A pH sensor based on the TiO2 nanotube array modified Ti electrode

In this paper, a novel solid state pH sensor was fabricated by anodization of titanium substrate electrode. The relationship between pH sensitivity and hydrophilicity or surface morphology of TiO₂ film was investigated. Amorphous TiO₂ nanotube has better pH response than anatase TiO₂ nanotube. After being irradiated by ultraviolet light (UV), the potential response of the electrode modified by amorphous TiO₂ nanotube was close to Nernst equation (59 mV/pH). SEM, XRD, and XPS were used to characterize electrodes. Possible mechanism was discussed by analyzing surface hydroxyl groups, crystal structure and hydrophilicity of the electrodes. The electrode has been used to detect some kinds of soft drinks and shows good response.     

Immobilization of horseradish peroxidase in three-dimensional macroporous TiO2 matrices for biosensor applications

Three-dimensional macroporous TiO₂ was synthesized by a sol-gel procedure using polystyrene colloidal crystals as templates. SEM showed that a face-centered cubic (FCC) 3D macroporous structure was obtained. Horseradish peroxidase (HRP) was successfully immobilized on the surface of an optically transparent electrode (OTE). Photoelectrochemical properties were characterized using a three electrodes system and an ultraviolet lamp. The HRP/TiO₂/OTE displays a rapid photocurrent response, approximately 178.7 nA, under UV illumination (380 nm). The sensitivity of H₂O₂ detection was 70.04 μA/mM without UV illumination, and it increased to 102.97 μA/mM when illuminated by UV. The amperometric response was also enhanced. The high response was due to the good biocompatibility of TiO₂ and excellent photoelectrical property and the large effective surface of the three-dimensionally ordered macroporous structure.     

Chlorophyll assembled electrode for photovoltaic conversion device

Chlorophyll-a (Chl-a) assembled in hydrophobic domain by fatty acid with long alkyl hydrocarbon chain such as myristic acid (Myr), stearic acid (Ste) and cholic acid (Cho) modified onto nanocrystalline TiO₂ electrode is prepared and the photovoltaic properties of the nanocrystalline TiO₂ film by Chl-a are studied. Incident photon to current efficiency (IPCE) value at 660 nm in photocurrent action spectrum of Chl-a/Ste-TiO₂, Chl-a/Myr-TiO₂ and Chl-a/Cho-TiO₂ electrodes are 5.0%, 4.1% and 4.1%, respectively. Thus, the IPCE is maximum using Chl-a/Ste-TiO₂ electrode. From the results of photocurrent responses with light intensity of 100 mW cm⁻² irradiation or monochromatic light with 660 nm, generated photocurrent increases using Chl-a/Ste-TiO₂ electrode compared with the other Chl-a assembled TiO₂ electrodes. These results show that the hydrophobic domain formed by stearic acid with long alkyl hydrocarbon chain is suitable for fixation of Chl-a onto TiO₂ film electrodes and photovoltaic performance is improved using Chl-a onto Ste-TiO₂ film electrode.     

Hierarchical structured TiO2 nano-tubes for formaldehyde sensing

Hierarchical structured TiO₂ nano-tubes were prepared following a two-step method: the highly ordered uniform TiO₂ nanotube arrays were first grown by the conventional electrochemical anodization of the Ti metal sheet followed by mechanical milling of the as-fabricated TiO₂ nanotube arrays. The obtained nanotubes with a length around 400 nm and opening diameter ∼100 nm were formed mixed with the spherical TiO₂ single crystals with a diameter around 10 nm indicating hierarchical nanostructure. The as-synthesized TiO₂ hierarchical nanotubes based resistive-type chemical sensor exhibits good sensitivity to formaldehyde at room temperatures with or without UV-irradiation. The response of the sensor increased almost linearly as a function of the concentration of formaldehyde from 10–50 ppm under UV irradiation. The response of the sensor to different relative humidity and other possible interferents such as ammonia, methanol and alcohol was investigated. The larger response of the sensor to formaldehyde relative to these interferents is suggested to be due to the deeper diffusion of formaldehyde into the TiO₂ nanotubes.     

Novel graphite/TiO2 electrochemical cells as a safe electric energy storage system

A graphite/TiO₂ full cell has been developed as a new safety energy storage system using a highly safety process. The crystal structures of the anatase TiO₂ electrode have been investigated with respect to the performance of the electrodes. Due to the large anion intercalation into the graphite positive electrode, the possible charging potential can be raised to around 5.3 V against the Li/Li⁺ electrode, which is a higher charging voltage than lithium-ion batteries (maximum voltage is around 4.3 V vs. Li/Li⁺). In situ XRD measurements have been carried out on both the cathode and anode electrodes of the graphite/TiO₂ cell during the charge process to elucidate the intercalation mechanism.     

