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Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

In this study, we used the electrochemical anodization to prepare TiO2 nanotube arrays and applied them on the photoelectrode of dye-sensitized solar cells. In the field emission scanning electron microscopy analysis, the lengths of TiO2 nanotube arrays prepared by electrochemical anodization can be obtained with approximately 10 to 30 μm. After titanium tetrachloride (TiCl4) treatment, the walls of TiO2 nanotubes were coated with TiO2 nanoparticles. XRD patterns showed that the oxygen-annealed TiO2 nanotubes have a better anatase phase. The conversion efficiency with different lengths of TiO2 nanotube photoelectrodes is 3.21%, 4.35%, and 4.34% with 10, 20, and 30 μm, respectively. After TiCl4 treatment, the efficiency of TiO2 nanotube photoelectrode for dye-sensitized solar cell can be improved up to 6.58%. In the analysis of electrochemical impedance spectroscopy, the value of Rk (charge transfer resistance related to recombination of electrons) decreases from 26.1 to 17.4 Ω when TiO2 nanotubes were treated with TiCl4. These results indicate that TiO2 nanotubes treated with TiCl4 can increase the surface area of TiO2 nanotubes, resulting in the increase of dye adsorption and have great help for the increase of the conversion efficiency of DSSCs.

Self-aligned nanoporous TiO2templates synthesized via dc current electrochemical anodization have been carefully analyzed. The influence of environmental temperature during the anodization, ranging from 2 °C to ambient, on the structure and morphology of the nanoporous oxide formation has been investigated, as well as that of the HF electrolyte chemical composition, its concentration and their mixtures with other acids employed for the anodization. Arrays of self-assembled titania nanopores with inner pores diameter ranging between 50 and 100 nm, wall thickness around 20–60 nm and 300 nm in length, are grown in amorphous phase, vertical to the Ti substrate, parallel aligned to each other and uniformly disordering distributed over all the sample surface. Additional remarks about the photoluminiscence properties of the titania nanoporous templates and the magnetic behavior of the Ni filled nanoporous semiconductor Ti oxide template are also included.

Controllable nanostructures in spin coated titanium oxide (TiO2) films have been achieved by a very simple means, through change of post deposition annealing temperature. Electron beam imaging and reciprocal space analysis revealed as-deposited TiO2 films to be characterized by a dominant anatase phase which converts to the rutile form at 600 °C and reverts to the anatase modification at 1,200 °C. The phase changes are also accompanied by changes in the film microstructure: from regular nanoparticles (as-deposited) to nanowires (600 °C) and finally to dendrite like shapes at 1,200 °C. Photoluminescence studies, Raman spectral results, and X-ray diffraction data also furnish evidence in support of the observed solid state phase transformations in TiO2.

Controllable nanostructures in spin coated titanium oxide (TiO2) films have been achieved by a very simple means, through change of post deposition annealing temperature. Electron beam imaging and reciprocal space analysis revealed as-deposited TiO2films to be characterized by a dominant anatase phase which converts to the rutile form at 600 °C and reverts to the anatase modification at 1,200 °C. The phase changes are also accompanied by changes in the film microstructure: from regular nanoparticles (as-deposited) to nanowires (600 °C) and finally to dendrite like shapes at 1,200 °C. Photoluminescence studies, Raman spectral results, and X-ray diffraction data also furnish evidence in support of the observed solid state phase transformations in TiO2.

An innovative fabrication method to produce a macroporous Si surface by employing an anodic aluminium oxide (AAO) nanopore array layer as an etching template is presented. Combining AAO with a reactive ion etching (RIE) processes, a homogeneous and macroporous silicon surface can be effectively configured by modulating AAO process parameters and alumina film thickness, thus hopefully replacing conventional photolithography and electrochemical etch methods. The hybrid process integration is considered fully CMOS compatible thanks to the low-temperature AAO and CMOS processes. The gas-sensing characteristics of 50 nm TiO2 nanofilms deposited on the macroporous surface are compared with those of conventional plain (or non-porous) nanofilms to verify reduced response noise and improved sensitivity as a result of their macroporosity. Our experimental results reveal that macroporous geometry of the TiO2 chemoresistive gas sensor demonstrates 2-fold higher (∼33%) improved sensitivity than a non-porous sensor at different levels of oxygen exposure. In addition, the macroporous device exhibits excellent discrimination capability and significantly lessened response noise at 500 °C. Experimental results indicate that the hybrid process of such miniature and macroporous devices are compatible as well as applicable to integrated next generation bio-chemical sensors.

