Fabrication of TiO2 nanotubes by using electrodeposited ZnO nanorod template and their application to hybrid solar cells

Vertically aligned TiO₂ nanotubes have been fabricated on the indium-doped tin oxide (ITO) by a simple and versatile technique using the electrochemically deposited ZnO nanorods, oriented along the c-axis, as a template in the spin-on based sol-gel reaction of a Ti precursor. The diameter, length, and shape of TiO₂ nanotubes were controlled by changing the initial ZnO nanorod template and the spin conditions during sol-gel process of a Ti precursor. Scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analysis, and X-ray diffraction (XRD) were used to confirm the successful formation of TiO₂ nanotubes and characterize their structure and morphology. Furthermore, as an application of the TiO₂ nanotubes, hybrid solar cells based on TiO₂ and poly[2-methoxy,5-(2′-ethyl-hexyloxy)1,4-phenylenevinylene] (MEH-PPV) were successfully fabricated.     

Preparation and characterization of CNTs-TiO2 composites

Carbon nanotubes-based TiO₂ composites were fabricated by hydrolysis, and the transmission electron microscopy(TEM) results showed that carbon nanotubes were partly coated with TiO₂. X-ray photoelectron spectroscopy (XPS) results of purified carbon nanotubes indicated that there were some polar oxygenated groups such as C-O, C=O and O-C=O which might stimulate formation of the composites, and enhance the interfacial combination of TiO₂ with carbon nanotubes. The formation of TiO₂ and its compounding with CNTs happened almost simultaneously in this process. The method is a convenient route to fabricate CNTs-based TiO₂ composites with different ratios.     

Synthesis and electrochemical properties of CeO2 nanoparticle modified TiO2 nanotube arrays

In this paper, a cerium dioxide (CeO₂) modified titanium dioxide (TiO₂) nanotube array film was fabricated by electrodeposition of CeO₂ nanoparticles onto an anodized TiO₂ nanotube array. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the CeO₂ nanoparticles grew uniformly on the walls of the TiO₂ nanotubes. The composite was composed of cubic-phase CeO₂ crystallites and anatase-phase TiO₂ after annealing at 450 °C. The cyclic voltammetry and chronoamperometric charge/discharge measurement results indicated that the CeO₂ modification obviously increased the charge storage capacity of the TiO₂ nanotubes. The charge transfer process at the surface, that is, the pseudocapacitance, was the dominate mechanism of the charge storage in CeO₂-modified TiO₂ nanotubes. The greater number of surface active sites resulting from uniform application of the CeO₂ nanoparticles to the well-aligned TiO₂ nanotubes contributed to the enhancement of the charge storage density.     

Immobilization of pamidronic acids on the nanotube surface of titanium discs and their interaction with bone cells

Self-assembled layers of vertically aligned titanium nanotubes were fabricated on a Ti disc by anodization. Pamidronic acids (PDAs) were then immobilized on the nanotube surface to improve osseointegration. Wide-angle X-ray diffraction, X-ray photoelectron microscopy, and scanning electron microscopy were employed to characterize the structure and morphology of the PDA-immobilized TiO₂ nanotubes. The in vitro behavior of osteoblast and osteoclast cells cultured on an unmodified and surface-modified Ti disc was examined in terms of cell adhesion, proliferation, and differentiation. Osteoblast adhesion, proliferation, and differentiation were improved substantially by the topography of the TiO₂ nanotubes, producing an interlocked cell structure. PDA immobilized on the TiO₂ nanotube surface suppressed the viability of the osteoclasts and reduced their bone resorption activity.     

Electrochemical lithium storage of titania nanotubes modified with NiO nanoparticles

The nanotubes of mixed TiO₂(B) and anatase phases, obtained by hydrothermal synthesis and subsequent calcination, are modified with NiO nanoparticles. In the modified products, NiO nanoparticles with poor crystallinity exist inside titania tubes and are attached to the outside surface of the nanotubes according to X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectra (EDS) analysis. The titania nanotubes, modified with 5 wt.% NiO in which NiO nanoparticles were distributed homogenously, exhibit the optimal cycle performance and a good capability for high rate discharge. The lithium ion diffusion is mainly related to the anatase phase, while the electrochemical reaction activity is attributed to the TiO₂(B) phase. Relative to titania nanotubes, NiO-modified nanotubes have a better electrochemical reaction activity, which is beneficial for the improvement of the high rate charge-discharge capability.     

