Fast Growth of Highly Ordered TiO2 Nanotube Arrays on Si Substrate under High-Field Anodization

Highly ordered TiO_2 nanotube arrays(NTAs) on Si substrate possess broad applications due to its high surfaceto-volume ratio and novel functionalities, however, there are still some challenges on facile synthesis. Here, we report a simple and cost-effective high-field(90–180V) anodization method to grow highly ordered TiO_2 NTAs on Si substrate,and investigate the effect of anodization time, voltage, and fluoride content on the formation of TiO_2 NTAs. The current density–time curves, recorded during anodization processes, can be used to determine the optimum anodization time. It is found that the growth rate of TiO_2 NTAs is improved significantly under high field, which is nearly 8 times faster than that under low fields(40–60 V). The length and growth rate of the nanotubes are further increased with the increase of fluoride content in the electrolyte.

Two-Step Anodization of Maltilayer TiO_2 Nanotube and Its Photocatalytic Activity under UV Light

A double-layer TiO2 nanotube arrays were formed by two-step anodization of Ti foils in different electrolytes. First, Ti in 0.5 wt% HF was anodized to form thin nanotube layer. Afterwards a second anodization was conducted in a formamide based electrolyte, which allowed the second layer of nanotube growing directly underneath the first one. From FESEM investigation we found that the thickness of second layer corresponded to the anodization time, the increasing of which would lead to the excessive etching on the first layer. The first layer protected the lower one from fluoride corrosion during anodization process. The double layer TiO2 nanotube arrays showed no benefit to photodegradation effect in methyl orange degradation experiments.

Formation Mechanistism Study of TiO2 Film Comprising Nanotubes and Nanoparticles

A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and its influence on the morphology of the TiO2 film was discussed. The results show that the electric field strength is enhanced by the covering. The growth rate of TiO2 increases with the assist of the local electric field. However, TiO2 dissolution is hindered since the local electric field prevents [TiF6]6- from diffusing. It means that the balance condition for the formation of nanotubes is broken, and TiO2 nanoparticles are formed. Moreover, the crystal structure of the TiO2 film was confirmed using X-ray diffraction and Raman analysis. The anatase is a main phase for the proposed film.

Synthesis and Characterization of Niobium-doped TiO_2 Nanotube Arrays by Anodization of Ti-20Nb Alloys

Well crystallized niobium-doped TiO; nanotube arrays （TiNbO-NT） were successfully synthesized via the anodization of titanium/niobium alloy sheets, followed with a heat treatment at 550 ℃ for 2 h. Morphology analysis results demonstrated that both the titanium/niobium alloy microstructure and the dissolution strength of electrolyte played major roles in the formation of nanotube structure. A single-phase microstructure was more favorable to the formation of uniform nanotube arrays, while modulating the dissolution strength of electrolyte was required to obtain nanotube arrays from the alloys with multi-phase microstructures. X-ray diffraction （XRD） and X-ray photoelectron （XPS） analysis results clearly demonstrated that niobium dopants （Nb^5＋） were successfully doped into TiO2 anatase lattice by substituting Ti^4＋ in this approach.

Unveiling the controversial mechanism of reversible Na storage in TiO2 nanotube arrays： Amorphous versus anatase TiO2

Due to their inherent safety, low cost, and structural stability, TiO2 nanostructures represent a suitable choice as anode materials in sodiumion batteries. In the recent years, various hypotheses have been proposed regarding the actual mechanism of the reversible insertion of sodium ions in the TiO2 structure, and previous reports are often controversial in this respect. Interestingly, when tested as binder- and conducting additive-free electrodes in laboratory-scale sodium cells, amorphous and crystalline （anatase） TiO2 nanotubular arrays obtained by simple anodic oxidation exhibit peculiar and intrinsically different electrochemical responses. In particular, after the initial electrochemical activation, anatase TiO2 shows excellent rate capability and very stable long-term cycling performance with larger specific capacities, and thus a clearly superior response compared with the amorphous counterpart. To obtain deeper insight, the present materials are thoroughly characterized by scanning electron microscopy and ex situ X-ray diffraction, and the insertion of sodium ions in the TiO2 bulk phases is systematically modeled by density functional theory calculations. The present results may contribute to the development of more systematic screening approaches to identify suitable active materials for highly efficient sodium-based energy storage systems.