Doping with other elements is one of the efficient ways to modify the physical and chemical properties of TiO2 nanomaterials. In the present work, anatase TiO2 nanofilms doped with Al and V elements were fabricated through anodic oxidation of Ti6Al4V alloy and further annealing treatment. Hydrogen sensing behavior of the crystallized Ti-Al-V-O nanofilms at various working temperatures was investigated through exposure to 1,000 ppm H2. Different from n-type hydrogen sensing characteristics of undoped TiO2 nanotubes, the Al- and V-doped nanofilms presented a p-type hydrogen sensing behavior by showing increased resistance upon exposure to the hydrogen-containing atmosphere. The Ti-Al-V-O nanofilm annealed at 450°C was mainly composed of anatase phase, which was sensitive to hydrogen-containing atmosphere only at elevated temperatures. Annealing of the Ti-Al-V-O nanofilm at 550°C could increase the content of anatase phase in the oxide nanofilm and thus resulted in a good sensitivity and resistance recovery at both room temperature and elevated temperatures. The TiO2 nanofilms doped with Al and V elements shows great potential for use as a robust semiconducting hydrogen sensor.

The vertically orientated TiO2 nanotube array (TNA) decorated with TiO2 nano-particles was successfully fabricated by electrochemically anodizing titanium (Ti) foils followed by Ti-precursor post-treatment and annealing process. The TNA morphology characterized by SEM and TEM was found to be filled with TiO2 nano-particles interior and exterior of the TiO2 nano-tubes after titanium (IV) n-butoxide (TnB) treatment, whereas TiO2 nano-particles were only found inside of TiO2 nano-tubes upon titanium tetrachloride (TiCl4) treatment. The efficiency in TNA-based DSSCs was improved by both TnB and TiCl4 treatment presumably due to the increase of dye adsorption.

Highly crystalline TiO2 nanostructures were prepared through a facile inorganic acid-assisted hydrothermal treatment of hexagonal-structured assemblies of nanocrystalline titiania templated by cetyltrimethylammonium bromide (Hex-ncTiO2/CTAB Nanoskeleton) as starting materials. All samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of hydrochloric acid concentration on the morphology, crystalline and the formation of the nanostructures were investigated. We found that the morphology and crystalline phase strongly depended on the hydrochloric acid concentrations. More importantly, crystalline phase was closely related to the morphology of TiO2 nanostructure. Nanoparticles were polycrystalline anatase phase, and aligned nanorods were single crystalline rutile phase. Possible formation mechanisms of TiO2 nanostructures with various crystalline phases and morphologies were proposed.

Highly crystalline TiO2 nanostructures were prepared through a facile inorganic acid-assisted hydrothermal treatment of hexagonal-structured assemblies of nanocrystalline titiania templated by cetyltrimethylammonium bromide (Hex-ncTiO2/CTAB Nanoskeleton) as starting materials. All samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of hydrochloric acid concentration on the morphology, crystalline and the formation of the nanostructures were investigated. We found that the morphology and crystalline phase strongly depended on the hydrochloric acid concentrations. More importantly, crystalline phase was closely related to the morphology of TiO2 nanostructure. Nanoparticles were polycrystalline anatase phase, and aligned nanorods were single crystalline rutile phase. Possible formation mechanisms of TiO2 nanostructures with various crystalline phases and morphologies were proposed.

Hierarchical anatase TiO2 nano-architecture arrays consisting of long TiO2 nanowire trunk and numerous short TiO2 nanorod branches on transparent conductive fluorine-doped tin oxide glass are successfully synthesized for the first time through a facile one-step hydrothermal route without any surfactant and template. Dye-sensitized solar cells based on the hierarchical anatase TiO2 nano-architecture array photoelectrode of 18 μm in length shows a power conversion efficiency of 7.34% because of its higher specific surface area for adsorbing more dye molecules and superior light scattering capacity for boosting the light-harvesting efficiency. The present photovoltaic performance is the highest value for the reported TiO2 nanowires array photoelectrode.

The as-grown structure of electrochemically synthesized titania nanotube arrays is investigated by scanning electron microscope (SEM) in combination with transmission electron microscope (TEM) as well as X-ray diffraction (XRD). The analysis reveals a preferred growth direction of the nanotubes relative to the substrate surface and the well control on the nanotube arrays morphology. The crystal structure of the anatase phase is detected and exists in the tube walls without any thermal treatment, which makes it possible to realize the application of as-formed TiO2 nanotubes avoiding the degradation of the nanotube structures when sintering. In addition, a new growth, layered model of the anodic TiO2 nanotubes is presented to obtain further understanding of the growth mechanism.

Uniform, spherical-shaped TiO2:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl3·6H2O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the 5D0 - 7Fj transition of Eu+3 ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions.