Anatase TiO2 spheres with high surface area and mesoporous structure via a hydrothermal process for dye-sensitized solar cells

Spherical pure anatase TiO₂ spheres with a mesoporous structure and high surface area of up to 116.5 m² g⁻¹ were prepared by a simple urea-assisted hydrothermal process and investigated as dye-sensitized solar-cell electrodes. Although the particle diameters of the prepared TiO₂ spheres ranged from 0.4 to 1.3 μm, due to the high specific surface area, mesoporous TiO₂ sphere electrode was obtained with enhanced light harvesting and a larger amount of dye loading. An overall light conversion efficiency of 7.54% under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) was achieved using the mesoporous TiO₂ spheres electrode, which was significantly higher than a commercial Degussa P25 TiO₂ nanocrystals electrode (5.69%).     

Amorphous Ru1−yCryO2 loaded on TiO2 nanotubes for electrochemical capacitors

Amorphous Ru_1−yCr_yO₂/TiO₂ nanotube composites were synthesized by loading different amount of Ru_1−yCr_yO₂ on TiO₂ nanotubes via a reduction reaction of K₂Cr₂O₇ with RuCl₃·nH₂O at pH 8, followed by drying in air at 150 °C. Cyclic voltammetry and galvanostatic charge/discharge tests were applied to investigate the performance of the Ru_1−yCr_yO₂/TiO₂ nanotube composite electrodes. For comparison, the performance of amorphous Ru_1−yCr_yO₂ was also studied. The results demonstrated that the three dimensional nanotube network of TiO₂ offered a solid support structure for active materials Ru_1−yCr_yO₂, allowed the active material to be readily available for electrochemical reactions, and increased the utilization of active materials. A maximum specific capacitance 1272.5 F/g was obtained with the proper amount of Ru_1−yCr_yO₂ loaded on the TiO₂ nanotubes.     

Anodic TiO2 Nanotube Arrays for Dye-Sensitized Solar Cells Characterized by Electrochemical Impedance Spectroscopy

This paper reports on the microstructure of anodic titanium oxide (TiO₂) and its use in a dye-sensitized solar cell (DSSC) device. When voltages of 60 V were applied to titanium foil for 2 hr under 0.25 wt% NH₄F+ 2 vol% H₂O+C₂H₄(OH)₂, TiO₂ with a nanotube structure was formed. The film, which had a large surface area, was used as an electron transport film in the DSSC. The DSSC device had a short-circuit current density (J_sc) of 12.52 mA cm⁻², a fill factor (FF) of 0.65, an open-voltage (V_oc) of 0.77 V, and a photocurrent efficiency of 6.3% under 100% AM 1.5 light. The internal impedance values under 100%, 64%, 11%, and 0% (dark) AM 1.5 light intensities were measured and simulated using the electrical impedance spectroscopy (EIS) technique. The impedance characteristics of the DSSC device were simulated using inductors, resistors, and capacitors. The Ti/TiO₂, TiO₂/Electrolyte, electrolyte, and electrolyte/(Pt/ITO) interfaces were simulated using an RC parallel circuit, and the bulk materials, such as the Ti, ITO and conducting wire, were simulated using a series of resistors and inductors. The impedance of the bulk materials was simulated using L₀+R₀+R_b, the impedance of the working electrode was simulated using (C₁//R₁)//(R_a+(C₂//R₂), the electrolyte was simulated using C₃//R₃, and the counter electrode was simulated using C₄//R₄.     

Stable TiO2 nanotube arrays with high UV photoconversion efficiency

This work is intended to define an optimal methodology for preparing highly ordered TiO₂ nanotube arrays by a 60-V anodization in a glycol ethylene solution. In order to obtain a mechanically stable structure with a high UV photoconversion efficiency, it is necessary to carefully control the growth mechanism through the anodization process. For this reason, the nanotube arrays have to be formed upon a compact titanium dioxide layer with well-defined thickness. Besides, both the fluoride concentration and anodization time are strictly correlated, because elevated concentrations and/or a long anodization time produce unstable structure with low photoconversion efficiency. The best result in the terms of reproducibility has been obtained previously for a three-minute galvanostatic oxide growth on the pickled titanium sheet, and anodic growth in ethylene glycol solution containing 1 wt.% H₂O and 0.20 wt.% NH₄F for a period lower than 4.5 h. The UV photoconversion efficiency was measured and a maximum value of 28.3% has been obtained, which is the highest result in the literature.     

