Amorphous TiO2 Nanotubes Research Articles

Mechanisms of ion irradiation induced ordering in amorphous TiO2 nanotubes: Effects of ion mass and energy

Amorphous TiO2 nanotubes were irradiated in-situ in a transmission electron microscope (TEM) with Kr+ ions at energies of 46 keV, 150 keV, and 1 MeV and with 46 keV Xe+ ions, to investigate the structural and morphological evolution of the nanotubes under irradiation. At all irradiation conditions, amorphous TiO2 nanotubes exhibited significant morphological instability, and tended to undergo volumetric swelling with increasing ion counts, often until collapse of the original nanotube structure. Molecular dynamics (MD) simulations confirmed that irradiation-induced defects can explain the observed swelling. Structurally, nanotubes remain amorphous following all Kr+ irradiation conditions, but irradiation with 46 keV Xe+ leads to the formation of anatase nanocrystallites. Importantly, through systematically varying ion energy and ion species, we try to elucidate the influence of nuclear and electronic stopping power on ion irradiation induced changes. By contextualizing these results within the existing literature, we propose that the observed changes in TiO2 nanotube morphology and structure could be due to a competition between two mechanisms: (1) disorder-induced swelling and (2) irradiation-induced amorphous-to-crystalline transformation.

Laser‐Crystallization of TiO2 Nanotubes for Photocatalysis: Influence of Laser Power and Laser Scanning Speed

AbstractTitanium dioxide (TiO2) nanotubes have raised significant attention in the field of photocatalysis. However, achieving locally‐confined, tunable, and efficient crystallization remains challenging. Laser crystallization that enables surface‐confined, fast, and localized annealing has emerged as an alternative to calcination of TiO2 nanotubes. Nonetheless, questions regarding crystallization parameters and mechanism remain open. In this work, amorphous TiO2 nanotubes are synthesized by a two‐step anodization process and laser exposed (515 nm, 1 MHz, 250 fs, 256–569 mW, 1–200 mm s−1) to study the impact of laser parameters and the mechanism of laser crystallization. A thorough analysis via Raman spectroscopy, X‐ray diffraction, scanning electron microscopy, UV–vis spectroscopy, transmission electron microscopy, and degradation of methylene blue is performed and the influence of laser processing parameters on the crystallization are studied and discussed. As laser power increases, a gradual transition from amorphous to anatase and rutile phase takes place, consistent with a thermal crystallization mechanism. Contrary, with increasing laser scanning speeds, thus lower pulse numbers, anatase is converted to rutile and melting occurs. The degradation of methylene blue with anatase samples crystallized by laser and calcination exhibits equal kinetic degradation constants of 0.013 s−1cm−2. This study enhances the understanding of laser crystallization of TiO2 nanotubes.

Crystallization of amorphous anodized TiO2 nanotube arrays.

Anodized TiO2 nanotube arrays (TNTAs) prepared by anodization have garnered widespread attention due to their unique structure and properties. In this study, we prepared TNTAs of varying lengths by controlling the anodization time. Among them, the nanotubes anodized for 2 h have an inner diameter of approximately 92 nm and a wall thickness of approximately 12 nm. Then we subjected amorphous TNTAs prepared by the anodization method to annealing treatments, systematically analyzing the evolution of morphology and structure with varying annealing temperatures. As the annealing temperature increases, the amorphous successively undergoes transitions to the anatase phase and then to the rutile phase. During the transition to the anatase phase, the structure of the nanotube array remains intact, with the complete preservation of the tubular array structure. However, during the transition to the rutile phase, the tubular array structure is destroyed. To address why the tubular array remains undamaged during the amorphous-to-anatase transition, we subjected amorphous TNTAs to annealing at 300 °C for different durations. Raman spectroscopy was employed for fit analysis, providing insights into the evolution of the molecular structure during the anatase phase transition. Finally, TNTAs annealed at different temperatures were incorporated into lithium-ion batteries. By combining XRD for semi-quantitative phase content and anatase particle size calculations, we established a correlation between structure and electrochemical performance. The results indicate a significant improvement in electrochemical performance for an amorphous-anatase structure obtained through annealing at 300 °C, providing insights for the design of high-performance energy storage materials.

Photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction to methane with simultaneous H2 production

This study assessed the photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti3+ and oxygen vacancies into the TiO2 structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO2 reduction with water vapor was evaluated under UV irradiation for 3 h, where CH4 and H2 were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 μmol gcat−1 h−1, followed by the amorphous film, which also exhibited an impressive formation rate of 64 μmol gcat−1 h−1. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H2 production (142 and 144 μmol gcat−1 h−1, respectively). The annealed catalyst also revealed a good performance for H2 production (132 μmol gcat−1 h−1) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).

In situ ion irradiation of amorphous TiO2 nanotubes

Understanding of structural and morphological evolution in nanomaterials is critical in tailoring their functionality for applications such as energy conversion and storage. Here, we examine irradiation effects on the morphology and structure of amorphous TiO2 nanotubes in comparison with their crystalline counterpart, anatase TiO2 nanotubes, using high-resolution transmission electron microscopy (TEM), in situ ion irradiation TEM, and molecular dynamics (MD) simulations. Anatase TiO2 nanotubes exhibit morphological and structural stability under irradiation due to their high concentration of grain boundaries and surfaces as defect sinks. On the other hand, amorphous TiO2 nanotubes undergo irradiation-induced crystallization, with some tubes remaining only partially crystallized. The partially crystalline tubes bend due to internal stresses associated with densification during crystallization as suggested by MD calculations. These results present a novel irradiation-based pathway for potentially tuning structure and morphology of energy storage materials.Graphical abstract

Single-step fabrication of highly stable amorphous TiO2 nanotubes arrays (am-TNTA) for stimulating gas-phase photoreduction of CO2 to methane

This study investigates the facile fabrication of interfacial defects assisted amorphous TiO2 nanotubes arrays (am-TNTA) for promoting gas-phase CO2 photoreduction to methane. The am-TNTA catalyst was fabricated via a one-step synthesis, without heat treatment, by anodization of Titanium in Ethylene glycol-based electrolyte in a shorter anodizing time. The samples presented a TiO2 nanostructured array with a nanotubular diameter of 100 ± 10 nm, a wall thickness of 26 ± 5 nm, and length of 3.7 ± 0.3 μm, resulting in a specific surface of 0.75 m2 g. The am-TNTA presented prolonged chemical stability, a high exposed surface area, and a large number of surface traps that can reduce the recombination of the charge carriers. The am-TNTA showed promising photoactivity when tested in the CO2 reduction reaction with water under UV irradiation with a methane production rate of 14.0 μmol gcat−1 h−1 for a pure TiO2 material without any modification procedure. This enhanced photocatalytic activity can be explained in terms of surface defects of the amorphous structure, mainly OH groups that can act as electron traps for increasing the electron lifetime. The CO2 interacts directly with those traps, forming carbonate species, which favors the catalytic conversion to methane. The am-TNTA also exhibited a high stability during six reaction cycles. The photocatalytic activity, the significantly reduced time for synthesis, and high stability for continuous CH4 production make this nanomaterial a potential candidate for a sustainable CO2 reduction process and can be employed for other energy applications.

Photocatalytic Crystalline and Amorphous TiO2 Nanotubes Prepared by Electrospinning and Atomic Layer Deposition.

