阳极氧化法制备Y型TiO2纳米管

在含有质量分数为0.5%的NH₄F和体积分数为5% 的H₂O的乙二醇混合溶液中,采用三步阳极氧化法制备了表面形貌高度有序的Y型TiO₂纳米管阵列。讨论了钛片预处理过程对优化TiO₂纳米管阵列表面形貌的影响以及采用升温法制备Y型TiO₂纳米管的内在机理,并在较宽的温度范围内(20~60 ℃)对钛片进行阳极氧化。实验结果表明当阳极氧化第三步的电解液温度设置在40 ℃以上时,Y型TiO₂纳米管阵列的顶端将出现环状纳米线、管壁破裂以及管长减小等现象,不利于保证Y型TiO₂纳米管阵列的整体质量。因此,30~40 ℃是选取阳极氧化第三步温度的理想范围。     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术,分别沉积Ti和Ti/Al膜,经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序,分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27 关键词： 2薄膜')" href="#">多孔TiO₂薄膜 阳极氧化 紫外光吸收     

CdS化学修饰TiO2纳米管阵列电极的传质特性分析

通过声电阳极氧化-化学沉积的方法制备CdS修饰的TiO₂纳米管阵列,并对其进行形貌表征及光电性能和传质特性的研究。结果表明;相对于未修饰的TiO₂纳米管列电极,CdS纳米粒子的化学修饰在增强电极对可见光吸收能力的同时,可减小电荷载流子的迁移阻力而有效提高光生电荷的分离和传递速率。在超声场中进行化学沉积,CdS纳米粒子可在TiO₂纳米管壁上均匀沉积,使得传质阻力进一步降低而获得相对最大的光电流和电荷载流子密度(9.29×10¹⁹cm^-3)。     

锐钛矿相TiO2纳米管的制备及其染料敏化太阳电池

以商用金红石相TiO₂粉末为原料,通过在碱性溶液中150℃水热48h的方法合成TiO₂纳米管.采用SEM,TEM,XRD分析手段对TiO₂纳米管的形貌和结构演变进行了表征.制成的TiO₂纳米管与TritonX-100,乙酰丙酮混合后,通过丝网印刷的方法涂敷到ITO导电玻璃衬底上,并且在450℃下烧结30min后得到可应用于染料敏化太阳电池的多孔光阳极.将此光阳极浸泡于N719染料敏化后,与镀铂对电极组装电池,两者之间灌 关键词： 2纳米管')" href="#">TiO₂纳米管 染料敏化太阳电池 水热法     

TiO$lt;sub$gt;2$lt;/sub$gt;纳米管电子结构和光学性质的第一性原理研究

运用基于密度泛函理论的第一性原理方法, 系统研究了小尺寸锐钛矿相(n,0)型TiO₂纳米管(D<16 Å)的几何构型、电子结构和光学性质. 结果表明: 随着管径增大, 体系单位TiO₂分子的形成能降低, 体系趋于稳定; 在管径14 Å左右, (n,0)型TiO₂纳米管会发生一次构型的转变. 能带分析显示, TiO₂纳米管的电子态比较局域化, 小管径下(D<14 Å)其导电性更好; 随着构型的转变, TiO₂纳米管由直接带隙转变为间接带隙, 并且带隙值随着管径的增大而增大, 这是由于π轨道重叠效应的影响大于量子限域效应所导致的结果. 两种效应的竞争, 使得TiO₂纳米管的介电函数虚部ε₂ (ω)谱的峰值位置随管径增大既可能红移也可能蓝移, 管径大于9 Å (即(8, 0)管)之后, TiO₂纳米管的光吸收会出现明显的增强. 关键词： 2纳米管')" href="#">TiO₂纳米管 第一性原理 电子结构 光学性质     

TiO2纳米管的力学和电子学性质

基于密度泛函理论研究了纤铁矿和锐钛矿型TiO₂纳米管的原子结构、稳定性、Young模量以及电子能带结构.计算结果显示：在纳米管直径较小时,锐钛矿型TiO₂纳米管的稳定性要好于纤铁矿型纳米管,随着管径的增大,纤铁矿型纳米管变得比锐钛矿型纳米管要更稳定.纤铁矿型TiO₂纳米管具有比锐钛矿型纳米管更大的Young模量,力学性能比较优异.另外,通过对电子能带结构的研究发现,手性对TiO₂纳米管的电子结构影响较大,纤铁矿（0,n）型和锐钛矿（n,0）型纳米管为间接带隙半导体,而纤铁矿（n,0）型和锐钛矿（0,n）型纳米管却具有直接带隙. 关键词： 2纳米管')" href="#">TiO₂纳米管 Young模量 间接带隙 直接带隙     

