Transparent titania nanotubes of micrometer length prepared by anodization of titanium thin film deposited on ITO

Transparent TiO₂ nanotube arrays of micrometer lengths were prepared by anodization of titanium thin film RF sputtered on indium tin oxide (ITO) which was coated on glass substrate. The sputtering process took place at elevated temperature of 500 °C. The structures of the films were studied using scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the optical properties of the films were investigated using UV-visible spectroscopy. Two types of electrolytes were used in this work: an aqueous mixture of acetic acid and HF solution and a mixture of NH₄F and water dissolved in ethylene glycol. The concentration of NH₄F, voltage and the thickness of the sputtered titanium film were varied to study their effect on the formation of TiO₂ nanotube arrays. It is demonstrated in this work that the nanoporous layer is formed on top of the ordered array of TiO₂ nanotubes. Furthermore, the optical transmittance of TiO₂ nanotubes annealed at 450 °C is much lower than the non annealed TiO₂ nanotubes in the visible wavelength region.     

Efficient visible light-induced photoelectrocatalytic degradation of rhodamine B by polyaniline-sensitized TiO<Subscript>2</Subscript> nanotube arrays

Self-organized anodic TiO₂ nanotube arrays were sensitized with polyaniline by a simple electrodeposite method. The morphological and structural properties studied by scanning electron microscopy and fourier transform infrared spectroscopy reveal the successful deposition of polyaniline on the nanotube arrays. The polyaniline-sensitized TiO₂ nanotube arrays exhibit a distinguishable red shift on the absorption spectrum. Electrochemical impedance investigation attested to a significant improvement of the interfacial electron-transfer kinetics for promoted electron–hole effective separation. The as-prepared samples showed a high efficiency for the photoelectrocatalytic degradation of rhodamine B under visible-light irradiation (λ > 400 nm). The enhanced photoelectrocatalytic activity could be attributed to the extended absorption in the visible-light region by the polyaniline and the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the polyaniline/TiO₂ nanotube arrays interface.     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

Effect of ZnS layers on optical properties of prepared CdS/TiO<Subscript>2</Subscript> nanotube arrays for photocatalyst

The TiO₂ nanotube arrays (TiO₂ NTAs) prepared by re-oxidation were chosen as basement. The NTAs prepared through re-oxidation show smoother surface and more uniform tube mouth on large scale compared with the first as-grown one. We use successive ionic layer adsorption and reaction method to deposit quantum dots (ZnS and CdS) onto the sample successively. The findings reveal that two kinds of quantum dots (～10 nm) distribute regularly and the nanotube mouth is open. From the UV–Vis absorption spectrum of samples, the red shift occurs after the sedimentation of the two quantum dots, which proves that the double modification can expand the absorption to 650 nm. Among all specimens, the sample produced by co-deposition has the highest speed of catalytic efficiency of 90.7% compared with bare TiO₂ NTAs (52.9%) and just CdS QDs sensitized sample (65.8%). In the test of photocatalysis durability, the decay percentages of CdS/TiO₂ NTAs and ZnS/CdS/TiO₂ NTAs were 35.8 and 48.4%, respectively, which means that the ZnS passivation layer plays a crucial role in enhancing photocatalytic activities.     

Effect of Sn doping on the structural,optical and electrical properties of TiO2 films prepared by spray pyrolysis

In this work, highly oriented pure and Tin-doped Titanium dioxide (Sn-doped TiO₂) with porous nature photoelectrodes were deposited on ITO glass plates using spray pyrolysis technique. The XRD pattern revealed the formation of anatase TiO₂ with the maximum intensity of (101) plane while doping 6 at% of Sn. The morphological studies depicted the porous nature with the uniform arrangement of small-sized grains. The presence of tin confirmed with the EDX spectra. The size of particles of 13 nm was observed from High Resolution Transmission Electron Microscopy (HR-TEM) analysis. The average transmittance was about 85% for the doped photoelectrode and was observed for the photoelectrode deposited with 6 at% of tin, with decreased energy band gap. The PL study showed the emission peak at 391 nm. The maximum carrier concentration and Hall mobility was observed for the photoelectrode deposited with 6 at% of tin. With these studies, the DSSCs were prepared separately with the dye extracted from Hibiscus Rosasinesis and Hibiscus Surttasinesis and their efficiency was maximum for the DSSC prepared with 6 at% of tin.     

