Anodic TiO2 Nanotube Arrays Research Articles

Boosted photoelectrochemical activity of anodic titanium dioxide nanotubes by electrophoretically decorated nickel–aluminum layered double hydroxide

The splitting of water using photoelectrochemical (PEC) processes is a promising method for generating renewable hydrogen. However, the practical efficiency of converting solar energy to fuel in PEC systems remains limited by inadequate light absorption and the swift recombination of photogenerated charge carriers within the photoelectrode material. In our research, we present a photoanode that addresses these challenges. In this work, we report on the electrophoretic deposition of nickel–aluminum layered double hydroxide (NiAl-LDH) under different voltages onto anodic TiO2 nanotube arrays (TNTAs) as a convenient and economically viable fabrication route of versatile and durable photoanodes. PEC and optical spectroscopy examinations, including linear sweep voltammetry, electrochemical impedance spectroscopy, Mott-Schottky plots, and diffuse reflectance spectroscopy, reveal that NiAl-LDH/TNTAs composites exhibit a superior enhancement of visible light absorption and consequently water splitting photocurrent. We interpret the improvement of PEC water splitting performance of the NiAl-LDH/TNTAs with the band structure speculated by the binding energy and the flat-band potential and band-gap measurements which features this nanocomposite as a novel photocatalyst for future hydrogen energy applications.

Glucose Oxidation Performance of Zinc Nano-Hexagons Decorated on TiO2 Nanotube Arrays

Electrochemically anodized TiO2 nanotube arrays (NTAs) were used as a support material for the electrodeposition of zinc nanoparticles. The morphology, composition, and crystallinity of the materials were examined using scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) was performed to evaluate the electrochemical properties of TiO2 NTAs. Annealing post-anodization was shown to be effective in lowering the impedance of the TiO2 NTAs (measured at 1 kHz frequency). Zinc nanohexagons (NHexs) with a mean diameter of ~300 nm and thickness of 10–20 nm were decorated on the surface of TiO2 NTAs (with a pore diameter of ~80 nm and tube length of ~5 µm) via an electrodeposition process using a zinc-containing deep eutectic solvent. EIS and CV tests were performed to evaluate the functionality of zinc-decorated TiO2 NTAs (Zn/TiO2 NTAs) for glucose oxidation applications. The Zn/TiO2 NTA electrocatalysts obtained at 40 °C demonstrated enhanced glucose sensitivity (160.8 μA mM−1 cm−2 and 4.38 μA mM−1 cm−2) over zinc-based electrocatalysts reported previously. The Zn/TiO2 NTA electrocatalysts developed in this work could be considered as a promising biocompatible electrocatalyst material for in vivo glucose oxidation applications.

Enhanced Photocatalytic Paracetamol Degradation by NiCu-Modified TiO2 Nanotubes: Mechanistic Insights and Performance Evaluation.

Anodic TiO2 nanotube arrays decorated with Ni, Cu, and NiCu alloy thin films were investigated for the first time for the photocatalytic degradation of paracetamol in water solution under UV irradiation. Metallic co-catalysts were deposited on TiO2 nanotubes using magnetron sputtering. The influence of the metal layer composition and thickness on the photocatalytic activity was systematically studied. Photocatalytic experiments showed that only Cu-rich co-catalysts provide enhanced paracetamol degradation rates, whereas Ni-modified photocatalysts exhibit no improvement compared with unmodified TiO2. The best-performing material was obtained by sputtering a 20 nm thick film of 1:1 atomic ratio NiCu alloy: this material exhibits a reaction rate more than doubled compared with pristine TiO2, enabling the complete degradation of 10 mg L-1 of paracetamol in 8 h. The superior performance of NiCu-modified systems over pure Cu-based ones is ascribed to a Ni and Cu synergistic effect. Kinetic tests using selective holes and radical scavengers unveiled, unlike prior findings in the literature, that paracetamol undergoes direct oxidation at the photocatalyst surface via valence band holes. Finally, Chemical Oxygen Demand (COD) tests and High-Resolution Mass Spectrometry (HR-MS) analysis were conducted to assess the degree of mineralization and identify intermediates. In contrast with the existing literature, we demonstrated that the mechanistic pathway involves direct oxidation by valence band holes.