In this work core/shell composite polymer/TiO2 nanofibers and from those TiO2 nanotubes were prepared. First, poly(vinyl alcohol) (PVA) and poly(vinylpyrrolidone) (PVP) fibers were synthetized by electrospinning. They were covered with a 100 nm thick amorphous TiO2 layer by atomic layer deposition at 50 °C. Later the polymer core was removed by two different methods: dissolution and annealing. In the case of dissolution in water, the as-prepared TiO2 nanotubes remained amorphous, while when annealing was used to remove the polymers, the TiO2 crystallized in anatase form. Due to this, the properties of amorphous and crystalline TiO2 nanotubes with exactly the same structure and morphology could be compared. The samples were investigated by SEM-EDX, ATR-IR, UV-Vis, XRD and TG/DTA-MS. Finally, the photocatalytic properties of the TiO2 nanotubes were studied by decomposing methyl-orange dye under UV light. According to the results, crystalline anatase TiO2 nanotubes reached the photocatalytic performance of P25, while amorphous TiO2 nanotubes had observable photocatalytic activity.

Array of single crystalline anatase TiO2 nanotubes with significant enhancement of photoresponse

Anatase TiO2 nanotubes array (ATONA) has attracted tremendous attention owing to its promising applications in solar cells, water splitting and organic pollutants photocatalytic degradation. However, the activity of ATONAs was greatly suppressed by the grain boundaries existed in the tube walls, which acted as carrier scattering and recombination centers. Herein, we report a novel strategy to prepare array of single crystalline anatase TiO2 nanotubes (SC-ATONAs) with significant enhancement of the photocatalytic activity and UV photo response performance compared to the polycrystalline counterparts. The growth of SC-ATONAs was achieved by establishing a crystallization temperature gradient along the tube wall, which ensured the crystallization started from the nucleation of a single nucleus at the bottom of amorphous TiO2 nanotubes prepared by Ti anodization. These findings pave the way to prepare single-crystalline nanotubes with superior performance for other materials.

Highly Ordered TiO2 Nanotube Arrays with Engineered Electrochemical Energy Storage Performances.

Nanoscale engineering of regular structured materials is immensely demanded in various scientific areas. In this work, vertically oriented TiO2 nanotube arrays were grown by self-organizing electrochemical anodization. The effects of different fluoride ion concentrations (0.2 and 0.5 wt% NH4F) and different anodization times (2, 5, 10 and 20 h) on the morphology of nanotubes were systematically studied in an organic electrolyte (glycol). The growth mechanisms of amorphous and anatase TiO2 nanotubes were also studied. Under optimized conditions, we obtained TiO2 nanotubes with tube diameters of 70–160 nm and tube lengths of 6.5–45 μm. Serving as free-standing and binder-free electrodes, the kinetic, capacity, and stability performances of TiO2 nanotubes were tested as lithium-ion battery anodes. This work provides a facile strategy for constructing self-organized materials with optimized functionalities for applications.

Self-assembly and activation of a titania-nanotube based photocatalyst for H2 evolution.

Constructing an efficient photocatalyst for H2 production generally requires the integration of several functional features in and on a semiconductor platform. This is conventionally done by a classic step-by-step synthesis. Here, we report the self-assembly of an amorphous titania nanotube based system when illuminated for extended time in suitable aqueous solutions. Over time, not only photodeposition of a co-catalyst can take place, but also in situ crystallization and morphology changes occur that can provide a higher H2 production than observed for a classically assembled photocatalyst.

TiO2 Nanotube Arrays on Flexible Kapton Substrates for Photo-Electrochemical Solar Energy Conversion

This work reports the growth of stable TiO2 nanotube arrays on flexible Kapton substrates by electrochemical anodization of a sputtered Ti (titanium) film. Although such nanotubes are conventionally fabricated on Ti foils, obtaining these on polymer-based flexible substrates remained a challenge because of higher annealing temperature not compatible with thermal stability of the substrates. Here, we demonstrate the fabrication of TiO2 nanotubes (1.5 μm long and 80 nm diameter) by anodization of the Ti film deposited using the RF sputtering technique at two different substrate temperatures (room temperature and 300 °C). Nanoindentation and nanoscratch techniques reveal better adhesion of the Ti film with an underlying Kapton substrate for 300 °C deposition temperature. Such investigations reveal a more than twofold enhancement of the “rear pileup” for the Ti film deposited at elevated temperature compared to that at room temperature. The amorphous TiO2 nanotubes are crystallized at 220 °C for 3 h using a solvothermal technique that allows crystallization at temperatures much lower than the annealing temperature. Application of these nanotubes for photo-electrochemical water splitting reveals a photocurrent density of 18 μA/cm2 under AM 1.5 G conditions. Furthermore, the charge density and flat band potential (VFB) are calculated from Mott–Schottky analysis, showing features comparable to the TiO2 nanotubes on the Ti foil crystallized through thermal annealing. The present work establishes a scalable approach for developing TiO2 nanotube arrays on the flexible substrate and its use for photo-electrochemical solar energy conversion.