Facile fabrication, characterization, and enhanced photoelectrocatalytic degradation performance of highly oriented TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays were successfully fabricated using ethanol and water mixture electrolytes (40 vol% ethanol and 0.2 wt% hydrofluoric acid) by a facile electrochemical anodization method. The as-prepared nanotube arrays were grown perpendicular to the titanium substrate with about 90 nm in diameter, 20 nm in wall thickness, and around 500 nm in length. The formation mechanism of the samples is briefly discussed. A blue shift in the spectrum of UV–Vis absorption was observed with respect to a piece of the sol–gel derived TiO₂ film. Moreover, photocurrent response and photoelectrocatalytic degradation of methyl orange under ultraviolet light irradiation were adopted to evaluate the photoelectrocatalytic properties of the TiO₂ nanotube arrays. We demonstrate that the highly ordered TiO₂ nanotube arrays possess much better photoelectrocatalytic activity than the sol–gel derived TiO₂ film and good stability.     

Binder-free combination of amorphous TiO<Subscript>2</Subscript> nanotube arrays with highly conductive Cu bridges for lithium ion battery anode

Binder-free combination of highly conductive Cu bridges with amorphous TiO₂ nanotube arrays for lithium ion battery anode were designed and achieved via one-step facile electrodeposition. The obtained composite Cu/TiO₂ nanotubes electrode was studied in terms of XRD, SEM, EDX, galvanostatic charge/discharge, cycle stability, rate performance, and AC impedance. As expected, the composite electrode delivered higher discharge capacity, rate performance, and cycle stability than the bare one, possibly due to improved electrical conductivity and the synergy effect between conductive Cu bridges and amorphous TiO₂ nanotube arrays.     

Synthesis and characterization of bamboo-like CdS/TiO<Subscript>2</Subscript> nanotubes composites with enhanced visible-light photocatalytic activity

In order to efficiently use the visible light in the photocatalytic reaction, a novel bamboo-like CdS/TiO₂ nanotubes composite was prepared by a facile chemical reduction method, in which CdS nanoparticles located in the TiO₂ nanotubes. The composition and structure of this nanocomposite were characterized by TEM, HRTEM, XRD, XPS, FTIR and UV-vis spectroscopy. This CdS/TiO₂ nanotubes composite exhibited much higher visible-light photocatalytic activity for the degradation of methylene blue than pure TiO₂ nanotubes and CdS nanoparticles, and the highest photodegradation efficiency after 6 h irradiation can reach 84.5%. It is inferred that the unique structure of CdS/TiO₂ nanotubes composites acts an important role for the improvement of their photocatalytic activity.     

Applying the statistical experimental method to evaluate the process conditions of TiO2 nanotube arrays by anodization method

Vertically oriented TiO₂ nanotube arrays were successfully produced by the anodization technique in NH₄F/H₃PO₄ electrolyte. The structure and morphology were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It is found that TiO₂ nanotube arrays annealed at 500 °C containing 100% anatase phase and entirely converted into rutile at 800 °C. The response surface methodology (RSM) and Box-Behnken design were applied to find the optimal factor conditions in production of TiO₂ nanotube arrays. Based on the results in preliminary experiments, we selected anodization time, anodization voltage and NH₄F concentration as the key factors to investigate their effects on responses. The regression models were built by fitting the experimental results with a second-order polynomial. By using the regression models, the optimal factor conditions were obtained as follows: anodization time of 300 min; anodization voltage of 15.39 V; NH₄F concentration of 0.50 M. Corresponding to the optimal factor conditions, the predicted average length and diameter of nanotube array were 1429 nm and 33 nm, respectively. Confirmation experiments using the optimized conditions were performed: TiO₂ nanotube arrays were obtained with an average tube length of 1420 nm and average tube diameter of 36 nm. The experimental results are in good agreement with the predicted results.     

TiO<Subscript>2</Subscript> Nanorod Arrays Sensitized with CdS Quantum Dots for Solar Cell Applications: Effects of Rod Geometry on Photoelectrochemical Performance

CdS quantum dot (QD) sensitized TiO₂ nanorod array (NRA) film electrodes with different rod geometries were fabricated via a solvothermal route followed by a sequentialchemical bath deposition (S-CBD) process. By controlling the solution growth conditions, the rod geometries, especially the tip structures, of the TiO₂ NRAs were tuned. The results indicated that the vertically aligned hierarchical NRAs possessed conically shaped tip geometry, which was favorable for film electrodes due to the reduced reflectance, enhanced light harvesting, fast charge-carrier separation and transfer, suppression of carrier recombination, sufficient electrolyte penetration and subsequent efficient QD assembly. CdS QD sensitized TiO₂ NRA film electrodes with tapered tips exhibited an enhanced photoelectrochemical (PEC) performance, a photocurrent intensity of 5.13 mA/cm² at a potential of 0 V vs. saturated calomel electrode, an open-circuit potential of −0.68 V vs. saturated calomel electrode and an incident photon to current conversion efficiency (IPCE) of 22% in the visible-light region from 400 to 500 nm. The effects of rod geometry on the optical absorption, reflectance, hydrophilic properties and PEC performance of bare TiO₂ and CdS QD sensitized TiO₂ NRA film electrodes were investigated. The mechanism of charge-carrier generation and transfer in these CdS QD sensitized solar cells based on vertically aligned TiO₂ nanorods is discussed.     