An innovative approach to electro-oxidation of dopamine on titanium dioxide nanotubes electrode modified by gold particles

Au/TiO₂/Ti electrodes were prepared by galvanic deposition of gold particles from an acidic bath containing KAu(CN)₂ in the presence of a citrate buffer onto TiO₂ nanotubes layer on titanium substrates. Titanium oxide nanotubes were fabricated by anodizing titanium foil in a DMSO fluoride-containing electrolyte. The morphology and surface characteristics of Au/TiO₂/Ti electrodes were investigated using scanning electron microscopy and energy-dispersive X-ray, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 40–80 nm diameters. The electro-catalytic behavior of Au/TiO₂/Ti electrodes for the dopamine electro-oxidation was studied by cyclic voltammetry and differential pulse voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electro-catalytic activity toward the oxidation of dopamine. The catalytic oxidation peak current showed a linear dependence on dopamine concentration and a linear calibration curve was obtained in the concentration range of 0.5–2.5 mM of dopamine.     

Crystalline phase of TiO2 nanotube arrays on Ti–35Nb–4Zr alloy: Surface roughness,electrochemical behavior and cellular response

An investigation was made into the electrochemical, structural and biological properties of self-organized amorphous and anatase/rutile titanium dioxide (TiO₂) nanotubes deposited on Ti–35Nb–4Zr alloy through anodization-induced surface modification. The surface of as-anodized and heat-treated TiO₂ nanotubes was analyzed by field emission scanning electron microscopy (FE-SEM), revealing morphological parameters such as tube diameter, wall thickness and cross-sectional length. Glancing angle X-ray diffraction (GAXRD) was employed to identify the structural phases of titanium dioxide, while atomic force microscopy (AFM) was used to measure surface roughness associated with cell interaction properties. The electrochemical stability of TiO₂ was examined by electrochemical impedance spectroscopy (EIS) and the results obtained were correlated with the microstructural characterization. The in vitro bioactivity of as-anodized and crystallized TiO₂ nanotubes was also analyzed as a function of the presence of different TiO₂ polymorphic phases. The results indicated that anatase TiO₂ showed higher surface corrosion resistance and greater cell viability than amorphous TiO₂, confirming that TiO₂ nanotube crystallization plays an important role in the material's electrochemical behavior and biocompatibility.     

Efficient synthesis of titania nanotubes and enhanced photoresponse of Pt decorated TiO2 for water splitting

We investigated the effect of HMT (hexamethylenetetraamine) on the anodic growth of TiO₂ nanotube arrays. The tube length increases to 4.3 μm with HMT concentration increasing to 0.04 mol·L⁻¹. Adsorption of HMT on the TiO₂ surface is shown to markedly decrease the chemical dissolution rate of tube mouth, resulting in longer nanotube length. Furthermore, Pt nanoparticles were successfully deposited on the surface of TiO₂ nanotubes by ac electrodeposition method. The TiO₂/Pt composites were characterized by field emission scanning electron microscope (FESEM), X-ray photoelectron spectra (XPS), and photoelectrochemistry. An enhancement in photocurrent density has been achieved upon modification of TiO₂ nanotubes with Pt nanoparticles.     

Aluminium-doped TiO2 nanotubes with enhanced light-harvesting properties

Titanium dioxide (TiO₂) application in light-harvesting processes is hindered by its wide band gap. Strategies such as morphology shifts from nanoparticles to nanotubes and doping of fabricated nanostructures are widely used to address this issue. Combining both approaches, this work successfully synthesizes, for the first time, aluminium-doped TiO₂ nanotubes via a single-step anodization method at three distinct potentials (20, 40 and 60 V). SEM images revealed the successful formation of remarkably thin layers of TiO₂ nanotubes produced at 40 and 60 V. X-ray diffractograms and Raman spectra suggest the successful insertion of aluminium into the anatase lattice. Diffuse reflectance confirmed the doping process through a marked effect on the absorbance of visible light for the higher voltages, as well as through a reduction in the optical band gap. For utilization purposes, the photoelectrochemical performance of 40 V Al–TiO₂ was able to deliver a comparable response to that of a compact TiO₂ layer of the same thickness. The current density developed by the 60 V sample was increased by 120% in comparison to the undoped material, despite having an absorbance much lower than that of the latter. Overall, synthesizing an Al-doped TiO₂ nanotubular structure has proven to be a great strategy in the development of materials for application in advanced light-harvesting electrodes.     

