiO2 nanotubular arrays via variations in wettability

Photocatalytic degradation of both aquatic and atmospheric organic pollutants on titanium dioxide has been extensively investigated in the past decades, but research on direct photocatalytic degradation of solid-phase organic pollutants is rather limited. In this work, photocatalytic degradation of n-C(7) asphaltene, which is composed of solid-phase organic substances found in crude oil, on highly ordered TiO(2) nanotubular arrays (TNAs) was studied using the wettability as an indicator. It was observed that the water contact angle rose linearly with increasing the concentration of n-C(7) asphaltene solution up to 0.02 g mL(-1). Further increasing the concentration of n-C(7) asphaltene only caused small augment in the contact angle, which eventually became stable around 98°. It is demonstrated that the water contact angle can be used as an indicator to reflect the residual solid-phase organic pollutants within a certain range of pollutant concentration. As observed, n-C(7) asphaltene film degraded on TNAs under UV illumination for 60 min, showing complete mineralization of ～80% of n-C(7) asphaltene that was released into air finally. The remaining 20% of asphaltene was partially decomposed into smaller organic molecules, e.g., -C(═O)- and -C(═O)-OH, confirmed by high-resolution X-ray photoelectron spectra analysis. TNAs can be reused to degrade the solid-phase n-C(7) asphaltene for a number of cycles without further treatment.     

Fabrication of multi-sectional TiO_2 nanotube arrays by anodization

We report a facile method to grow multi-sectional TiO2 nanotube arrays consisting of alternating bamboo-shaped and smooth-walled nanotube sections by anodization.Two key factors are necessary for obtaining these morphologies.First,in order to avoid possible disruptions between the conjoint sections of the nanotube,the distribution of hydrogen ions is suggested not to be fiercely disturbed when switching from the first to the second stage.Second,to avoid the disruption of the nanotube at the joint which resu...     

Ultrahigh sensitivity assays for human cardiac troponin I using TiO2 nanotube arrays

Rapid, highly sensitive troponin assays for the analysis of serum at the point-of-care are particularly desirable for the effective treatment of myocardial infarction (MYI). TiO(2) nanotube arrays constitute a low cost, high surface area, semiconducting architecture with great promise for biosensing applications due to their compatibility with multiple detection techniques. Using TiO(2) nanotube arrays functionalized with highly robust and ordered carboxyalkylphosphonic acid self-assembled monolayers, we have developed a simple and highly sensitive fluorescence immunoassay which can detect concentrations of human cardiac troponin I as low as 0.1 pg ml(-1) without the use of enzymatic amplification. Varying the morphological parameters of the nanotube arrays allows tuning the detection range over 6 orders of magnitude of the troponin concentration from 0.1 pg ml(-1)-100 ng ml(-1).     

Nanostructured ultrathin catalyst layer with ordered platinum nanotube arrays for polymer electrolyte membrane fuel cells

Fabrication of novel electrode architectures with nanostructured ultrathin catalyst layers is an effective strategy to improve catalyst utilization and enhance mass transport for polymer electrolyte membrane fuel cells (PEMFCs).Herein,we report the design and construction of a nanostructured ultrathin catalyst layer with ordered Pt nanotube arrays,which were obtained by a hard-template strategy based on ZnO,via hydrothermal synthesis and magnetron sputtering for PEMFC application.Because of the crystallographically preferential growth of Pt (111) facets,which was attributed to the structural effects of ZnO nanoarrays on the Pt nanotubes,the catalyst layers exhibit obviously higher electrochemical activity with remarkable enhancement of specific activity and mass transport compared with the state-of-the-art randomly distributed Pt/C catalyst layer.The PEMFC fabricated with the as-prepared catalyst layer composed of optimized Pt nanotubes with an average diameter of 90(±10) nm shows excellent performance with a peak power density of 6.0W/mg~(Pt) at 1 A/cm~2,which is 11.6%greater than that of the conventional Pt/C electrode.     

Photocatalytic decompositions of gaseous HCHO and methylene blue with highly ordered TiO2 nanotube arrays

The highly ordered Ti O₂nanotubes（NTs） were fabricated by the anodic oxidation method.Their morphology,structure and crystalline phase were characterized by scanning electron microscopy（SEM） and X-ray diffractometer（XRD）.The effects of morphology,specific surface area,pore structures and photocatalytic activity of the Ti O₂ NTs were investigated.UV–vis spectra analysis showed that its light absorption had been extended to the visible light range.The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic oxidation of gaseous HCHO and MB aqueous solution.The samples had better adhesion strength in the dark and showed a higher photocatalytic activity than nanoparticles.Especially,with ultraviolet light pretreatment,the nanotubes exhibited more stable active for photocatalytic decomposition and the photodecomposition rate remained at high level after 3 cycles of the photocatalysis experiment.Thus,how the number of surface active group ·OH increased and the mechanism for the great improvement for the photocatalytic activity are discussed.     