Flexible TiO<Subscript>2</Subscript> nanotube-based dye-sensitized solar cells using laser-drilled microhole array electrodes

Here we report on the growth of TiO₂ nanotube arrays (TNAs) on Ti foil with laser-drilled microhole arrays (MHAs). The MHAs promoted the adhesion of the TNA film to Ti substrate, which is well suited for flexible dye-sensitized solar cells (DSSCs). The MHA photoanode and TNAs were characterized by SEM, 3D optical profiling, XRD and TEM. For such a flexible MHA photoanode, the TNA-based DSSC was assembled using a platinized conductive glass counter electrode, and a conversion efficiency of 3.45% was achieved under AM 1.5 condition. A flexible TNA-based DSSC was also fabricated using a flexible MHA photoanode combined with a platinized indium tin oxide-polyethylene naphthalate counter electrode, which achieved 2.67% photovoltaic conversion efficiency under simulated AM 1.5 sunlight.     

Anodic TiO<Subscript>2</Subscript> nanotubes powder and its application in dye-sensitized solar cells

An increasing energy demand and environmental pollution create a pressing need for clean and sustainable energy solutions. TiO₂ semiconductor material is expected to play an important role in helping solve the energy crisis through effective utilization of solar energy based on photovoltaic devices. Dye-sensitized solar cells (DSSCs) are potentially lower cost alternative to inorganic silicon-based photovoltaic cells. In this study, we report on the fabrication of DSSCs from anodic TiO₂ nanotubes (NT) powder, produced by rapid breakdown potentiostatic anodization of Ti foil in 0.1 M HClO₄ electrolyte, as photoanode. TiO₂ NT powders with a typical NT outer diameter of approximately 40 nm, wall thickness of approximately 8–15 nm, and length of about 20–25 μm, have been synthesized. The counter electrode was made by electrodeposition of Pt from an aqueous solution of 5 mM H₂PtCl₆ onto fluorine-doped tin oxide (FTO) glass substrate. The above front-side illuminated DSSCs were compared with back-side illuminated DSSCs fabricated from anodic TiO₂ NTs that were grown on the top of Ti foil as photoanode. The highest cell efficiency was 3.54% under 100 mW/cm² light intensity (1 sun AM 1.5G light, Jsc = 14.3 mA/cm², Voc = 0.544 V, FF = 0.455). To the best of our knowledge, this is the first report on the fabrication of DSSC from anodic TiO₂ NTs powder. The TiO₂/FTO photoanodes were characterized by FE-SEM, XRD, and UV–Visible spectroscopy. The catalytic properties of Pt/FTO counter electrodes have been examined by cyclic voltammetry.     

Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.     

Fabrication of Ag/TiO2 nanotube array with enhanced photo-catalytic degradation of aqueous organic pollutant

In this paper, the fabrication of Ag/TiO₂ nanotube arrays and their photo-catalytic activity have been studied. The SEM, TEM and XRD were performed to characterize the morphology and crystalline phase of the TiO₂ nanotube array and Ag/TiO₂ nanotube array. Ag nanoparticles with different loadings, which are aimed to suppress the electron–hole recombination so as to enhance the photo-catalytic oxidation efficiency, were systematically coated onto TiO₂ nanotubes. The photo-catalytic activity of these nano-materials was evaluated by the degradation of two different pollutants: methyl orange and glyphosate. The effects of various parameters, such as the amount of the photo-catalyst, the illumination time, and pH value on the photo-catalytic oxidation activity, were studied.     

Orientation ordering of N<Subscript>2</Subscript> molecules in vertically aligned CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanotubes

Arrays of vertically aligned nitrogen-doped carbon (CN _x ) nanotubes have been synthesized by decomposition of aerosol mixture of acetonitrile and ferrocene at 850°C. Nitrogen concentration in the outer shells of the CN _x nanotubes was found from X-ray photoelectron spectroscopy (XPS) data to reach ∼6%. The XPS N 1s spectra and N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra identified three chemical forms of nitrogen in the CN _x nanotube arrays: pyridine-like, graphitic, and molecular nitrogen. The π ^* resonance of molecular nitrogen showed clear polarization dependence that indicates predominant orientation of N₂ molecules along the nanotubes axis. The estimated range of the polar angle distribution of the N₂ molecules orientation in the CN _x nanotube array amounts to 15°.     