Preparation of cobalt coated TiO2 and WO3–TiO2 nanotube films via photo-assisted deposition with enhanced photocatalytic activity under visible light illumination

Highly ordered TiO₂ and WO₃–TiO₂ nanotubes were prepared by one-step electrochemical anodizing method and cobalt has been successfully deposited on these nanotubes by photo-assisted deposition process. The morphology, crystal structure, elemental composition and light absorption capability of samples were characterized by field emission scanning electron microscope, X-ray diffraction, energy dispersive X-ray spectrometer and ultraviolet–visible spectroscopy methods. All cobalt loaded samples show an appearance of red shift relative to the unloaded samples. The degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of these novel visible-light-responsive photocatalysts. Results showed that the photocatalytic activity of bare WO₃–TiO₂ samples is higher than that with undoped TiO₂ sample. Compared with unmodified TiO₂ and WO₃–TiO₂, the Co/TiO₂ and Co/WO₃–TiO₂ samples exhibited enhanced photocatalytic activity in the degradation of methylene blue. Kinetic research showed that the reaction rate constant of Co/WO₃–TiO₂ is approximately 2.26 times higher than the apparent reaction rate constant of bare WO₃–TiO₂. This work provides an insight into designing and synthesizing new TiO₂–WO₃ nanotubes-based hybrid materials for effective visible light-activated photocatalysis. The catalysts prepared in this study exhibit industrially relevant interests due to the low cost and high photocatalytic activity.     

Effect of the solvent on growth of titania nanotubes prepared by anodization of Ti in HCl

The effect of the solvent on the anodic growth of titania nanotubes in HCl dissolved in water, ethylene glycol and 2-propanol was studied. These nanotubes grow with locally rapid breakdown of the passive TiO₂ film forming a forest of nanotubes-bearing microtowers with the background of passive TiO₂ Film. These bundles of assembled-groups of titania nanotubes look like Pillars corals. The low relative permittivity of the 2-propanol led to lowering of dissociation of HCl and hence lowering the activity of H⁺ and Cl⁻ ions which in turn led to suppress of dissolution of titania and increasing the growth rate of the titania nanotubes. The X-ray diffraction pattern showed that the titania nanotubes after annealing change to the crystalline anatase phase. The anodic films showed characteristic coloration with intensity and color that changes (qualitatively) with time of anodization.     

Preparation of titania/carbon nanotube composites using supercritical ethanol and their photocatalytic activity for phenol degradation under visible light irradiation

Titanium dioxide (anatase, TiO₂) nanoparticles have been successfully deposited onto multi-walled carbon nanotubes (MWCNTs) via hydrolysis of titanium isopropoxide in supercritical ethanol. The as-prepared composites were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. It was demonstrated that the MWCNTs were decorated with well-dispersed anatase nanoparticles less than 7 nm in diameter. The size and loading content of the nanoparticles on MWCNTs could be tuned by manipulating the ratio of precursor to MWCNTs, and the formation mechanism of the composites was also discussed. The absorbance spectrum of the resultant TiO₂/MWCNT composites extended to the whole UV-visible region due to the decoration of TiO₂ on MWCNTs. The TiO₂/MWCNT composites were used as photocatalyst for phenol degradation under irradiation of visible light, which showed higher efficiency compared to a mixture of TiO₂ and MWCNTs.     

Morphology and Microstructure of As-Synthesized Anodic TiO2 Nanotube Arrays

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.     

Effect of synthesis highly ordered TiO<Subscript>2</Subscript> nanotube arrays with enhanced photocatalytic properties by time,electrolytic voltage,heating temperature and Polyvinyl pyrrolidone

Highly ordered TiO₂ nanotube arrays were prepared by anodization method with doped Polyvinyl pyrrolidone (PVP) addition. The as-prepared samples were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and transmission electron microscopy. The results suggested that TiO₂ nanotubes arrays modified by 0.10 wt% PVP were better uniform and more highly ordered than that of pure TiO₂. The average inner diameter and the tube length of TiO₂ nanotubes were extended approximately 77 nm and 5.21 μm, respectively. Meanwhile, the optimum synthesis conditions (40 V, 4 h and 450 °C) were determined by SEM and XRD. In addition, the photocatalytic activity of the as-prepared samples was investigated for the degradation of RhB under UV-lamp irradiation. The results showed that almost 100 % of RhB was degradation within 80 min by the as-prepared nanotubes in the optimum synthesis conditions. It was indicated that the photocatalytic activity of the as-prepared nanotubes was improved greatly due to their well morphology, enhanced UV-light absorption property and electron transmission ability. In general, this study could provide a principle method to synthesize TiO₂ nanotube arrays with enhanced photocatalytic activity and improved microstructure by anodization process with PVP addition.     

A highly active bi-crystalline photocatalyst consisting of TiO2 (B) nanotube and anatase particle for producing H2 gas from neat ethanol

Sodium titanate nanotubes (NaTNTs) are converted into monoclinic TiO₂ (B) nanotubes by rinsing with 0.10 M HCl followed by drying at 573 K. As calcination temperature is increased to 673 K, these TiO₂ (B) nanotubes start to transform into anatase nanoparticles producing a bi-crystalline mixture consisting of TiO₂ (B) nanotubes and anatase nanoparticles. The primary particle size of the anatase particles was estimated to be around 10 nm using Scherrer equation. After being promoted with 1% Pt, this bi-crystalline material becomes a very active photocatalyst producing 20% more H₂ gas than 1% Pt/Degussa P-25 TiO₂ in the photocatalytic dehydrogenation of neat ethanol after 2 h of UV light irradiation.     