Preparation and magnetic properties of iron titanium oxide nanotube arrays

FeTi alloy was prepared by a vacuum smelting method, iron titanium oxide nanotube arrays have been made directly by anodization of the FeTi alloy. Morphologies and microstructures of the samples were characterized by scanning electron microscope, transmission electron microscope, and X-ray diffractometer. Influences of temperature and H₂O concentration on the morphologies of the nanotube arrays have been discussed in detail. Magnetic properties of the samples have also been investigated. The as-prepared samples were amorphous. When annealed at 500 °C and 550 °C, pesudobrookite Fe₂TiO₅ was obtained. At 600 °C, there were mixed Fe₂TiO₅, rutile TiO₂, and α-Fe₂O₃. Magnetic performance of the nanotube arrays exhibited high sensitivity to temperature and changed interestingly upon annealing. The values of the coercivity and remanence were 340 Oe and 0.061 emu/g respectively for the sample annealed at 550 °C.     

Properties of sol-gel SnO2/TiO2 electrodes and their photoelectrocatalytic activities under UV and visible light illumination

A visible light active binary SnO₂-TiO₂ composite was successfully prepared by a sol-gel method and deposited on Ti sheet as a photoanode to degrade orange II dye. Titanium and SnO₂ can promote the development of rutile phase of TiO₂ and inhibit the formation of anatase phase of TiO₂. Formation of SnO₂ crystalline is insignificant even when the calcination temperature increases to 700 °C. Heterogenized interface between SnO₂ and TiO₂ inhibits growth of TiO₂ linkage and leads to the particle-filled surface morphology of SnO₂-containing films. The carbonaceous, Ti-O-C bonds and Ti³⁺ species are likely to account for the photoabsorption and photoelectrocatalytic (PEC) activity under visible light illumination. The electrode with 30% SnO₂ exhibits higher photocurrent when compared with those in the region of 0-50%. The 600 °C-calcined SnO₂-TiO₂ electrode indicates higher activity when compared with those at 400, 500, 700 and 800 °C. PEC degradation of orange II follows the Langmuir-Hinshelwood model and takes place much effectively in a solution of pH 3.0 than those in pH 7.0 and pH 11.0.     

Meldola blue immobilized on a new SiO2/TiO2/graphite composite for electrocatalytic oxidation of NADH

Meldola blue immobilized on a new SiO₂/TiO₂/graphite composite was applied in the electrocatalytic oxidation of NADH. The materials were prepared by the sol-gel processing method and characterized by several techniques including scanning electronic microscopy coupled to energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electronic microscopy (HRTEM). Si and Ti mapping profiles on the surface showed a homogeneous distribution of the components. Ti2p binding energy peaks indicate that the formation of Si-O-Ti linkage is presumably the responsible for the high rigidity of the matrices. The good electrical conductivity presented by the composites (5 and 11 S cm⁻¹) can be related to a homogeneous distribution of graphite particles observed by TEM. After the materials characterization, a SiO₂/TiO₂/graphite electrode was prepared and some chemical modifications were performed on its surface to promote the adsorption of meldola blue. The resulting system presented electrocatalytic properties toward the oxidation of NADH, decreasing the oxidation potential to −120 mV. The proposed sensor showed a wide linear response range from 0.018 to 7.29 mmol l⁻¹ and limit of detection of 0.008 mmol l⁻¹. SiO₂/TiO₂/graphite has shown to be a promising material to be used as a suitable support in the construction of new electrochemical sensors.     

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 tuning of titania nanotube morphology in inhibitor electrolytes

The electrochemical behavior of fluorine containing electrolytes and its influence in controlling the lateral dimensions of TiO₂ nanotubes is thoroughly investigated. Potentiostatic anodization is carried out in three different electrolytes, viz., aqueous hydrofluoric acid (HF), HF containing dimethyl sulphoxide (DMSO) and HF containing ethylene glycol (EG). The experiments were carried out over a broad voltage range from 2 to 200 V in 0.1-48 wt% HF concentrations and different electrolytic compositions for anodization times ranging from 5 s to 70 h. The chemistry that dictates how the nature of electrolytes influences the morphology of nanotubes is discussed. Electrochemical impedance spectra were recorded for varying compositions of all the electrolytes. It was observed that composition of the electrolyte and its fluorine inhibiting nature has significant impact on nanotube formation as well as in controlling the aspect ratio. The inhibiting nature of EG is helpful in holding fluorine at the titanium anode, thereby allowing controlled etching at appropriate voltages. Thus our study demonstrates that HF containing EG is a promising electrolytic system providing wide tunability in lateral dimensions and aspect ratio of TiO₂ nanotubes by systematically varying the anodization voltage and electrolyte composition.     

