Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.     

Microwave assisted rapid and complete degradation of atrazine using TiO(2) nanotube photocatalyst suspensions

A technology, microwave-assisted photocatalysis on TiO(2) nanotubes, which can be applied to degrade atrazine rapidly and completely, was investigated. TiO(2) nanotubes were prepared, and confirmed by XRD, TEM and ESR. Microwave-assisted photocatalytic degradation of atrazine in aqueous solution was investigated. The result indicates that atrazine is completely degraded in 5min and the mineralization efficiency is 98.5% in 20min, which is obviously more efficient than that by the traditional photocatalytic degradation methods. It may be attributed to the intense UV radiation generated by electrodeless discharge lamps under microwave irradiation, the increased number of OH, additional defect sites on TiO(2) under the irradiation of microwave and larger specific surface area of TiO(2) nanotubes which could adsorb more organic substances to degrade than TiO(2) nanoparticles. Along with the degradation of atrazine, the concentrations of Cl(-) and NO(3)(-) increase gradually. In 20min [Cl(-)] and [NO(3)(-)] are 3, 27.8mg/L, respectively, which are close to their stoichiometric values. The major intermediates of atrazine were identified by HPLC/MS and possible degradation pathways of atrazine in microwave-assisted photocatalysis on TiO(2) nanotubes were proposed.     

Fabrication of TiO2 nanotubes by atomic layer deposition and their photocatalytic and photoelectrochemical applications

The formation of TiO(2) nanotubes was conducted by atomic layer deposition (ALD) with tris-(8-hydroxyquinoline) gallium (GaQ(3)) nanowires as a template at different substrate temperatures, 50, 100, and 200?°C. TiO(2) nanotubes were formed only at 50 and 100?°C. Although a higher growth rate at 50?°C was observed, nanotubes with better uniformity, conformality, and less residual chloride were obtained at 100?°C because of a different formation mechanism. A photocatalysis test of TiO(2) nanotubes prepared by different cycle numbers at 100?°C was conducted. It showed that TiO(2) nanotubes prepared by 400 cycles of ALD and treated at 700?°C for 1 h to form anatase phase had the best photocatalytic performance. Compared with P-25, the nanotubes showed higher photocatalytic degradation of rhodamine B and water splitting efficiency.     

TiO2纳米管的“兼并”现象及机理分析

采用电化学阳极氧化法制备了高度有序Ti02纳米管阵列,并提出纳米管“兼并”的概念.结合FE-SEM分析并验证了Macak等人提出的pH值梯度理论,并在此基础上用双电层理论解释了“兼并”的形成机理,同时解释了初期纳米管管径进一步增大的原因.     

ZnO/TiO2纳米管晶膜电极的制备及光电性能

采用水热法制备了ZnO纳米棒,以ZnO纳米棒为原料制备出ZnO/TiO2纳米管晶膜电极并应用于染料敏化太阳能电池.用扫描电镜(SEM)、X射线衍射仪(XRD)、X射线能谱仪(EDX)和N2吸脱附分析等研究了样品的结构、表面形貌和化学组成,并通过紫外可见光度计和电化学工作站探讨了煅烧温度在80~600℃范围内ZnO/TiO2纳米管电极的光电化学性能.此外,研究经TiCl4化学处理的ZnO/TiO2纳米管电极光电性能的改善情况.结果表明,600℃煅烧的ZnO/TiO2纳米管电极制备的染料敏化太阳能电池表现出较优的光电性能,其短路电流密度(Jsc)为2.28 mA/cm2,开路电压(Voc)为0.631 V,光电转换效率η为0.66%.600℃煅烧的ZnO/TiO2纳米管经TiCl4处理后的染料敏化太阳能电池的光电性能得到显著改善,其光电转换效率η提高到1.06%.     

Fabrication and characterization of photoelectrode thin films with different morphologies of TiO2 nanoparticles for dye-sensitized solar cells

This study deals with the fabrication of three different morphologies of TiO2 nanoparticles to fabricate two-layer photoelectrode thin film for dye-sensitized solar cells (DSSC). The four different TiO2 morphologies are titania nanotubes (Tnt), TiO2 nanoparticles (H220), TiO2 nanoparticle (SP) and commercial DP-25 nanoparticles (P-25). To prepare the thin films of the photoelectrodes, the first layer is coated by H220 TiO2 nanoparticles, and the second is coated by 3 kinds of materials optimally proportionally mixed - P25, SP and Tnt. The photoelectric conversion efficiency of DSSCs with photoelectrodes fabricated using H220 reached 6.31%. Finally, the TiO2 nanaomaterials with four different morphologies were used to prepare a two layer photoelectrode with the structure of H220/P25-Tnt-SP which was combined with a Pt counter electrode to assemble DSSCs. These DSSCs had photoelectric conversion efficiencies of as high as 7.47%.     