Fabrication of aligned TiO2 one-dimensional nanostructured arrays using a one-step templating solution approach

In this letter, we report a one-step templating synthetic strategy to prepare aligned TiO2 nanotube and nanowire arrays on Si substrate from a solution at ambient temperature. The deposition of TiO2 and the selective-etching of the ZnO template proceeded at the same time through the careful control of process parameters. The different thickness of TiO2 sheaths, leading to the formation of nanotubes or nanorods, can be precisely controlled by the deposition time. The idea of selective etching and deposition is applicable to other oxide materials, and such a facile method is expected to find widespread applications.     

Fabrication and characterization of ordered microsized tubular TiO2 films by using various anodizing conditions

In this study, we investigated the oxidation process of titanium in two different electrolytic solutions in order to understand the effect of the electrolyte on the microsized tubular TiO₂ formation and their structure. In the first set of experiments, we used 0.5% HF electrolyte by applying 23?V for 50?min. The second set of experiments was performed using glycerol electrolyte with 0.27?M NH₄F and 1.5% H₂O under 40?V for 19?h. Both experiments were performed at room temperature. After the anodizing process, the samples were annealed at 550?°C in O₂ atmosphere. In both electrolytic conditions well-ordered microsized tubular TiO₂ were obtained. The morphologies, structures, and microsized tubular TiO₂ array films were characterized by FE-SEM, EDS, and XRD.     

Assembly of highly ordered 2D arrays of silver-PNIPAM hybrid microgels

A strategy was developed for the synthesis of highly ordered 2D arrays of Ag-PNIPAM hybrid microgel.The highly ordered 2D arrays of PNIPAM microgel were prepared by dispersing PNIPAM microgel on a charge-reversible substrate.The microgel spheres self-assembled into a 3D colloidal crystal,and the first 111 plane was fixed in situ onto the substrate as a result of spontaneous charge reversal of the substrate,leaving a high-quality 2D array of PNIPAM microgel.Ag nanoparticles were then synthesized in situ inside the microgel spheres by introduction of Ag+ ions into the microgel spheres and reduction with sodium borohydride.The resulting 2D arrays are highly ordered.The inter-particle distance in the array can be tuned.In addition,the method allows the synthesis of large size arrays and the use of nonplanar substrate.     

Adsorption and photoelectrocatalytic characteristics of organics on TiO2 nanotube arrays

The adsorption and photoelectrocatalytic characteristics of four different kinds of organic compounds (d-fructose, glutamic acid, fumaric acid, and nicotinic acid) on TiO₂ nanotube arrays (TNAs) were investigated using a thin-layer cell, wherein the compounds were rapidly and exhaustively oxidized. The photogenerated current–time (I _ph–t) profiles were found to be related to the adsorption, the degradation rate, and the reaction mechanism. The relationship between the initial organic compounds concentrations and photocurrent peaks (I _0ph) fit the Langmuir type adsorption model well, thereby confirming that the adsorption of organic compounds on TNAs was via monolayer adsorption. The adsorption equilibrium constant was obtained from the Langmuir equation. The results indicate that the adsorption performance of the organic compounds on TNAs were in the following order: nicotinic acid < d-fructose < glutamic acid < fumaric acid. The degradation of organic compounds on TNAs was classified as either easy or difficult based on the time of complete mineralization (t _end) of the organic samples under an equal holes consumption; the degree of degradation were as follows: fumaric acid < d-fructose < glutamic acid < nicotinic acid. The photoelectrocatalytic characteristics of the organic compounds on TNAs were also discussed by analyzing the changes in the I _ph –t profiles.     

Preparation of dye-sensitized solar cells using template free TiO2 nanotube arrays for enhanced power conversion

Journal of Sol-Gel Science and Technology - By using the vertically aligned ZnO nanorod arrays (NRAs), TiO2 nanoparticles attached ZnO nanorods (TiO2@ZnO) and TiO2 nanotube arrays (NTAs) were...