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.     

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.     

有序TiO2纳米管阵列结构的可控生长及其物相研究

分别在HF水溶液、含NH₄F和H₂O的乙二醇有机溶液中对Ti箔进行阳极氧化,得到TiO₂纳米管阵列结构.该结构高度有序、分布均匀、垂直取向,且通过阳极氧化工艺条件(如阳极氧化电压、电解液的选择与配比以及氧化时间等)可实现对其结构参数(如管径、管壁厚度、管密度、管长等)的有效控制.利用XRD研究了TiO₂纳米管阵列的物相结构.结果表明：退火前的TiO₂纳米管阵列为无定形结构;分别在真空和氧气氛中50 关键词： 2纳米管阵列')" href="#">TiO₂纳米管阵列 阳极氧化 可控生长     

From anodic TiO2 nanotubes to hexagonally ordered TiO2 nanocolumns

We report on the formation of hexagonally ordered TiO₂ nanocolumnar layers by electrochemical oxidation in a fluoride containing electrolyte, using self-organizing nanotube formation conditions at elevated potentials and low temperatures. The influence of the substrate temperature on the nanocolumn morphology and composition is investigated and characterized by FE-SEM and EDX. The origin of these nanocolumns can be attributed to a thickening of the inner tube wall of the double wall structure of self-organized TiO₂ nanotubes. Furthermore, a transition from nanocolumnar to nanotubular structure can be established by changing the applied voltage or applying a post-immersion treatment.     

Fabrication of open-ended TiO2 nanotube arrays by anodizing a thermally evaporated Ti/Au bilayer film

Fabrication of TiO₂ nanotube arrays (TNAs) with through-hole morphology is practical significance to enhance the photocatalytic activity of TNAs, as well as expanding their applications. In present work, open-ended TNAs are synthesized on a conductive Au layer by anodizing a thermally evaporated Ti/Au bilayer film. In the anodizing process, the upper Ti layer is transformed into well-aligned TNAs. The barrier layer under the growing TNAs ultimately touches the Au layer and is completely dissolved by the electrochemical etching. In order to avoid the bubble disruption of TNAs caused by the water electrolysis after the Au layer is exposed to the electrolyte, a specific non-aqueous electrolyte is used. The XRD results reveal that the as-formed open-ended TNAs are amorphous and can be transformed into anatase by annealing at 350 °C.     

Photoelectrochemical property and photocatalytic activity of N-doped TiO2 nanotube arrays

N-doped TiO₂ nanotube arrays (NTN) were prepared by anodization and dip-calcination method. Hydrazine hydrate was used as nitrogen source. The surface morphology of samples was characterized by SEM. It showed that the mean size of inner diameter was 65 nm and wall thickness was 15 nm for NTN. The ordered TiO₂ nanotube arrays on Ti substrate can sustain the impact of doping process and post-heat treatment. The atomic ratio of N/Ti was 8/25, which was calculated by EDX. Photoelectrochemical property of NTN was examined by anodic photocurrent response. Results indicated the photocurrent of NTN was nearly twice as that of non-doped TiO₂ nanotube arrays (TN). Photocatalytic activity of NTN was investigated by degrading dye X-3B under visible light. As a result, 99% of X-3B was decomposed by NTN in 105 min, while that of TN was 59%.     

Fabrication, characterization and photoelectrochemical properties of Fe2O3 modified TiO2 nanotube arrays

TiO₂ nanotube (NT) arrays modified by Fe₂O₃ with high sensibility in the visible spectrum were first prepared by annealing anodic titania NTs pre-loaded with Fe(OH)₃ which was uniformly clung to the titania NTs using sequential chemical bath deposition (S-CBD). The photoelectrochemical performances of the as-prepared composite nanotubes were determined by measuring the photo-generated currents and voltages under illumination of UV-vis light. The titania NTs modified by Fe₂O₃ showed higher photopotential and photocurrent values than those of unmodified titania NTs. The enhanced photoelectrochemical behaviors can be attributed to the modified Fe₂O₃ which increases the probability of charge-carrier separation and extends the range of the TiO₂ photoresponse from ultraviolet (UV) to visible region due to the low band gap of 2.2 eV of Fe₂O₃.     

Synthesis and field emission of diamond-like carbon nanorods on TiO2/Ti nanotube arrays

Highly ordered TiO₂/Ti nanotube arrays were fabricated by anodic oxidation method in 0.5 wt% HF. Using prepared TiO₂/Ti nanotube arrays deposited Ni nanoparticles as substrate, high quality diamond-like carbon nanorods (DLCNRs) were synthesized by a conventional method of chemical vapor deposition at 750 °C in nitrogen atmosphere. DLCNRs were analyzed by filed emission scanning electron microscopy and Raman spectrometer. It is very interesting that DLCNRs possess pagoda shape with the length of 3–10 μm. Raman spectra show two strong peaks about 1332 cm⁻¹ and 1598 cm⁻¹, indicating the formation of diamond-like carbon. The field emission measurements suggest that DLCNRs/TiO₂/Ti has excellent field emission properties, a low turn-on field about 3.0 V/μm, no evident decay at 3.4 mA/cm² in 480 min.     