Pt-TiO2纳米管电极的制备及电催化性能

采用电化学阳极氧化-阴极还原法制备Pt-TiO2纳米管电极.扫描电镜(SEM)结果显示TiO2纳米管平均管径100nm,管长470nm,管壁厚20nm,且其比表面积大,同时纳米Pt微粒分散在TiO2纳米管上,且粒径细小,Pt微粒充分裸露,使得Pt-TiO2纳米管电极活性点多,电催化性能高.对甲醇的电催化性能测试表明:同纯Pt电极和Pt-TiO2电极(Pt微粒固定在TiO2致密膜上)相比,Pt-TiO2纳米管电极对甲醇具有更高的电催化活性,其氧化峰电流密度是在纯Pt片电极上的20倍以上.     

Efficient inverted solar cells using TiO(2) nanotube arrays

Using a vertical titania (TiO(2)) nanotube array, an inverted polymer solar cell was constructed with power conversion efficiency up to 2.71%. In this study, self-organized TiO(2) nanotubes arrays were grown by anodizing Ti metal in glycerol electrolyte containing 0.5?wt% NH(4)F and 1.0?wt% H(2)O with 20?V potential. The tube length (～100?nm) was controlled by the thickness of the sputtered titanium layer on the indium-tin oxide (ITO) substrate. The diameter of the tube was approximately 15-25?nm. After annealing in air at 500?°C for 1?h, nanotubes arrays were crystallized to the anatase phase from the initial amorphous state. Following the infiltration of polymeric semiconductor (poly(3-hexylthiophene) and (6,6)-phenyl C(60) butyric acid methyl ester, P3HT:PCBM), the filled TiO(2) layer had an optical absorption over a range from UV to visible light. The high surface-to-volume ratio of the nanotube arrays structure increased the effective area of the active region. The high efficiency of our solar cell is attributed to the vertical TiO(2) nanotube array's enhanced conduction of photo-induced current due to its charge transport capability.     

A Two-step anodization to grow high-aspect-ratio TiO2 nanotubes

High-aspect-ratio TiO₂ nanotubes with small diameter are favored in dye-sensitized solar cells for large dye loading provided by high surface areas. However, long TiO₂ nanotubes with small diameter are difficult to grow under usual anodizing conditions due to unavoidable chemical dissolution of the top portion of the as-fashioned tubes. In the present work, two kinds of double-layered TiO₂ nanotube arrays were prepared by changing voltage from high to low (i.e., from 30 V to 15 V) or from low to high (i.e., from 15 V to 30 V). It is found that the top layer can serve as a sacrificial layer to protect the continuous growth of the bottom layer from chemical dissolution. Accordingly, the two-step anodization from high voltage to low voltage is proposed to produce high-aspect-ratio TiO₂ nanotubes with small diameter underneath a sacrificial top layer.     

银掺杂TiO2纳米管制备与性能研究

常压碱熔-水热法制备了银掺杂TiO2复合纳米管。氮吸附法测定其比表面积与原料相比,增加了2.3倍,达82m2/g。用XRD、TEM和XPS进行了表征。TiO2纳米管由锐钛矿相和金红石相组成,研究表明复合纳米管中银元素以金属银和氧化银状态共存。因长径比增大,其XRD衍射峰峰高和峰强均大幅度降低。UV-Vis吸收光谱显示,银掺杂TiO2复合纳米管的吸收光谱发生了红移,带边红移近40nm。这是因为在TiO2纳米管表面形成了肖特基结,TiO2禁带宽度之间形成了杂质能级,使其表观禁带宽度减小,有助于光生电子的迁移,减少电子-空穴复合;纳米管表面羟基氧(—OH)使其表面的酸性活性点增加,增强了价带中光生空穴的氧化能力。     

Electro-oxidation of methanol on TiO2 nanotube supported platinum electrodes

TiO2 nanotubes have been synthesized using anodic alumina membrane as template. Highly dispersed platinum nanoparticles have been supported on the TiO2 nanotube. The supported system has been characterized by electron microscopy and electrochemical analysis. SEM image shows that the nanotubes are well aligned and the TEM image shows that the Pt particles are uniformly distributed over the TiO2 nanotube support. A homogeneous structure in the composite nanomaterials is indicated by XRD analysis. The electrocatalytic activity of the platinum catalyst supported on TiO2 nanotubes for methanol oxidation is found to be better than that of the standard commercial E-TEK catalyst.     