Fabrication of TiO_2 Nanotube Arrays by Rectified Alternating Current Anodization

Anodization is a popular method of preparing TiO2nanotube array films（TiNTs） by using direct current（DC）power as the driving voltage.In this study,three driving voltage modes,namely,the sine alternating current（sine） mode,the full-wave rectification of sine waves via four diodes（sine-4D,where D means diode） mode,and the DC mode,were used to prepare TiNTs by anodization.At 20 V,TiNTs were formed under sine-4D mode but only irregular porous TiO2films were formed under DC mode.At 50 V,TiNTs formed under both the sine-4D and DC modes.No TiNTs formed in the sine mode anodization at either 20 or 50 V.Compared with the DC mode,the sine-4D mode required a lower oxidation voltage for TiNT formation,which suggests that sine-4D is an economical,convenient,and efficient driving voltage for TiNT preparation by anodization.The morphologies and structures of TiNT samples anodized at 50 V in the sine-4D and DC modes at different oxidation time（1,5,10,30,60,and 120 min） were analyzed.TiNT growth processes were similar between the studied modes.However,the growth rate of the films was faster under the sine-4D mode than the DC mode during the first 30 min of anodization.

Effect of Anodization Parameters on Morphology and Photocatalysis Properties of TiO_2 Nanotube Arrays

Highly ordered TiO2 nanotube arrays were fabricated via electrochemical anodization of high purity Ti foil in fluoride-containing electrolyte. The effects of applied anodization potential, anodization time on the formation of TiO2 nanotube arrays and the photocatalytic degradation of methylene blue （MB） were discussed. The TiO2 nanotube arrays calcined at 500 ℃ for 2 h show pure anatase phase. The pore diameters of TiO2 nanotube arrays can be adjusted from 30 to 90 nm using a different anodization voltage. Anodization time mainly influenced TiO2 tube length, and by increasing the anodization time, the nanotube length became longer gradually. When the anodization potential was 40 V, the average growth rate of TiO2 nanotube was about 4.17 μm/h. Both anodization potential and time had important effects on the photocatalytic efficiency. The TiO2 nanotube arrays obtained at anodization potential of 40 V for I h showed the best photocatalytic degradation ratio of MB.

Study of Cell Behaviors on Anodized TiO_2 Nanotube Arrays with Coexisting Multi-Size Diameters

It has been revealed that the different morphologies of anodized TiO_2 nanotubes, especially nanotube diameters, triggered different cell behaviors. However, the influence of TiO_2 nanotubes with coexisting multi-size diameters on cell behaviors is seldom reported. In this work, coexisting four-diameter TiO_2 nanotube samples, namely,one single substrate with the integration of four different nanotube diameters(60, 150, 250, and 350 nm), were prepared by repeated anodization. The boundaries between two different diameter regions show well-organized structure without obvious difference in height. The adhesion behaviors of MC3T3-E1 cells on the coexisting fourdiameter TiO_2 nanotube arrays were investigated. The results exhibit a significant difference of cell density between smaller diameters(60 and 150 nm) and larger diameters(250 and 350 nm) within 24 h incubation with the coexistence of different diameters, which is totally different from that on the single-diameter TiO_2 nanotube arrays. The coexistence of four different diameters does not change greatly the cell morphologies compared with the singlediameter nanotubes. The findings in this work are expected to offer further understanding of the interaction between cells and materials.

Crack initiation,propagation and saturation of TiO_2 nanotube film

Vertically orientated TiO2 nanotube array with diameters ranging from 60 up to 80 nm and length of 4 μm was grown on titanium by anodization.Crack initiation,propagation and saturation were studied using the substrate straining test.The results show that annealing obviously modifies the interfaces.With the increase of tensile strain,cracks in TiO2 nanotube films propagate rapidly and reach the saturation within a narrow strain gap.Interfacial shear strengths of TiO2 nanotube films without annealing,with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 163.3,370.2 and 684.5 MPa,respectively.The critical energy release rates of TiO2 nanotube films are calculated as 49.6,102.6 and 392.7 J/m2,respectively.The fracture toughnesses of TiO2 nanotube films are estimated as 0.996,1.433 and 2.803 MPa-m1/2,respectively.The interfacial bonding mechanism of TiO2 nanotube film is chemical bonding.