An efficient method based in template wetting is applied for fabrication of ordered Poly(9,9-dioctylfluorene) (PFO) nanopillars with β-phase morphology. In this process, nanoporous alumina obtained by anodization process is used as template. PFO nanostructures are prepared under ambient conditions via infiltration of the polymeric solution into the pores of the alumina with an average pore diameter of 225 nm and a pore depth of 500 nm. The geometric features of the resulting structures are characterized with environmental scanning electron microscopy (ESEM), luminescence fluorimeter (PL) and micro μ-X-ray diffractometer (μ-XRD). The characterization demonstrates the β-phase of the PFO in the nanopillars fabricated. Furthermore, the PFO nanopillars are characterized by Raman spectroscopy to study the polymer conformation. These ordered nanostructures can be used in optoelectronic applications such as polymer light-emitting diodes, sensors and organic solar cells.

We improve the conversion efficiency of Ag2S quantum dot (QD)-sensitized TiO2 nanotube-array electrodes by chemically depositing ZnO recombination barrier layer on plain TiO2 nanotube-array electrodes. The optical properties, structural properties, compositional analysis, and photoelectrochemistry properties of prepared electrodes have been investigated. It is found that for the prepared electrodes, with increasing the cycles of Ag2S deposition, the photocurrent density and the conversion efficiency increase. In addition, as compared to the Ag2S QD-sensitized TiO2 nanotube-array electrode without the ZnO layers, the conversion efficiency of the electrode with the ZnO layers increases significantly due to the formation of efficient recombination layer between the TiO2 nanotube array and electrolyte.

We present a novel method to fabricate complete and highly oriented anodic titanium oxide (ATO) nano-porous structures with uniform and parallel nanochannels. ATO nano-porous structures are fabricated by anodizing a Ti-foil in two different organic viscous electrolytes at room temperature using a two-step anodizing method. TiO2 nanotubes covered with a few nanometer thin nano-porous layer is produced when the first and the second anodization are carried out in the same electrolyte. However, a complete titania nano-porous (TNP) structures are obtained when the second anodization is conducted in a viscous electrolyte when compared to the first one. TNP structure was attributed to the suppression of F-rich layer dissolution between the cell boundaries in the viscous electrolyte. The structural morphologies were examined by field emission scanning electron microscope. The average pore diameter is approximately 70 nm, while the average inter-pore distance is approximately 130 nm. These TNP structures are useful to fabricate other nanostructure materials and nanodevices.

This study reports the deposition of cuprous oxide [Cu2O] onto titanium dioxide [TiO2] nanowires [NWs] prepared on TiO2/glass templates. The average length and average diameter of these thermally oxidized and evaporated TiO2 NWs are 0.1 to 0.4 μm and 30 to 100 nm, respectively. The deposited Cu2O fills gaps between the TiO2 NWs with good step coverage to form nanoshells surrounding the TiO2 cores. The p-Cu2O/n-TiO2 NW heterostructure exhibits a rectifying behavior with a sharp turn-on at approximately 0.9 V. Furthermore, the fabricated p-Cu2O-shell/n-TiO2-nanowire-core photodiodes exhibit reasonably large photocurrent-to-dark-current contrast ratios and fast responses.

Nanostructures composited of vertical rutile TiO2 nanorod arrays and Sb2S3 nanoparticles were prepared on an F:SnO2 conductive glass by hydrothermal method and successive ionic layer adsorption and reaction method at low temperature. Sb2S3-sensitized TiO2 nanorod solar cells were assembled using the Sb2S3-TiO2 nanostructure as the photoanode and a polysulfide solution as an electrolyte. Annealing effects on the optical and photovoltaic properties of Sb2S3-TiO2 nanostructure were studied systematically. As the annealing temperatures increased, a regular red shift of the bandgap of Sb2S3 nanoparticles was observed, where the bandgap decreased from 2.25 to 1.73 eV. At the same time, the photovoltaic conversion efficiency for the nanostructured solar cells increased from 0.46% up to 1.47% as a consequence of the annealing effect. This improvement can be explained by considering the changes in the morphology, the crystalline quality, and the optical properties caused by the annealing treatment.

In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure.

A silicon nanocrystals (Si-ncs) conjugated-polymer-based bulk-heterojunction represents a promising approach for low-cost hybrid solar cells. In this contribution, the bulk-heterojunction is based on Si-ncs prepared by electrochemical etching and poly(3-hexylthiophene) (P3HT) polymer. Photoelectric properties in parallel and vertical device-like configuration were investigated. Electronic interaction between the polymer and surfactant-free Si-ncs is achieved. Temperature-dependent photoluminescence and transport properties were studied and the ratio between the photo- and dark-conductivity of 1.7 was achieved at ambient conditions. Furthermore the porous titanium dioxide (TiO2) nanotubes’ template was used for vertical order of photosensitive Si-ncs/P3HT-based blend. The anodization of titanium foil in ethylene glycol-based electrolyte containing fluoride ions and subsequent thermal annealing were used to prepare anatase TiO2 nanotube arrays. The arrays with nanotube inner diameter of 90 and 50 nm were used for vertical ordering of the Si-ncs/P3HT bulk-heterojunction.