自供能TiO2纳米管紫外探测器的制备与性能研究

采用液相沉积法在ITO衬底上以ZnO纳米棒阵列为模板合成了TiO₂纳米管阵列,并采用SEM、XRD对样品的形貌、结构等进行表征。在此基础上,以空白ITO导电玻璃为对电极制备了光电化学型紫外探测器,并对其光响应特性进行测试。实验结果表明,制得的TiO₂纳米管轻微弯曲,由单一稳定的锐钛矿相组成。制得的自供能TiO₂纳米管紫外探测器对300~400 nm紫外波段非常敏感而对可见光区无响应。在无外加偏压的条件下,TiO₂纳米管紫外探测器能够对紫外光实现探测,表现出自供能特性并且具有较高的光敏性。循环测试结果表明,制得的自供能TiO₂纳米管紫外探测器能够循环工作且性能稳定,上升时间和下降时间分别为0.33 s和0.38 s。     

超亲水性SiO2-TiO2纳米颗粒阵列结构的制备与性能研究

用分子自组装的方法在玻璃衬底上分别制备了TiO₂纳米颗粒层和SiO₂-TiO₂复合纳米颗粒阵列结构. 其中,SiO₂ 纳米颗粒层用旋涂法制备,得到密排阵列结构,而TiO₂纳米颗粒层则用浸渍提拉法制备. 文章分析了TiO₂纳米颗粒层和SiO₂-TiO₂复合纳米颗粒阵列结构的理论粗糙度,并通过扫描电子显微镜研究了它们的微观结构,用接触角 关键词： 自清洁 表面粗糙度 光催化 分子自组装     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输     

双金属粒子在光–氢转换中的作用分析

本文采用两步阳极氧化法在TiO₂纳米环/管阵列表面负载Ag、Cu纳米粒子,与单金属修饰样品对比分析得到双金属对TiO₂光电响应和电极/电解液界面性质的影响。同时,XPS、UV-Vis和U-t测试表明AgCu-TiO₂光阳极金属抗氧化性强、可见光吸收好、光生电子寿命长,光电流密度达0.76 mA·cm^-2,对应产氢速率376μL·h^-1·cm^-2。对AgCu-TiO₂/H₂O、Ag-TiO₂/H₂O和Cu-TiO₂/H₂O体系进行分子动力学模拟计算,双金属体系相对较宽的耗尽层可促进光生电子–空穴分离、转移。最终结合热力学、动力学分析得到双金属修饰TiO₂光阳极的电子传输路径。     

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.     

Effect of calcination temperature on the morphology and surface properties of TiO2 nanotube arrays

Well-ordered TiO₂ nanotube arrays were prepared by electrochemical anodization of titanium in aqueous electrolyte solution of H₃PO₄ + NH₄F at a constant voltage of 20 V for 3 h, followed by calcined at various temperatures. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) were used to characterize the samples. The results showed that the as-prepared nanotube arrays before being calcined were amorphous and could transform to anatase phase at a heat treatment temperature higher than 400 °C. As the calcination temperatures increased, crystallization of anatase phase enhanced and rutile phase appeared at 600 °C. However, further increasing the calcination temperature would cause the collapse of nanotube arrays. PL intensity of the nanotube arrays annealed at 500 °C was the lowest, which was probably ascribed to better crystallization together with fewer surface defects of the nanotube arrays.     

Effects of impurities containing phosphorus on the surface properties and catalytic activity of TiO2 nanotube arrays

TiO₂ nanotube arrays were prepared by titanium anodic oxidation with either HF or H₃PO₄/NH₄F aqueous electrolyte solutions. The samples were characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscope, photoluminescence spectra (PL) and photocurrent response. Aqueous solutions of methylene blue or Cr(VI) ions were used as the target pollutants to compare catalytic activities of the two nanotube array types. The amorphous impurities containing phosphorus were confirmed by XRD and IR, for the sample synthesized with H₃PO₄/NH₄F electrolytes. They closed a portion of the active sites, acted as recombination centers of photo-generated charges, and were also involved in the negative reactions of competing photo-generated holes or OH radicals. The TiO₂ nanotube arrays formed in the H₃PO₄/NH₄F electrolytes exhibited a stronger fluorescence spectrum, a weaker photocurrent and a lower catalytic activity than the sample fabricated with HF electrolyte without phosphorus impurities.     