Buckling pattern of TiO_2 nanotube film

Substrate straining test was carried out to study the buckling pattern of TiO2 nanotube film. The results show that the tensile strains of buckling occurrence of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing are 2.5%, 8.9% and 7.8%, respectively, which indicates the modifying effects of temperature annealing. Through the SEM observation, the critical buckling stresses of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 180.4, 410.2 and 619.5 MPa, respectively. The critical buckling stress of TiO2 nanotube films with 250 ℃ annealing from AFM observation is estimated as 470.2 MPa, which indicates good agreement with the critical buckling stress from SEM observation. The true stress and the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing are given as 840.3 MPa and 77.2 J/m2, respectively. Excellent agreement of the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing in terms of buckling perspective and crack perspective is obtained.

Nitrogen-doped carbon encapsulated in mesoporous TiO2 nanotubes for fast capacitive sodium storage

Controllable synthesis of insertion-type anode materials with beneficial micro-and nanostructures is a promising approach for the synthesis of sodium-ion storage devices with high-reactivity and excellent electrochemical performance.In this study,we developed a sacrificial-templating route to synthesize TiO_(2)@N-doped carbon nanotubes(TiO_(2)@NC-NTs)with excellent electrochemical performance.The asprepared mesoporous TiO_(2)@NC-NTs with tiny nanocrystals of anatase TiO_(2) wrapped in N-doped carbon layers showed a well-defined tube structure with a large specific surface area of 198 m^(2) g^(-1) and a large pore size of~5 nm.The TiO_(2)@NC-NTs delivered high reversible capacities of 158 m A h g^(-1) at 2 C(1 C=335 m A g^(-1))for 2200 cycles and 146 m A h g^(-1) at 5 C for 4000 cycles,as well as an ultrahigh rate capability of up to 40 C with a capacity of 98 m A h g^(-1).Even at a high current density of 10 C,a capacity of 138 m A h g^(-1) could be delivered over 10,000 cycles.Thus,the synthesis of mesoporous TiO_(2)@NC-NTs was demonstrated to be an efficient approach for developing electrode materials with high sodium storage and long cycle life.

Analysis of the factors controlling performances of Au-modified TiO2 nanotube array based photoanode in photo-electrocatalytic(PECa)cells

The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.

Electrochemical oxidation of rhodamine B by PbO_2/Sb-SnO_2/TiO_2 nanotube arrays electrode

A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.

Preparation and photoelectric effect of Zn^(2+)-TiO_2 nanotube arrays

Zn 2+-TiO2 nanotube arrays were prepared by anodic oxidation method.The current-time curves were used to investigate their growth mechanism.Scanning electron microscopy and X-ray diffractometry were applied to characterizing their structures and properties.The photoelectrochemical properties were studied by electrochemical impedance spectrum(EIS).The optimised working conditions for TiO2 nanotube arrays were found to be pH 1,0.5%HF(mass fraction),20 V oxidation voltage and for 2 h.The produced sample was in anatase form,with length of 70-100 nm,thickness of 10 nm,uniform diameter and structure that does not collapse under the preparation conditions.The EIS results show that TiO2 nanotube arrays prepared with 0.5%HF(mass fraction) present a low impedance and TiO2 nanotube arrays loaded by Zn 2+could have a decreased resistance.This decrease could likely accelerate the transfer of carriers and even increase photoelectric conversion.

Electrochemical Preparation and Photoelectric Properties of Cu_2O-loaded TiO_2 Nanotube Arrays

TiO2 nanotube （TNT） arrays were fabricated by anodic oxidation of titanium foil in a fluoride- based solution, on which Cu20 particles were loaded via galvanostatic pulse electrodeposition in cupric acetate solutions in the absence of any other additives. The structure and optical properties of Cu2O-loaded TiO2 nanotube arrays （Cu2O-TNTs） were analyzed by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and UV-Vis absorption, and the photoelectrochemical performance was measured using an electrochemical work station with a three-electrode configuration. The results show that the Cu2O particles distribute uniformly on the highly ordered anatase TiO2 nanotube arrays. The morphologies of Cu2O crystals change from branched, truncated octahedrons to dispersive single octahedrons with increasing deposition current densities. The Cu2O- TNTs exhibited remarkable visible light responses with obvious visible light absorption and greatly enhanced visible light photoelectrochemical performance. The I-V characteristics under visible light irradiation show a distinct plateau in the region between approximately -0.3 and 0 V, resulting in higher open-circuit voltages and larger short-circuit currents with increased Cu2O deposition.

