Aligned metal oxide nanotube arrays: key-aspects of anodic TiO2 nanotube formation and properties

Over the past ten years, self-aligned TiO2 nanotubes have attracted tremendous scientific and technological interest due to their anticipated impact on energy conversion, environment remediation and biocompatibility. In the present manuscript, we review fundamental principles that govern the self-organized initiation of anodic TiO2 nanotubes. We start with the fundamental question: Why is self-organization taking place? We illustrate the inherent key mechanistic aspects that lead to tube growth in various different morphologies, such as rippled-walled tubes, smooth tubes, stacks and bamboo-type tubes, and importantly the formation of double-walled TiO2 nanotubes versus single-walled tubes, and the drastic difference in their physical and chemical properties. We show how both double- and single-walled tube layers can be detached from the metallic substrate and exploited for the preparation of robust self-standing membranes. Finally, we show how by selecting the right growth approach to TiO2 nanotubes specific functional features can be significantly improved, e.g., an enhanced electron mobility, intrinsic doping, or crystallization into pure anatase at extremely high temperatures can be achieved. This in turn can be exploited in constructing high performance devices based on anodic TiO2 in a wide range of applications.Comment: from Nanoscale Horiz., 2016, Advance Articl

TiO2 nanotubes for room temperature toluene sensor

TiO2 nanotubes were used to prepare gas sensor and the gas sensing properties towards toluene were analyzed. Titania nanotube arrays were fabricated via electrochemical anodization method in glycerol electrolytes containing NH4F. The sensor fabricated from these nanotubes exhibits a good response to toluene at room temperature with good sensitivity. The toluene sensing properties were tested from 20 to 150 ppm concentrations.Fil: Perillo, Patricia Maria. Comisión Nacional de Energía Atómica. Gerencia de Área de Investigación y Aplicaciones no Nucleares. Gerencia de Desarrollo Tecnológico y Proyectos Especiales. Departamento de Micro y Nanotecnología; ArgentinaFil: Rodriguez, Daniel Fabian. Comisión Nacional de Energía Atómica. Gerencia de Área de Investigación y Aplicaciones no Nucleares. Gerencia de Desarrollo Tecnológico y Proyectos Especiales. Departamento de Micro y Nanotecnología; ArgentinaFil: Boggio, Norberto Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia de Área de Investigación y Aplicaciones no Nucleares. Gerencia de Desarrollo Tecnológico y Proyectos Especiales. Departamento de Micro y Nanotecnología; Argentin

Stability and Electronic Properties of TiO2 Nanostructures With and Without B and N Doping

We address one of the main challenges to TiO2-photocatalysis, namely band gap narrowing, by combining nanostructural changes with doping. With this aim we compare TiO2's electronic properties for small 0D clusters, 1D nanorods and nanotubes, 2D layers, and 3D surface and bulk phases using different approximations within density functional theory and GW calculations. In particular, we propose very small (R < 0.5 nm) but surprisingly stable nanotubes with promising properties. The nanotubes are initially formed from TiO2 layers with the PtO2 structure, with the smallest (2,2) nanotube relaxing to a rutile nanorod structure. We find that quantum confinement effects - as expected - generally lead to a widening of the energy gap. However, substitutional doping with boron or nitrogen is found to give rise to (meta-)stable structures and the introduction of dopant and mid-gap states which effectively reduce the band gap. Boron is seen to always give rise to n-type doping while depending on the local bonding geometry, nitrogen may give rise to n-type or p-type doping. For under coordinated TiO2 surface structures found in clusters, nanorods, nanotubes, layers and surfaces nitrogen gives rise to acceptor states while for larger clusters and bulk structures donor states are introduced

Hierarchical DSSC structures based on single walled TiO2 nanotube arrays reach back-side illumination solar light conversion efficiency of 8%

In the present work we introduce a path to the controlled construction of DSSCs based on hierarchically structured single walled, self-organized TiO2 layers. In a first step we describe a simple approach to selectively remove the inner detrimental shell of anodic TiO2 nanotubes (NTs). This then allows controlled well-defined layer-by-layer decoration of these TiO2-NT walls with TiO2 nanoparticles (this in contrast to conventional TiO2 nanotubes). We show that such defined multiple layered decoration can be optimized to build dye sensitized solar cells that (under back-side illumination conditions) can yield solar light conversion efficiencies in the range of 8 %. The beneficial effects observed can be ascribed to a combination of three factors : 1) improved electronic properties of the single walled tubes themselves, 2) a further improvement of the electronic properties by the defined TiCl4 treatment, and 3) a higher specific dye loading that becomes possible for the layer-by-layer decorated single walled tubes.Comment: arXiv admin note: text overlap with arXiv:1610.0643

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This paper reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160^{\circ}C and 24 h. A band gap of 3.06\pm0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 minutes of irradiation of a 10 ppm dye aqueous solution and 1 g/L of TNS catalyst.Comment: 29 pages, 10 figures, accepted for publication in Journal of Materials Scienc