Effect of electrochemical reduction on the structural and electrical properties of anodic TiO2 nanotubes

The effect of electrochemical reduction on the structural and electrical properties of amorphous as well as annealed TiO₂ nanotubes (TNTs) is investigated under ambient conditions. TNTs were prepared by anodizing titanium sheet in ethylene glycol electrolyte containing NH₄F and de-ionized water at 40 V for 6 h. Electrochemical reduction is carried out in 1 M aqueous KOH solution for ∼15 s at 3 V. TNTs are characterized by SEM, XRD, XPS and impedance spectrometer. XRD results confirm an increase in d-spacing for (101) and (200) planes, after electrochemical reduction. XPS data reveal that electrochemical reduction produced prominent shifts of ∼0.7–1.0 eV in the binding energies of TNTs. Interestingly, these shifts recover completely (in case of amorphous TNTs) and partially (in case of anatase TNTs) within ∼7 days after reduction process due to oxygen uptake. Partial recovery in the binding energies of anatase TNTs is due to the fact that the oxygen vacancies are thermodynamically more stable as compared to amorphous TNTs. Similarly, the electrochemical reduction process decreases the impedance values of TNTs by more than three orders of magnitudes (from MΩ to kΩ). The impedance values also recover to the similar values before reduction in a span of ∼7days.     

Oxygen defect dependent variation of band gap,Urbach energy and luminescence property of anatase,anatase–rutile mixed phase and of rutile phases of TiO2 nanoparticles

TiO₂ nanoparticles are prepared by a sol–gel method and annealed both in air and vacuum at different temperatures to obtain anatase, anatase–rutile mixed phase and rutile TiO₂ nanoparticles. The phase conversion from anatase to anatase–rutile mixed phase and to rutile phase takes place via interface nucleation between adjoint anatase nanocrystallites and annealing temperature and defects take the initiate in this phase transformation. The samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis and photoluminescence spectroscopy (PL). Anatase TiO₂ exhibits a defect related absorption hump in the visible region, which is otherwise absent in the air annealed samples. The Urbach energy is very high in the vacuum annealed and in the anatase–rutile mixed phase TiO₂. Vacuum annealed anatase TiO₂ has the lowest emission intensity, whereas an intense emission is seen in its air annealed counterpart. The oxygen vacancies in the vacuum annealed samples act as non-radiative recombination centers and quench the emission intensity. Oxygen deficient anatase TiO₂ has the longest carrier lifetime. Time resolved spectroscopy measurement shows that the oxygen vacancies act as efficient trap centers of electrons and reduce the recombination time of the charge carriers.     

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.     

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.     

Influence of anodization parameters on the morphology of TiO2 nanotube arrays

TiO₂ nanotube arrays can be fabricated by electrochemical anodization in organic and inorganic electrolytes. Morphology of these nanotube arrays changes when anodization parameters such as applied voltage, type of electrolyte, time and temperature are varied. Nanotube arrays fabricated by anodization of commercial titanium in electrolytes containing NH₄F solution and either sulfuric or phosphoric acid were studied at room temperature; time of anodization was kept constant. Applied voltage, fluoride ion concentration, and acid concentrations were varied and their influences on TiO₂ nanotubes were investigated. The current density of anodizing was recorded by computer controlled digital multimeter. The surface morphology (top-view) of nanotube arrays were observed by SEM. The nanotube arrays in this study have inner diameters in range of 40-80 nm.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

Preparation of F-doped titania nanoparticles with a highly thermally stable anatase phase by alcoholysis of TiCl4

Pure anatase is a metastable phase and inclined to (transform) be transformed into rutile structure under heating over than 500 °C, which limits its suitability for high-temperature applications. Hitherto much research efforts have been made to increase the stability temperature of anatase structure. However, metallic doping usually introduced metallic oxides into titania at high temperature, and many nonmetallic doping are not competent for increasing the stability temperature of anatase structure up to 900 °C. In this study, F-doped anatase TiO₂ nanoparticles were conveniently prepared via the alcoholysis of TiCl₄ and the as-prepared product shows very high stability temperature up to 1000 °C before being transformed into rutile structure phase. On the basis of XPS results of F-doped titania annealed at different temperature, it is learned that the F atoms were anchored on the crystal planes of anatase in favor of decreasing the energy faces of anatase and stabilizing the anatase structure till annealed at 1300 °C all the anatase were transformed into rutile phase.