Fabrication of nanoporous TiO_2 films with novel surface morphology on conducting glass(FTO) substrate

The crystalline structure and surface morphology of TiO2 semiconductor coating play an important role in the conversion efficiency of dye-sensitized solar cells. In order to obtain TiO2 coating with controllable morphology and high porosity, nanoporous TiO2 films were fabricated on conducting glass （FTO） substrates, Ti thin films （1.5-2 gin） were deposited on conducting glass （FTO） substrates via the DC sputtering method, and then electrochemically anodized in NH4F/ethylene glycol solution. The crystalline structure and surface morphology of the samples were characterized by X-ray diffraction （XRD） and field emission scanning electron microscopy （FESEM）, respectively. The influences of anodizing potential, electrolyte composition, and pH value on the surface morphology of nanoporous TiO2 films were extensively studied. The growth mechanism of nanoporous TiO2 films was discussed by current density variations with anodizing time. The results demonstrate that nanoporous TiO2 films with high porosity and three-dimensional （3D） networks are observed at 30 V, when the NH4F concentration in ethylene glycol solution is 0.3% （mass fraction） and the electrolyte pH value is 5.0.

Ti/TiO_2界面的整流特性研究

采用电化学阳极氧化法在钛片表面构筑了一层结构有序、纳米级的TiO2纳米管阵列膜层,考察了制备电压对TiO2纳米管阵列形貌和尺寸的影响,应用扫描电子显微镜(SEM)对膜层的形貌进行了表征,测量了Ti/TiO2界面的整流特性,研究了TiO2纳米管阵列膜层结构与Ti/TiO2界面的整流特性的关系。结果表明:制备电压对TiO2纳米管阵列的结构起到关键的作用,二氧化钛纳米管之所以具有整流特性是由于Ti/TiO2界面具有类似p-n结的性质。利用二氧化钛纳米管的整流特性,人们可以制备出各种性能优良的材料和器件。

水热法合成TiO_2纳米管及形成机理的研究进展

综述了水热法合成TiO2纳米管的研究进展,分析了由水热法制备TiO2纳米管的形成机理以及形成TiO2纳米管的影响因素,并展望其发展趋势.

钛网表面TiO2纳米管表征及光催化性能研究

采用阳极氧化的方法在钛网基体上制备了二氧钛纳米管.利用SEM、XRD、TEM和XPS对试样进行了表征,并对其紫外光光催化性能进行了测试.结果显示,以钛网为载体试样,SEM照片显示出特别的背脊结构.XRD分析表明TiO2纳米管在热处理温度450℃与550℃之间发生了锐钛矿相向金红石相的转变.由XPS拟合分峰后表明,试样表面Ti元素存在方式有TiO2和Ti2O3.经热处理TiO2纳米管降解罗丹明B实验表明,锐钛矿与金红石混合结构较单纯锐钛矿结构光催化效率高,金红石含量存在一个最佳值.

含氟电解液对TiO_(2)纳米管阵列生长的影响

以含NH4F的乙二醇溶液作为电解液,通过重复使用电解液的方式,对金属Ti箔进行阳极氧化处理,在其表面制得形貌可控的TiO2纳米管阵列结构;利用扫描电子显微镜(SEM)对TiO2纳米管阵列的形貌进行表征,并对TiO2纳米管阵列的形成机理进行分析。结果表明:所获得的TiO2纳米管呈现圆锥状,H+和F–离子是形成TiO2纳米管阵列的关键;重复使用含氟电解液,可将可溶性氟化物完全转化成TiF62–离子,从而减少对环境的危害,含氟电解液可重复使用6次;随着含氟电解液使用次数的增加,TiO2纳米管的尺寸能够被有效调控;TiO2纳米管阵列的管长呈现先增大后减小的趋势,可在20μm内自由调控,纳米管管口处直径最高可达110 nm左右。