Plasma-Enabled Amorphous TiO2 Nanotubes as Hydrophobic Support for Molecular Sensing by SERS.

We devise a unique heteronanostructure array to overcome a persistent issue of simultaneously utilizing the surface-enhanced Raman scattering, inexpensive, Earth-abundant materials, large surface areas, and multifunctionality to demonstrate near single-molecule detection. Room-temperature plasma-enhanced chemical vapor deposition and thermal evaporation provide high-density arrays of vertical TiO2 nanotubes decorated with Ag nanoparticles. The role of the TiO2 nanotubes is 3-fold: (i) providing a high surface area for the homogeneous distribution of supported Ag nanoparticles, (ii) increasing the water contact angle to achieve superhydrophobic limits, and (iii) enhancing the Raman signal by synergizing the localized electromagnetic field enhancement (Ag plasmons) and charge transfer chemical enhancement mechanisms (amorphous TiO2) and by increasing the light scattering because of the formation of vertically aligned nanoarchitectures. As a result, we reach a Raman enhancement factor of up to 9.4 × 107, satisfying the key practical device requirements. The enhancement mechanism is optimized through the interplay of the optimum microstructure, nanotube/shell thickness, Ag nanoparticles size distribution, and density. Vertically aligned amorphous TiO2 nanotubes decorated with Ag nanoparticles with a mean diameter of 10-12 nm provide enough sensitivity for near-instant concentration analysis with an ultralow few-molecule detection limit of 10-12 M (Rh6G in water) and the possibility to scale up device fabrication.

The storage mechanism difference between amorphous and anatase as supercapacitors

Although TiO2 nanotubes is a promising electrode as supercapacitors due to its high energy density, easy synthesis and chemical stability, there are draw backs such as low conductivity and capacitance. Many studies concentrated on improving its electrochemical performance itself but little attention was payed to the reason of capacitance differences caused by its different crystal structures. Herein, we prepare amorphous and anatase TiO2 nanotubes and hydrogenated them by a simple electrochemical hydrogenation method to improve their conductivity and capacitance. And then study and compare their morphology and structure differences by SEM, TEM, XRD and BET. The results show that the pore size distribution, internal structure order and internal carrier concentration are the main reasons for their electrochemical performance differences. The microporous structure less than 2 nm in amorphous nanotubes act as a trap of electrolyte ions at current density larger than 0.1 μA cm−2, leading to small charge and discharge capacitance. The long-range ordered crystal structure of anatase is more favorable for the orderly diffusion of carriers, reducing the inelastic scattering of carrier diffusion process and the electron hole-complexing probability, making anatase nanotubes exhibit higher coulomb efficiency and cycle stability than that of amorphous ones.

Surface Wettability of ZnO-Loaded TiO2 Nanotube Array Layers

Herein we report on the synthesis and the effects of gradual loading of TiO2 nanotube array layers with ZnO upon surface wettability. Two-step preparation was chosen, where TiO2 nanotube layers, grown in a first instance by anodization of a Ti foil, were gradually loaded with controlled amounts of ZnO using the reactive RF magnetron sputtering. After crystallization annealing, the formerly amorphous TiO2 nanotubes were converted to predominantly anatase crystalline phase, as detected by XRD measurements. The as-prepared nanotubes exhibited a well-aligned columnar structure, 1.6 μm long and 88 nm in diameter, and a small concentration of oxygen vacancies. Ti2+ and Ti3+ occur along with the Ti4+ state upon sputter-cleaning the layer surfaces from contaminants. The Ti2+ and Ti3+ signals diminish with gradual ZnO loading. As demonstrated by the VB-XPS data, the ZnO loading is accompanied by a slight narrowing of the band gap of the materials. A combined effect of material modification and surface roughness was taken into consideration to explain the evolution of surface super-hydrophilicity of the materials under UV irradiation. The loading process resulted in increasing surface wettability with approx. 33%, and in a drastic extension of activation decay, which clearly points out to the effect of ZnO-TiO2 heterojunctions.