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.

A Carbon-Free and Free-Standing Cathode From Mixed-Phase TiO2 for Photo-Assisted Li-CO2 Battery.

Li-CO2 battery provides a new strategy to simultaneously solve the problems of energy storage and greenhouse effect. However, the severe polarization of CO2 reduction and CO2 evolution reaction impede the practical application. Herein, anodic TiO2 nanotube arrays are first introduced as carbon-free and free-standing cathode for photo-assisted Li-CO2 battery, and the photo-assisted charge and discharge mechanism is first clarified from the perspective of photocatalysis. Mixed-phase TiO2 exhibits a long cycling life of 580h (52 cycles) at 0.025mA cm-2 and delivers a high discharge specific capacity of 3001 µAh cm-2 under UV illumination. The charge voltage dramatically reduces from 4.53 to 3.03V under UV illumination. The improvement of photo-assisted Li-CO2 battery performance relies on the synergistic effect of the hierarchical porous structure, strong UV absorption, efficient separation, and transfer of photo-generated electrons and holes at hetero-phase junction, and the facilitation of photo-generated electrons and holes on CO2 reduction and CO2 evolution reaction. This work can provide useful guidance for designing efficient photocathode for photo-assisted Li-CO2 battery and other metal-air batteries.

Tube length optimization of titania nanotube array for efficient photoelectrochemical water splitting

Anodic TiO2 nanotube arrays (TNTAs) have attracted much attention due to their excellent photoelectrochemical (PEC) properties. In this work, the tube length of TNTAs was optimized for efficient PEC water splitting under two different conditions, in which very few or a massive amount of gas bubbles were generated on the electrodes. As a result, relatively longer TNTAs were found to be preferable for higher PEC performance when a larger number of bubbles were generated. This suggests that the mass transport in the electrolyte is assisted by the generated bubbles, so that the electrode surfaces are more easily exposed to the fresh electrolyte, leading to the higher PEC performance.

Photocatalytic Decomposition of Ethanol Vapour by Anodic TiO2 Nanotube Arrays Modified by Metal Nanoparticles

Photocatalytic Decomposition of Ethanol Vapour by Anodic TiO2 Nanotube Arrays Modified by Metal Nanoparticles

Hybrid TiNb oxides/nitrides nanotube arrays as active catalyst supports

In order to improve the thermal stability of anodized TiO2 nanotube arrays, this paper proposed to fabricate the hybrid TiNb oxide nanotube arrays (TiNb ONA) on β-phase TiNb alloy plates by anodic oxidation. Then, TiNb ONA precursors were transformed into conductive nitride nanotube arrays (TiNb NNA) by nitridation at 800 °C. Introducing Nb contributes to the higher structural stability and easier nitridation of TiNb ONA compared with TiO2 nanotube arrays. After that, the spinel CuFe2O4 and nanosized Re-Ni alloy were respectively loaded on TiNb ONA and TiNb NNA to form CuFe2O4/TiNb ONA and Re-Ni/ TiNb NNA composite electrodes, and their performances in the photoelectrochemical reduction of CO2 and hydrogen evolution reactions were assessed respectively. Results showed that the well-maintained TiNb ONA improved the photo-response performance of the thermally-synthesized CuFe2O4, and TiNb NNA support also boosted the hydrogen evolution reaction because of the conductivity and catalytic activity of TiNb nitrides.