Growth of ultra-thin TiO2 films by spray pyrolysis on different substrates

In the present study TiO₂ films were deposited by spray pyrolysis method onto ITO covered glass and Si (1 0 0) substrates. The spray solution containing titanium(IV) isopropoxide, acetylacetone and ethanol was sprayed at a substrate temperature of 450 °C employing 1-125 spray pulses (1 s spray and 30 s pause). According to AFM, continuous coverage of ITO and Si substrates with TiO₂ layer is formed by 5-10 and below 5 spray pulses, respectively. XPS studies revealed that TiO₂ film growth on Si substrate using up to 4 spray pulses follows 2D or layer-by-layer-growth. Above 4 spray pulses, 3D or island growth becomes dominant irrespective of the substrate. Only 50 spray pulses result in TiO₂ layer with the thickness more than XPS measurement escape depth as any signal from the substrate could not be detected. TiO₂ grain size remains 30 nm on ITO and increases from 10-20 nm to 50-100 nm on Si substrate with the number of spray pulses from 1 to 125.     

Raman investigations of TiO2 nanotube substrates covered with thin Ag or Cu deposits

A tubular array of TiO₂ nanotubes on Ti matrix was used as a support for Ag or Cu sputter‐deposited layers intended for surface‐enhanced Raman scattering (SERS) investigations. The composite samples of Ag/TiO₂–nanotube/Ti and Cu/TiO₂–nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) [and scanning Auger microscopy (SAM)] to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured after it had been adsorbed on the TiO₂–nanotube/Ti substrates covered with thin Ag or Cu deposit as well as on the bulk electrochemically roughened Ag or Cu reference substrates. It was found that the SERS spectra measured for pyridine adsorbed on the bulk silver substrate were significantly different than the spectra measured on the TiO₂–nanotube/Ti substrates covered the Ag layer. The spectra measured for pyridine adsorbed on the Ag/TiO₂–nanotube/Ti suggest that on the surface of such a composite substrate there are many Lewis acidic sites. Spectra typical for pyridine adsorbed on acidic sites were observed even after deposition of a relatively thick silver layer (e.g. an Ag layer with an average thickness of 80 nm) on the TiO₂–nanotube/Ti support. Our findings suggest that TiO₂–nanotube/Ti support is a promising substrate for the preparation of metallic nano‐clusters on a support containing acidic active sites. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly ordered anodic TiO2 nanotube arrays and their stabilities as photo(electro)catalysts

Highly ordered TiO₂ nanotube arrays with an average diameter of 230 nm, a wall thickness of 30 nm and a length of 1.8 μm were fabricated within a large domain by electrochemically anodizing of a titanium foil in a mixed solution of glycerol and NH₄F aqueous electrolyte. The TiO₂ nanotubes exhibit an anatase structure after annealing at 450 °C in air for 3 h. The direct photolysis (DP), photocatalytic (PC), electrocatalytic (EC) and photoelectrocatalytic (PEC) activities of the TiO₂ nanotube arrays were investigated using methyl orange (MO) as the model pollutant. The degradation of MO in PC process is faster than that in DP process, which confirms the photocatalysis of TiO₂ nanotube arrays. The degradation rate in PEC process is much higher than those in EC and PC processes, which demonstrates the synergetic effect between PC and EC processes. The synergetic factor is 4.1, which suggests that the synergetic effect is strong. Moreover, the stabilities of morphology, structure and photo(electro)catalytic degradation performance of the TiO₂ nanotube arrays were studied in order to evaluate their applicability as photo(electro)catalysts. The photo(electro)catalytic experiments bring neither morphological nor structural modifications to the nanotube arrays. The photo(electro)catalytic degradation rates of the TiO₂ nanotube arrays maintain stable in 10 cycles, which indicates that the TiO₂ nanotube arrays are appropriate to be applied as photo(electro)catalysts.     

TiO2 Nanoparticles Produced by Electric-Discharge-Nanofluid-Process as Photoelectrode of DSSC

利用自制TiO₂纳米粒子研究敏化染敏太阳能电池. 使用自制的旋转涂布加热平台装置将产出的TiO₂粒子均匀的涂布在ITO导电玻璃上形成薄膜,浸泡于N-719 染料中12小时以上作为DSSCs的光电极 元件,最后完成染料敏化太阳能电池的系统组装并进行光电转换效率测量. 实验结果表明,放电过程产出的TiO₂纳米粒子具有锐钛矿晶相,粒径尺寸可控制在20～70 nm,粒子表面电位约为-30 mV,是稳定的纳米悬浮夜. 添加0.5 mL 的Triton X-100在导电玻璃表面上,利用的旋转涂布加热到22 oC可以制得厚度均匀缜密的薄膜结构,不但粒子不受到热处理效应与介面活性剂的影响而发生晶相改变,并且薄膜也有良好的染料吸附效果. 较厚二氧化钛薄膜的光电极会提升敏化染敏太阳能电池的效率. 实验结果得知,以15 μm的二氧化钛薄膜组装DSSCs测得最高效率2.15%,但是当薄膜厚度超过15 μm 则会导致开路电压与充填因子逐渐下降,光电转换效率变差.     

Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.