TiO2 nanotube arrays annealed in CO exhibiting high performance for lithium ion intercalation

Anatase titania nanotube arrays were fabricated by means of anodization of Ti foil and annealed at 400 °C in respective CO and N₂ gases for 3 h. Electrochemical impendence spectroscopy study showed that CO annealed arrays possessed a noticeably lower charge-transfer resistance as compared with arrays annealed in N₂ gas under otherwise the same conditions. TiO₂ nanotube arrays annealed in CO possessed much improved lithium ion intercalation capacity and rate capability than N₂ annealed samples. At a high charge/discharge current density of 320 mA g⁻¹, the initial discharge capacity in CO annealed arrays was found to be as high as 223 mAh g⁻¹, 30% higher than N₂ annealed arrays, ∼164 mAh g⁻¹. After 50 charge/discharge cycles, the discharge capacity in CO annealed arrays remained at ∼179 mAh g⁻¹. The improved intercalation capacity and rate capability could be attributed to the presence of surface defects like Ti-C species and Ti³⁺ groups with oxygen vacancies, which not only improved the charge-transfer conductivity of the arrays but also possibly promoted phase transition.     

Light energy storage and photoelectrochemical behavior of the titanate nanotube array/Ni(OH)2 electrode

A new kind of TiO₂ nanotube array/Ni(OH)₂ (TiO₂/Ni(OH)₂) composite electrode with the storage ability of light energy was prepared by the deposition of Ni(OH)₂ on the TiO₂ nanotube array, which was synthesized by anodizing Ti foils in an HF aqueous solution. SEM and XRD results showed that Ni(OH)₂ particles were well distributed on high density, well-ordered and uniform TiO₂ nanotube arrays. The photoelectrochemical properties of the TiO₂/Ni(OH)₂ electrode were investigated in NaHCO₃/NaOH buffer solution (pH 10) by means of UV-vis absorption spectra, cyclic voltammogram (CV) and photocurrent measurements. It was found that the TiO₂/Ni(OH)₂ electrode was highly sensitive to light and exhibited excellent photoelectrochromic properties. Upon UV irradiation, the photogenerated holes by TiO₂ nanotube arrays can oxidize Ni(OH)₂ to NiOOH, and thus the TiO₂/Ni(OH)₂ electrode can be photo-charged by light.     

Photoelectro-Fenton combined with photocatalytic process for degradation of an azo dye using supported TiO2 nanoparticles and carbon nanotube cathode: Neural network modeling

In this work, treatment of an azo dye solution containing C.I. Basic Red 46 (BR46) by photoelectro-Fenton (PEF) combined with photocatalytic process was studied. Carbon nanotube-polytetrafluoroethylene (CNT-PTFE) electrode was used as cathode. The investigated photocatalyst was TiO₂ nanoparticles (Degussa P25) having 80% anatase and 20% rutile, specific surface area (BET) 50 m²/g, and particle size 21 nm immobilized on glass plates. A comparison of electro-Fenton (EF), UV/TiO₂, PEF and PEF/TiO₂ processes for decolorization of BR46 solution was performed. Results showed that color removal follows the decreasing order: PEF/TiO₂ > PEF > EF > UV/TiO₂. The influence of the basic operational parameters such as initial pH of the solution, initial dye concentration, the size of anode, applied current, kind of ultraviolet (UV) light and initial Fe³⁺ concentration on the degradation efficiency of BR46 was studied. The mineralization of the dye was investigated by total organic carbon (TOC) measurements that showed 98.8% mineralization of 20 mg/l dye at 6 h using PEF/TiO₂ process. An artificial neural network (ANN) model was developed to predict the decolorization of BR46 solution. The findings indicated that artificial neural network provided reasonable predictive performance (R² = 0.986).     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Preparation and characterisation of visible light responsive iodine doped TiO2 electrodes

Characteristics are presented of new iodine doped TiO₂ (I-TiO₂) prepared via the hydrothermal method, where titania (IV) complexes with a ligand containing an iodine atom have been used as a precursor. The structure of samples has been examined by XPS, XRD, UV-vis and FT-IR-ATR techniques. These studies confirm that the obtained powder exhibits a decrease in the bandgap energy value (E_g = 2.8 eV). The report presents electrochemical studies of I-TiO₂ films on a Pt electrode, which allow determination of the flatband potential E_fb = −0.437 V vs. SCE (in 0.5 M Na₂SO₄). Cyclic voltammetry measurements show anodic and cathodic activities under Vis and UV-vis radiation. The photocurrent enhancement due to visible light radiation reached 30% of the whole photoacitivity exhibited under UV-vis illumination.     

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.