Sn-doped TiO2 nanotubular thin film for photocatalytic degradation of methyl orange dye

We fabricated Sn-doped TiO2 nanotubular film via annealing of anodized TiO2 nanotubes grown on F–SnO2 (FTO) glass. Annealing was carried out at 500 °C in ambient air. Anatase crystal structure was achieved with no change in nanotubular morphology in respect to as-anodized amorphous TiO2 nanotubes. The X-ray photoelectron spectroscopy analysis revealed Sn on the surface of TiO2 film, following the thermal treatment, probably caused by the diffusion from FTO glass. Depth profile examination of the film chemical composition was conducted by elastic recoil detection analysis, which showed that in addition to the diffusion of Sn from FTO, diffusion of Ti to FTO concurrently occurred. Thus, a higher concentration of Sn was found at the bottom of the tubes, while a lower concentration was present on the tubes’ surface top. This explains the improved optical response revealed by a diffuse reflectance spectroscopy. The absorption enhancement demonstrated that Sn-doped TiO2 film was efficient in the degradation of methyl orange dye under visible light.

Surface-Dependent Osteoblasts Response to TiO2 Nanotubes of Different Crystallinity.

One of the major challenges of implantology is to design nanoscale modifications of titanium implant surfaces inducing osseointegration. The aim of this study was to investigate the behavior of rat osteoblasts cultured on anodized TiO2 nanotubes of different crystallinity (amorphous and anatase phase) up to 24 days. TiO2 nanotubes were fabricated on VT1–0 titanium foil via a two-step anodization at 20 V using NH4F as an electrolyte. Anatase-phase samples were prepared by heat treatment at 500 °C for 1 h. VT1–0 samples with flat surfaces were used as controls. Primary rat osteoblasts were seeded over experimental surfaces for several incubation times. Scanning electron microscopy (SEM) was used to analyze tested surfaces and cell morphology. Cell adhesion and proliferation were investigated by cell counting. Osteogenic differentiation of cells was evaluated by qPCR of runt-related transcription factor 2 (RUNX2), osteopontin (OPN), integrin binding sialoprotein (IBSP), alkaline phosphatase (ALP) and osteocalcin (OCN). Cell adhesion and proliferation, cell morphology and the expression of osteogenic markers were affected by TiO2 nanotube layered substrates of amorphous and anatase crystallinity. In comparison with flat titanium, along with increased cell adhesion and cell growth a large portion of osteoblasts grown on the both nanostructured surfaces exhibited an osteocyte-like morphology as early as 48 h of culture. Moreover, the expression of all tested osteogenic markers in cells cultured on amorphous and anatase TiO2 nanotubes was upregulated at least at one of the analyzed time points. To summarize, we demonstrated that amorphous and anodized TiO2 layered substrates are highly biocompatible with rat osteoblasts and that the surface modification with about 1500 nm length nanotubes of 35 ± 4 (amorphous phase) and 41 ± 8 nm (anatase phase) in diameter is sufficient to induce their osteogenic differentiation. Such results are significant to the engineering of coating strategies for orthopedic implants aimed to establish a more efficient bone to implant contact and enhance bone repair.