A silicon nanocrystals (Si-ncs) conjugated-polymer-based bulk-heterojunction represents a promising approach for low-cost hybrid solar cells. In this contribution, the bulk-heterojunction is based on Si-ncs prepared by electrochemical etching and poly(3-hexylthiophene) (P3HT) polymer. Photoelectric properties in parallel and vertical device-like configuration were investigated. Electronic interaction between the polymer and surfactant-free Si-ncs is achieved. Temperature-dependent photoluminescence and transport properties were studied and the ratio between the photo- and dark-conductivity of 1.7 was achieved at ambient conditions. Furthermore the porous titanium dioxide (TiO2) nanotubes’ template was used for vertical order of photosensitive Si-ncs/P3HT-based blend. The anodization of titanium foil in ethylene glycol-based electrolyte containing fluoride ions and subsequent thermal annealing were used to prepare anatase TiO2nanotube arrays. The arrays with nanotube inner diameter of 90 and 50 nm were used for vertical ordering of the Si-ncs/P3HT bulk-heterojunction.

Aim

To investigate morphological alterations of malignant cancer cells (T24) of urothelial origin seeded on flat titanium (Ti) and nanotubular titanium dioxide (TiO2) nanostructures.

Methods

Using anodization method, TiO2 surfaces composed of vertically aligned nanotubes of 50-100 nm diameters were produced. The flat Ti surface was used as a reference. The alteration in the morphology of cancer cells was evaluated using scanning electron microscopy (SEM). A computational model, based on the theory of membrane elasticity, was constructed to shed light on the biophysical mechanisms responsible for the observed changes in the contact area of adhesion.

Results

Large diameter TiO2 nanotubes exhibited a significantly smaller contact area of adhesion (P < 0.0001) and had more membrane protrusions (eg, microvilli and intercellular membrane nanotubes) than on flat Ti surface. Numerical membrane dynamics simulations revealed that the low adhesion energy per unit area would hinder the cell spreading on the large diameter TiO2 nanotubular surface, thus explaining the small contact area.

Conclusion

The reduction in the cell contact area in the case of large diameter TiO2 nanotube surface, which does not enable formation of the large enough number of the focal adhesion points, prevents spreading of urothelial cells.

In this paper, hydroxyapatite-carbon nanotube/titania (HA-CNT/TiO2) double layer coatings were successfully developed on titanium (Ti) substrates intended for biomedical applications. A TiO2 coating was firstly developed by anodization to improve bonding between HA and Ti, and then the layer of HA and CNTs was coated on the surface by the sol-gel process to improve the biocompatibility and mechanical properties of Ti. The surfaces of double layer coatings were uniform and crack-free with a thickness of about 7 μm. The bonding strength of the HA-CNT/TiO2 coating was higher than that of the pure HA and HA-CNT coatings. Additionally, in vitro cell experiments showed that CNTs promoted the adhesion of preosteoblasts on the HA-CNT/TiO2 double layer coatings. These unique surfaces combined with the osteoconductive properties of HA exhibited the excellent mechanical properties of CNTs. Therefore, the developed HA-CNT/TiO2 coatings on Ti substrates might be a promising material for bone replacement.

Background

Titania dioxide (TiO2) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO2 photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved.

Methodology/Principal Findings

Using thermal reduction method, here we synthesized silver-nanostructures coated TiO2 thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO2, carbon-doped TiO2 [TiO2 (C)] and nitrogen-doped TiO2 [TiO2 (N)], TiO2 (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO2 (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials.

Conclusion/Significance

Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.

Summary

Two dimensional island arrays and honeycomb patterns consisting of ZnO nanocrystal clusters were fabricated on predefined TiO2 seed patterns prepared by vacuum free, aerosol assisted wet-chemical synthesis. The TiO2 seed patterns were prepared by applying an aerosol of a water soluble titanium complex on hexagonally close-packed polystyrene bead arrays for different lengths of time. Scanning electron microscopy revealed that a dot array grows into a honeycomb shape as increasing amounts of the precursor were deposited. ZnO nucleation on substrates with a dot array and honeycomb patterns resulted in the formation of two discrete patterns with contrasting fill fractions of the materials.