SYNTHESIS FACTORS THAT IMPACT TiO2 NANOTUBE ACTIVITY DURING GAS-PHASE PHOTOCATALYTIC OXIDATION OF METHANOL

Statistically designed experiments determined which steps in the hydrothermal synthesis of TiO₂ nanotubes significantly impacted the rate of photocatalytic oxidation of gas-phase methanol. This study investigated the following synthesis steps: sodium hydroxide treatment time, conductivity of the first and second washings, acid treatment time and pH, calcination temperature, and H₂O₂ post-treatment. The synthesis procedure produced a highly active photocatalyst; the maximum catalyst activity of the TiO₂ nanotubes was approximately seven times that of the starting material, Degussa P-25. Characterization with transmission electron microscopy, X-ray diffraction, and temperature-programmed oxidation revealed that the nanotubes were 10–12 nm in diameter with an average length of approximately 100 nm.     

Metal nanoparticle chains embedded in TiO2 nanotubes prepared by one-step electrodeposition

Arrays of Ni nanoparticle chains embedded in TiO₂ nanotubes (TiO₂/Ni) were fabricated by one-step electrodeposition in anodic aluminum oxide membranes. The formation of spacing Ni nanoparticles or continuous nanorods in the TiO₂ nanotubes depends on the deposition potential, the potential waveform, and the pH value in the electrolyte. The growth mechanism is attributed to the generation of H₂ bubbles and their periodical evolution outside of the TiO₂ nanotubes.     

Electrochemical characterization of TiO2/WOx nanotubes for photocatalytic application

TiO₂/WO_x nanotubes have unique photo-energy retention properties that have gathered scientific interest. Herein, we report the synthesis, morphological characterization, and the electrochemical characterization of TiO₂/WO_x nanotubes compared with pure TiO₂ nanotubes, prepared by anodization technique. Significant structural differences were not observed in TiO₂/WO_x nanotubes as observed by using scanning electron microscopy and transmission electron microscopy. The charge transfer resistance of TiO₂/WO_x before and after photo irradiation determined by using electrochemical impedance spectroscopy proves the inherent energy retention property which was not observed in pure TiO₂ nanotubes.     

Fabrication and corrosion behavior of TiO2 nanotubes on AZ91D magnesium alloy

The major drawback of magnesium alloys in biomedical applications is the rapid degradation rate and the lack of biological activity. In this study, TiO₂ nanotubes were fabricated on the surface of AZ91D magnesium alloy (TiO₂-Mg) to overcome such limitations. The corrosion behavior of TiO₂-Mg nanotubes was studied in simulated body fluid solution using open circuit potentials (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The high polarization resistance and open circuit potentials of TiO₂-Mg nanotubes indicate the formation of highly stable TiO₂ layer in simulated body fluid than that of titanium layer on magnesium alloy (Ti-Mg). TiO₂ nanotubes on AZ91D magnesium alloy (AZ91D) can effectively decrease the degradation rate of magnesium alloy, thus can be further applied in orthopedic implants.     

Effects of Y-TZP blank manufacturing control and addition of TiO2 nanotubes on structural reliability of dental materials

Titanium dioxide (TiO₂) nanotubes have been applied to enhance the mechanical and biological properties of dental materials. Yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) have been increasingly used in dentistry as a substructure for crowns and fixed partial prostheses. Aside from its optimal clinical results, Y-TZP is prone to failures due to microstructure-related defects introduced in the manufacturing process that may lower its structural and clinical reliability. The purpose of this study was to evaluate the role of the manufacturing process of blanks as well as their original composition modification by addition of TiO₂ nanotubes (0%, 1%, 2% and 5% in volume) while controlling all manufacturing steps. Materials were subjected to a biaxial flexural strength test, a fractographic qualitative analysis by scanning electron microscopy (SEM), a microstructure evaluation in field emission-SEM and X-ray diffraction. Values of flexural strength were subjected to ANOVA, Tukey (α = 0.05) and Weibull statistics. Grain size values were subjected to Kruskal-Wallis and Dunn tests (α = 0.05). Highlights of the results include that for experimental Y-TZP added 2% vol TiO₂ nanotube ceramics presented flexural strength values at 577 MPa and Weibull modulus (m) at 8.1. The addition of TiO₂ nanotubes in different blends influenced experimental Y-TZP properties, leading to lower flexural strength, although they presented higher m than the commercial Y-TZP. Nanotubes also led to bigger grain sizes, more pores and a slight increase in the monoclinic phase, influencing the microstructure of Y-TZP. Y-TZP blank manufacturing control as well as addition of TiO₂ nanotubes led to higher m values and, hence, greater structural reliability.