Facile synthesis and enhanced photo-electrocatalytic performance of TiO2 nanotube/g-C3N4 composite catalyst by a novel synthesis approach

TiO2 nanotube/graphene-like carbon nitride (g-C3N4) composite structure was fabricated by a novel synthesis approach. Amorphous TiO2 nanotube arrays was synthesized by anodization. Afterward, g-C3N4 structures were decorated on the amorphous TiO2 nanotube arrays by using thermal polymerization process while anatase phase transformation of TiO2 in progress for the first time. The nanocomposite electrodes were further used for photo-electrochemical degradation of Rhodamine B dye. The homogenous surface morphology, higher crystallinity and more efficient photo-electrochemical performance were obtained by TiO2 nanotube/g-C3N4 composite structure due to better electrical contact and electron transportation by described synthesis approach.

Laser-induced crystallization of anodic TiO2 nanotube layers.

In this study, crystallization of amorphous TiO2 nanotube (TNT) layers upon optimized laser annealing is shown. The resulting anatase TNT layers do not show any signs of deformation or melting. The crystallinity of the laser annealed TNT layers was investigated using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM). The study of the (photo-)electrochemical properties showed that the laser annealed TNT layers were more defective than conventional TNT layers annealed in a muffle oven at 400 °C, resulting in a higher charge recombination rate and lower photocurrent response. However, a lower overpotential for hydrogen evolution reaction was observed for the laser annealed TNT layer compared to the oven annealed TNT layer.

Enhanced performance of lithium ion batteries from self-doped TiO2 nanotube anodes via an adjustable electrochemical process

In this work, we report on fabricating of self-doped TiO2 nanotube arrays via a facile electrochemical method by modify the electrochemical anodized amorphous TiO2 nanotube arrays with cathodic pulse doping. The self-doped TiO2 nanotube arrays is black appearance with abundant oxygen vacancy and hydroxyl groups in comparison with that of as-anodized ones. The initial discharge specific capacity of self-doped TiO2 nanotube anode is 1355 μA h/cm2 which is more than four times higher than 338 μA h/cm2 of the as-anodized TiO2 nanotube anode in lithium ion batteries. After 100 cycles, the specific capacity of the self-doped TiO2 nanotube electrodes still much higher than that of the as-anodized samples, which is attributed to good tubular morphology retention and secondary growth of the self-doped TiO2 nanotube arrays through the process of insertion/extraction Li+. The controllable regulation of the capacity of self-doped TiO2 anode is also achieved by adjusting electrochemical cathode pulse parameters. It is noteworthy that the cycled anode materials can be used as a catalyst for photocatalytic degradation of methylene blue which may shed light on the resource recovery and the environmental protection.

Anodic Voltage Dependence of Ti-6Al-4V Substrates and Hydroxyapatite Coating

Ti-6Al-4V alloys were anodized in a solution containing 0.15 M HF and 2 M H₃PO₄ for 30 min under different voltages and then coated with hydroxyapatite (HA) by hydrothermal-electrochemical deposition. The effects of anodizing voltage on the morphology and bioactivity of the HA coating and on the bonding strength between the HA coating and the anodized substrates were investigated. Results indicated that highly ordered amorphous TiO₂ nanotube arrays formed on the Ti-6Al-4V surface after anodic oxidation. The pore size of the nanotube increased up to approximately 100 nm with increasing anodic voltage until 25 V. The nanotube was damaged at anodic voltages above 25 V. The crystal structure of TiO₂ changed from amorphous to anatase when the anodized substrates were heated at 450 °C for 3 h. The contact angle between the Ti-6Al-4V surfaces and the simulated body fluid evidently decreased after anodic oxidation. The roughness increased with increasing anodic voltage, and Ra reached about 0.56 μm under 25 V. The HA coating exhibited layered growth. The deposition of rod-like HA crystals as well as the crystallinity of the HA coating initially increased and then decreased with the further increase of the anodic volatage. The degree of crystallinity reached the maximum of approximately 73% at 25 V. The bonding strength between the coating and the anodized substrates increased and then slightly decreased with increasing voltage. The bonding strength was about 20.0 MPa when titanium substrate was anodized under 25 V. The results of simulated body fluid immersing experiments suggest that the HA coating exhibits promising bioactivity.