High-specific-capacitance electrolytic capacitors based on anodic TiO2 nanotube arrays

Electrolytic capacitors have been increasingly used in almost all electronic devices because of their large specific capacitance, broad operating voltage range and good price to performance ratio. To satisfy the continuing miniaturization trend of electronic devices, researchers have continuously maintained efforts to increase the specific capacitance of electrolytic capacitors. Herein, we report a novel way to achieve high-specific-capacitance electrolytic capacitors starting from titanium dioxide nanotube arrays (TDNAs) formed by anodization. The anodized TDNAs are first transformed into titanium nitride nanotube arrays (TNNAs) by nitridation. Then TNNAs covered with a BaTiO3 film (BaTiO3@TNNAs) are obtained through electrochemical deposition and subsequent annealing. Thus, the fabricated BaTiO3@TNNAs are employed as anode of an electrolytic capacitor. The capacitor cathode is also derived from the anodized TDNAs by an electrochemical doping approach. The capacitor made of the BaTiO3@TNNAs anode and TDNAs cathode shows excellent electrical properties with a high specific capacitance of 292.8 μF cm−2, considerably higher than previously reported values for the modified aluminum anode foils. This study can provide new directions in increasing specific capacitance of electrolytic capacitors.

Characteristics of anodic TiO2 nanotube arrays mediated IrO2 Active Anode in the Oxygen Evolution Reaction

Characteristics of anodic TiO2 nanotube arrays mediated IrO2 Active Anode in the Oxygen Evolution Reaction

Intricate behaviors of gas phase CO2 photoreduction in high vacuum using Cu2O-loaded TiO2 nanotube arrays

Photoreduction of carbon dioxide (CO2) in gas phase was investigated over composites of Cu2O nanoparticles (CNPs) and anodized TiO2 nanotube arrays (TNAs). CNPs with an average size of 90 nm were pulse-electrodeposited on vertically aligned hollow TiO2 nanotubes having average pore size of 90 nm. Radical trapping experiments with electron spin resonance spectroscopy suggest that photoinduced charge separation occurs via direct Z-scheme mechanism in Cu2O-loaded TNA (CNP/TNA) sample. Successively, CO2 photoreduction for CNP/TNA from water/CO2 mixture was monitored using a quadrupole mass analyzer in high vacuum, where the partial pressures of intermediate and final reaction species were measured in real time under ultraviolet-visible (UV–VIS) light irradiation (300–600 nm). The photoreduction of CO2 on CNP/TNA happens through preferred generation of formaldehyde (HCHO) and methanol (CH3OH), while platinum-loaded TNA (Pt/TNA) produced methane (CH4) and hydrogen (H2) instead of HCHO and CH3OH. Carbon monoxide (CO) formation was commonly observed for both CNP/TNA and Pt/TNA specimens. These results reveal that CO2 photoreduction occurs through hydrogenation in gas phase over CNP/TNA even in high vacuum, although CO2 deoxygenation to CH4 is conventionally dominant for gas phase reactions.

Reduced TiO2 nanotube array as an excellent cathode for hydrogen evolution reaction in alkaline solution

Anodic TiO2 nanotube (TNT) arrays have been intensively investigated as anodes in water splitting (WS) cells because of their excellent chemical stability. However, anodic TNT is seldom considered as a cathode for the hydrogen evolution reaction (HER) in an electrochemical WS cell. This study shows that a reduced TNT (R-TNT) sample prepared with a cathodic reduction technique without loading any co-catalyst can achieve remarkable HER performance. At − 1.0 V vs reversible hydrogen electrode in 1 M NaOH in dark, R-TNT achieved a current of − 221 mA, which is 17000-times of that achieved when using TNT and 5-times of that with Ti-foil as cathode. Chronopotentiometry tests were carried out sequentially at @ −100, − 50 and − 10 mA for 24 h and decay rates of 1.3%, 5.2% and 18.4% were measured, which indicate a good stability of the R-TNT sample.