Informing Selection of Nanomaterial Concentrations for ToxCast In Vitro Testing based on Occupational Exposure Potential

Background: Little justification is generally provided for selection of in vitro assay testing concentrations for engineered nanomaterials (ENMs). Selection of concentration levels for hazard evaluation based on real-world exposure scenarios is desirable. Objectives: Our goal is to use estimates of lung deposition following occupational exposure to nanomaterials to recommend in vitro testing concentrations for the U.S. Environmental Protection Agency’s ToxCastTM program. We provide testing concentrations for carbon nanotubes (CNTs), titanium dioxide (TiO2) and silver (Ag) nanoparticles. Methods: We reviewed published ENM concentrations measured in air in manufacturing and R&D labs to identify input levels for estimating ENM mass retained in the human lung using the Multiple-Path Particle Dosimetry (MPPD) model. Model input parameters were individually varied to estimate alveolar mass retained for different particle sizes (5-1000 nm), aerosol concentrations (0.1, 1 mg/m3), aspect ratios (2, 4, 10, 167), and exposure durations (24 hours and a working lifetime). The calculated lung surface concentrations were then converted to in vitro solution concentrations. Results: Modeled alveolar mass retained after 24 hours is most affected by activity level and aerosol concentration. Alveolar retention for Ag and TiO2 nanoparticles and CNTs for a working lifetime (45 years) exposure duration is similar to high-end concentrations (~ 30-400 μg/mL) typical of in vitro testing reported in the literature. Conclusions: Analyses performed are generally applicable to provide ENM testing concentrations for in vitro hazard screening studies though further research is needed to improve the approach. Understanding the relationship between potential real-world exposures and in vitro test concentrations will facilitate interpretation of toxicological results

Tunable Functionality and toxicity studies of Titanium Dioxide Nanotube Layers

In this work, we have developed economic process to elaborate scalable titanium dioxide nanotube layers which show a tunable functionality. The titanium dioxide nanotube layers was prepared by electrochemical anodization of Ti foil in 0.4 wt% hydrofluoric acid solution. The nanotube layers structure and morphology were characterized using x-ray diffraction and scanning electron microscopy. The surface topography and wettability was studied according to the anodization time. The sample synthesized while the current density reached a local minimum displayed higher contact angle. Beyond this point, the contact angles decrease with the anodization time. Photo-degradation of acid orange 7 in aqueous solution was used as a probe to assess the photo-catalytic activity of titanium dioxide nanotube layers under UV irradiation. We obtained better photocatalitic activity for the sample elaborate at higher current density. Finally we use the Ciliated Protozoan T. pyriformis, an alternative cell model used for in vitro toxicity studies, to predict the toxicity of titanium dioxide nanotube layers in biological system. We did not observe any characteristic effect in the presence of the titanium dioxide nanotube layers on two physiological parameters related to this organism, non-specific esterases activity and population growth rate

Aminated TiO2 nanotube as a Photoelectrochemical Water Splitting photoanode

The present work reports on the enhancement of TiO2 nanotubes photoelectrochemical water splitting rate by decorating the nanostructure with an amine layer in a hydrothermal process using diethylenetriamine (DETA). The aminate coated TiO2 tubes show a stable improvement of the photoresponse in both UV and visible light spectrum and under hydrothermal conditions, 4-fold increase of the photoelectrochemical water splitting rate is observed. From intensity modulated photocurrent spectroscopy (IMPS) measurements significantly faster electron transport times are observed indicating a surface passivating effect of the N-decoration.Comment: In Catalysis Today, Available online 21 July 201

Microstructure and properties of nanostructured coating on Ti6Al4V

Implant surface properties of Ti6Al4V alloy that is currently used as a biocompatible material because of a variety of unique properties can be improved by a self-organized TiO2 layer. The TiO2 nanotubes forming on the titanium-based materials is a relatively recent technology for the surface properties modification and represents pronounced potential in promoting cell adhesion, proliferation, and differentiation that facilitate an implant osseointegration. This work focuses on the influence of surface treatment quality and anodic oxidation parameters on the structure features and properties of TiO2 nanotube coatings. The nanotubes were formed on Ti6Al4V alloy substrates by simultaneous surface oxidation and controlled dissolving of an oxide film in the presence of fluorine ions. The anodization process on ground or polished samples was performed at experimental condition of 30 V for 1 h. The selected anodized samples were heat treated for 2 h at 500 degrees C under flowing argon. All samples were characterized by scanning electron microscopy, X-ray diffraction analysis, and Raman spectroscopy. The corrosion rate in physiological solution reached 0.0043, 0.0182, and 0.0998 mm per year for the samples in polished and not-anodized, as-anodized, and anodized-heat treated conditions, respectively.Web of Science133art. no. 70