TiO2 nanotubes/MWCNTs nanocomposite photocatalysts: synthesis, characterization and photocatalytic hydrogen evolution under UV-vis light illumination

Nanocomposite of TiO2 nanotubes (TiO2NTs) and multiwalled carbon nanotubes (MWCNTs) has been synthesized by a hydrothermal method and firstly used in photocatalytic hydrogen production. The obtained TiO2 NTs/MWCNTs composites were characterized by X-ray diffraction, transmission electron microscopy, Raman spectrum and ultraviolet-visible diffuse reflectance spectroscopy. The experimental results revealed that the MWCNTs were decorated with well dispersed anatase TiO2 nanotubes with a diameter of 8-15 nm. A slight blue shift and weak symmetry was observed for the strongest Raman peak which resulted from strain gradients originating from interface integration between TiO2 nanotubes and MWCNTs. The photocatalytic activity of the as-prepared samples was evaluated by hydrogen evolution from water splitting using Na2S and Na2SO3 as sacrificial reagents under UV-vis light irradiation. Enhanced photocatalytic activity compared with P25 has been observed for the resulted samples. The nanocomposite with optimized MWCNTs content of 1% displayed a hydrogen production rate of 161 micromol x h(-1) x g(-1). Good photocatalytic stability of the as-synthesized samples was observed as well.     

Site-specific and patterned growth of TiO(2) nanotube arrays from e-beam evaporated thin titanium film on Si wafer

Growth of TiO(2) nanotubes on thin Ti film deposited on Si wafers with site-specific and patterned growth using a photolithography technique is demonstrated for the first time. Ti films were deposited via e-beam evaporation to a thickness of 350-1000?nm. The use of a fluorinated organic electrolyte at room temperature produced the growth of nanotubes with varying applied voltages of 10-60?V (DC) which remained stable after annealing at 500?°C. It was found that variation of the thickness of the deposited Ti film could be used to control the length of the nanotubes regardless of longer anodization time/voltage. Growth of the nanotubes on a SiO(2) barrier layer over a Si wafer, along with site-specific and patterned growth, enables potential application of TiO(2) nanotubes in NEMS/MEMS-type devices.     

TiO2-聚吡咯纳米复合材料的电化学制备及其在锂硫电池中的应用

采用电化学沉积的方法,以阳极氧化法制备的二氧化钛纳米管阵列为基底,制备出高度有序的TiO_2-聚吡咯(PPy)纳米阵列,再通过共热法,将单质硫颗粒负载到基底阵列中,得到S/PPy/TiO_2纳米阵列结构复合材料。扫描电镜(SEM)、透射电镜(TEM)、能谱(EDX)、傅里叶变换红外光谱(FT-IR)和热重分析(TGA)表征结果表明,TiO_2纳米管高度有序平行排列,管径约120nm,聚吡咯均匀沉积在纳米管壁上,复合材料中硫的质量分数约为61.9%。电化学测试结果表明,在0.1C电流密度下,S/PPy/TiO_2纳米复合材料首次循环比容量达1155mAh·g-1,100次循环后比容量为648.4mAh·g-1,库伦效率保持在96.8%。高容量下良好的循环稳定性能显示出S/TiO_2/PPy纳米阵列结构复合材料作为锂硫电池正极材料的优势。     

聚氨酯TiO2纳米管复合材料的制备与光催化特性研究

为了解决水体中光催化剂的分离和回收问题,对纳米TiO2的改性和固载化及其光催化特性进行了研究。首先以纳米TiO2为原料,采用水热合成法制备TiO2纳米管;再对TiO2纳米管硅烷化,改善其表面性质;然后以聚氨酯(PU)膜片为载体负载TiO2纳米管,制成了负载型PU/TiO2薄膜的光催化材料。采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、衰减全反射傅里叶变换红外光谱(ATR-FTIR)和扫描电子显微镜(SEM)等手段对催化剂进行了表征,结果表明硅烷化后的TiO2纳米管能很好地接枝在PU薄膜表面。以300 W高压汞灯为光源,萘普生为目标降解物,研究了负载PU/TiO2薄膜的光催化活性和稳定性,结果表明其对目标物的降解具有较高活性,用乙醇冲洗即可多次重复使用,其催化活性能较长时间保持稳定。     