Phase transformation kinetics of anodic titania nanotube arrays in oxygen-rich atmosphere

Titania substrate and ambient atmosphere are pivotal in influencing the thermal stability of anodic TiO2 nanotube arrays (TNTs) due to anatase-to-rutile phase transition (ATRPT). This paper aimed to investigate detailed relationships between morphology and the crystallite structure and phase kinetics of O2-annealed TNTs with tube length > 10 μm and the inner diameter 60–80 nm. The study shows that below 700 °C, ARPT was very slow, but accelerated above 700 °C as nanotube structures showed signs of dramatic collapse, indicating that the thermal stability became poor. The resulting phase transformation kinetics of the O2-annealed TNTs are described by the general equation Ea= -∂ln(xr)·R/∂(1/T)·1000 , yielding approximate activation energy values of E1 = 150.71 ± 14.67 kJ/mol and E2 = 31.17 ± 1.53 kJ/mol for ARPT at temperatures below and above 600 °C, respectively. The transformation kinetics were found to be dominated by a “feeding effect” and a “size effect”, respectively. These findings serve to provide a useful method for preparing anodic TNTs with anticipant phase composition and thermal stability.

Enhanced Photocatalytic Performance of Anodized TiO2 Nanotube Arrays Decorated with BiVO4 Nanoparticles and Its Application for Rhodamine B Degradation

Enhanced Photocatalytic Performance of Anodized TiO2 Nanotube Arrays Decorated with BiVO4 Nanoparticles and Its Application for Rhodamine B Degradation

Investigation of Effects of Copper, Zinc, and Strontium Doping on Electrochemical Properties of Titania Nanotube Arrays for Neural Interface Applications

Direct interaction with the neuronal cells is a prerequisite to deciphering useful information in understanding the underlying causes of diseases and functional abnormalities in the brain. Precisely fabricated nanoelectrodes provide the capability to interact with the brain in its natural habitat without compromising its functional integrity. Yet, challenges exist in terms of the high cost and complexity of fabrication as well as poor control over the chemical composition and geometries at the nanoscale, all imposed by inherent limitations of current micro/nanofabrication techniques. In this work, we report on electrochemical fabrication and optimization of vertically oriented TiO2 nanotube arrays as nanoelectrodes for neural interface application. The effects of zinc, strontium, and copper doping on the structural, electrochemical, and biocompatibility properties of electrochemically anodized TiO2 nanotube arrays were investigated. It was found that doping can alter the geometric features, i.e., the length, diameter, and wall thickness, of the nanotubes. Among pure and doped samples, the 0.02 M copper-doped TiO2 nanotubes exhibited superior electrochemical properties, with the highest specific storage capacitance of 130 F g−1 and the lowest impedance of 0.295 KΩ. In addition, regeneration of Vero cells and neurons was highly promoted on (0.02 M) Cu-doped TiO2 nanotube arrays, with relatively small tube diameters and more hydrophilicity, compared with the other two types of dopants. Our results suggest that in situ doping is a promising method for the optimization of various structural and compositional properties of electrochemically anodized nanotube arrays and improvement of their functionality as a potential nanoelectrode platform for neural interfacing.

In-situ evolution of anodic TiO2 nanotubes to ammonium oxofluorotitanate mesocrystals and their conversion to mesocrystalline TiO2

3D ordered superstructures of mesocrystalline NH4TiOF3 and (NH4)2TiOF4 are synthesized via in-situ evolution from anodic TiO2 nanotube arrays grown on the Ti metal substrate under high current density. As revealed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy characterizations, the obtained NH4TiOF3 and (NH4)2TiOF4 mesocrystals consist of well aligned nanoparticle subunits at atomic level and can be converted to TiO2 (anatase) mesocrystals with their original exterior shapes retained upon thermal annealing. Close examination suggests that NH4TiOF3 and (NH4)2TiOF4 mesocrystals form via a nonclassical crystal growth process involving fast oriented aggregation of particles assisted by electric field-dipole interaction.

Anodic TiO2 nanotube arrays for photocatalytic CO2 conversion: comparative photocatalysis and EPR study

Titania (TiO2) is a widely used semiconductor for the photocatalytic decomposition of organic impurities in air, water and the conversion of CO2 into hydrocarbon fuel precursors. TiO2 in the form of nanotubes arrays is the most attractive for practical use because of the morphological advantages providing more favorable diffusion of photocatalytic reaction products and a low recombination rate of photogenerated electrons and holes. We have carried out a comparative study of the photocatalytic activity of gas-phase conversion of CO2 to hydrocarbon products and the defect properties of multi-walled and single-walled arrays of TiO2 nanotubes. Methanol and methane have been detected in the CO2 photoreduction process. The photocatalytic evolution rate of multi-walled TiO2 nanotubes is twice as fast for methane as for single-walled TiO2 nanotubes after four hours of irradiation and four times faster for methanol. The type and features of the structural defects have been investigated by EPR spectroscopy. For the first time, it has been shown that Ti3+/oxygen vacancy centers are mainly located inside the outer layer of nanotubes, while carbon dangling bonds have been observed directly on the surface of the inner layer. Carbon defects have been found to be the centers of adsorption and accumulation of photoinduced charge carriers. The results are entirely new; they clarify the role of different types of defects in the photocatalytic conversion of CO2 to hydrocarbon compounds and show good prospects for applying TiO2 nanotube arrays.

TiO2NTs bio-inspired coatings: revisiting electrochemical, morphological, structural, and mechanical properties

By altering some synthesis variables, the morphology and structural properties of anodic TiO2 nanotube arrays (TiO2NTs) can be tailored to a specific application. This study aims to investigate the effect of electrolyte-containing ions from human plasma and annealing temperature on structural, morphological, and mechanical parameters of TiO2NTs films, targeting its potential biomedical applications. Bio-inspired TiO2NTs were grown from Ticp and its Ti6Al4V alloy by potentiostatic anodization in the recently developed SBF-based electrolyte, maintained at 10 °C and 40 °C. The thermal investigation was performed by TGA/DSC and used to define the phase transition temperatures used for annealing (450 °C and 650 °C). Morphological and structural parameters were evaluated by FE-SEM, XRD, contact angle measurements, and nanoindentation. Results show that self-organized as-formed TiO2NTs were grown under all synthesis conditions with different wettability profiles for each substrate group. At 450 °C annealing temperature, the beginning of nanostructures collapse starts, becoming evident at 650 °C. The nanoindentation characterization reveals that both electrolyte and thermal annealing exhibited low effects on the hardness and Young’s modulus. The tailoring of specific properties by different synthesis conditions could allow the individualization of treatments and better performance in vivo.

Enhanced Visible Light-driven Photocatalytic Activities of Ag3PO4 Modified Electrochemically Anodized TiO2 Nanotube Arrays

Enhanced Visible Light-driven Photocatalytic Activities of Ag3PO4 Modified Electrochemically Anodized TiO2 Nanotube Arrays

Visible light responsive photocatalytic hydrogen production over composites of anodized TiO2 nanotube array and graphitic carbon nitride measured with a gas circulating reactor

Gas phase photocatalysis over composites of electrochemically anodized titania nanotube (TNT) arrays and graphitic carbon nitride (g-C3N4) nanoparticles were examined with a home-made, gas-circulating reactor system. g-C3N4 nanoparticles were deposited onto anodized TNT surfaces by facile thermal polymerization using melamine and urea as precursors. The existence of g-C3N4 on TNT arrays clearly improved hydrogen production from gas phase photocatalytic decomposition of water/methanol mixture under visible light (VIS) irradiation (370–800 nm). The enhanced production of hydroxyl radicals via water photooxidation for TNT/g-C3N4 composites was also ascertained by photoluminescence measurement using terephthalic acid as a radical trap. These results deriving from synergetic effects of TNT and g-C3N4 can be attributed to the photogenerated hole–electron separation enhanced at TNT/g-C3N4 interface, suggesting that g-C3N4 is a metal-free sensitizer for enabling VIS responsive photocatalysis in anodized TNTs even for gas phase reactions.