Effect of bath type on the formation of TiO2 nanotubes in fluoride containing aqueous solution

TiO2 nanotubes were formed on Ti electrochemically by the application of anodic current in 1 M H3PO4 + 0.3 M HF solution in a glass and Teflon bath. The TiO2 nanotubes could be partly grown in the glass bath while a uniform growth of TiO2 nanotubes was observed over the whole surface in the Teflon bath. The TiO2 nanotubes fabricated in the glass bath broke off readily during ultrasonic cleaning in distilled water while the TiO2 nanotubes formed in the Teflon bath was not damaged by the ultrasonic cleaning up to 5 minutes. The ultrasonic cleaning could remove the surface residuals which are obtained inevitably if TiO2 nanotubes are fabricated in aqueous solutions.     

Self-organized TiO2 nanotube arrays: synthesis by anodization in an ionic liquid and assessment of photocatalytic properties

Self-organized TiO(2) nanotube (NT) arrays were produced by anodization in ethylene glycol (EG) electrolytes containing 1-n-butyl-3-methyl-imidazolium tetrafluoroborate (BMI.BF(4)) ionic liquid and water. The morphology of the as-formed NTs was considerably affected by changing the anodization time, voltage, and water and ionic liquid electrolyte concentrations. In general, a nanoporous layer was formed on the top surface of the TiO(2) NTs, except for anodization at 100 V with 1 vol % of BMI.BF(4), where the NT's mouth was revealed. The length and bottom diameter of the NTs as well as the pore diameter of the top layer showed a linear relationship with increased anodization voltage. These TiO(2) NTs were tested as photocatalysts for methyl orange photodegradation and hydrogen evolution from water/methanol solutions by UV light irradiation. The results show that the TiO(2) NTs obtained by anodization in EG/H(2)O/BMI.BF(4) electrolytes are active and efficient for both applications.     

Sol-gel assisted ZnO nanorod array template to synthesize TiO(2) nanotube arrays

A TiO(2) nanotube array with a large surface area is fabricated on a glass substrate using a ZnO nanorod array and sol-gel process, and the structural characteristics of the TiO(2) nanotube array are investigated. The well-aligned ZnO nanorod array, which is deposited on ZnO seed layer coated glass substrates by the wet-chemical route, is used as a template to synthesize TiO(2)/ZnO composite nanostructures through the sol-gel process. Then, by selectively removing the ZnO template, a TiO(2) nanotube with contours of the ZnO nanorods is fabricated on the ZnO seed layer coated glass. The resultant TiO(2) nanotubes are 1.5?μm long and 100-120?nm in inner diameter, with a wall thickness of ～10?nm. In addition, by adjusting the experimental parameters, such as the dip-coating cycle number or heating rate, porous TiO(2) thick films can also be obtained.     

结合溶胶-凝胶和微波法制备二氧化钛纳米管

以溶胶-凝胶法制备得到的TiO_2纳米粉体为原料,采用微波法制备TiO_2纳米管,用透射电子显微镜和扫描电子显微镜对纳米管和纳米粉体进行表征,结果表明,制得的TiO_2纳米管形貌比较完整,其外径为8-15nm、内径为5-10nm、长50-100nm,同时发现,未经HCl酸洗的TiO_2纳米管在电镜下非常完整,而经过HCl酸洗的TiO_2纳米管则局部遭到破坏。     

The fabrication of CNTs/TiO(2) photoanodes for sensitive determination of organic compounds

Titanium dioxide (TiO(2)) and carbon nanotubes (CNTs) are the two most popular functional materials in recent years. In this study, CNTs/TiO(2) composite and TiO(2) photoanodes were fabricated by a dip-coating technique, followed by subsequent calcination. The resultant photoanodes were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and UV-visible spectroscopy (UV-vis). The results suggest that the carbon nanotubes were successfully incorporated with the TiO(2) nanoparticulates without damage and that the resultant TiO(2) nanoparticles consisted of anatase and rutile. The CNTs/TiO(2) photoanodes were capable of oxidizing various types of organic compounds (e.g.?glucose, potassium hydrogen phthalate, and phenol) in aqueous solutions in a photoelectrochemical bulk cell. In comparison with the pure TiO(2) photoanode, the sensitivity of the photoanode for the detection of organic compounds has been improved by 64%, while the background current was reduced by 80% due to the introduction of the CNTs. These advantages can be ascribed to the improved adsorptivity to organic compounds, increased absorption of UV light and enhanced electron transport at the CNTs/TiO(2) photoanode due to the introduction of the CNTs.