Optical and electrical characterization of TiO2 nanotube arrays on titanium substrate

Novel oriented aligned TiO₂ nanotube (TN) arrays were fabricated by anodizing titanium foil in 0.5% HF electrolyte solution. It is indicated that the sizes of the TNs greatly depended on the applied voltages to some extent. The electrical properties of the TN arrays were characterized by current-voltage (I-V) measurements. It exhibits a nonlinear, asymmetric I-V characterization, which can be explained that there exists an n-type semiconductor/metal Schottky barrier diode between TN arrays and titanium substrate interface. The absorption edges shift towards shorter wavelengths with the decrease of the anodizing voltages, which is attributed to the quantum size effects. At room temperature, a novel wide PL band consisting of four overlapped peaks was observed in the photoluminescence (PL) measurements of the TN arrays. Such peaks were proposed to be resulted from the direct transition X₁ → X₂/X₁, indirect transition Γ₁ → X₂/X₁, self-trapped excitons and oxygen vacancies, respectively.     

Photoelectrocatalytic degradation of organic contaminants at Bi2O3/TiO2 nanotube array electrode

In the current work, TiO₂ nanotube array was prepared via electrochemical anode method. Then the Bi₂O₃ nanoparticles were deposited onto the TiO₂ nanotube array via dip-coating method from an amorphous complex precursor. The crystal structures were characterized via X-ray diffraction analysis. Their surface textures were observed via electron-scanning microscope. The prepared composite array electrode exhibited high photoelectrocatalytic activities towards degrading organic contaminants under visible light irradiation. High photoelectrocatalytic activities were also exhibited under UV light irradiation. The catalytic mechanism was discussed based on the analysis of electrochemical and degradation kinetics results. It is suggested a P (Bi₂O₃)-N (TiO₂) junction was formed to increase the catalytic activates. The stability of the electrode materials was confirmed finally.     

Effect of crystallographic orientation on the anodic formation of nanoscale pores/tubes in TiO2 films

Self-organized nanopores and nanotubes have been produced in thin films of titanium (Ti) prepared using filtered cathodic vacuum arc (FCVA), DC- and RF-sputter deposition systems. The anodization process was performed using a neutral electrolyte containing fluoride ions with an applied potential between 2 and 20 V (for clarity the results are only presented for 5 V). Scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) techniques were used to characterise the films. It was found that the crystallographic orientation of the Ti films played a significant role in determining whether pores or tubes were formed during the anodic etching process.     

由纳米管和纳米颗粒构成的TiO2膜的制备与机理研究

采用聚苯乙烯小球修饰Ti片表面,并进行阳极氧化,制备出一种由纳米颗粒和纳米管构成的TiO₂膜．通过数值模拟,分析了氧化表面附近的局部电场分布对TiO₂膜形貌的影响．结果表明,覆盖物增强了局部电场,从而加快了O^2-与Ti的反应速率,有利于TiO₂的生长;与此同时,[TiF₆]^6-的扩散受到阻碍,使得TiO₂的溶解速率减慢．可见,覆盖物打破了TiO₂纳米管形成的平衡条件,导致纳米颗粒的生成．此外,通过X射线衍射和Raman光谱的测试分析发现,所制备的TiO₂为锐钛矿结构.     

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     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.     

The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes

CdS/TiO₂ nanocomposites were prepared via a simple wet chemical method, and characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their ability to degrade Acid Rhodamine B was investigated under visible light irradiation. The results indicate that CdS/TiO₂ nanocomposite with a mass ratio of 4:1(TiO₂:CdS) showed high photocatalytic activity and the CdS loaded on TiO₂ nanotube surface exhibited a hexagonal phase. The dispersion of CdS on TiO₂ nanotube surface had an important effect on the degradation efficiency of pollutant, which provides a strategy for practical industry application.     

TiO2分子在GaN(0001)表面吸附的理论研究

采用基于密度泛函理论的平面波超软赝势法,计算了TiO₂分子在GaN(0001)表面的吸附成键过程、吸附能量和吸附位置. 计算结果表明不同初始位置的TiO₂分子吸附后,Ti在fcc或hcp位置,两个O原子分别与表面两个Ga原子成键,Ga-O化学键表现出共价键特征,化学结合能达到7.932-7.943eV,O-O连线与GaN[1120]方向平行,与实验观测(100)[001] TiO₂//(0001)[1120]GaN一致. 通过动力学过程计算分析,TiO₂分子吸附过程经历了物理吸附、化学吸附与稳定态形成的过程,稳定吸附结构和优化结果一致. 关键词： GaN(0001)表面 2分子')" href="#">TiO₂分子 密度泛函理论 吸附     

Growth of branched rutile TiO2 nanorod arrays on F-doped tin oxide substrate

Branched rutile TiO₂ nanorod arrays were directly synthesized on the F-doped tin oxide (FTO) substrate through a two-step hydrothermal treatment by a seeding method with TiO₂-nanorods as seeds. The samples were characterized respectively by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and field-emission scanning electron microscopy (FESEM). Results showed that TiO₂ nanorods with nanobranches (TiO₂-NB) grew vertically on the FTO substrate. XRD and HRTEM results confirmed that the TiO₂-NB arrays were single-crystalline rutile. The optical properties of the samples were studied with a UV-vis spectrometer. The photocatalytic activity of the TiO₂-NB film is better than that of P25 particulate film. Direct electrical pathway and improved light-harvesting efficiency were crucial for the superior photocatalytic activity of the TiO₂-NB arrays.     

Enhanced Photoelectrochemical Property of Zn Loaded TiO2 Nanotube Arrays Electrode

采用计时电流法制备了负载Zn纳米粒子的TiO₂纳米管阵列电极．通过阳极氧化法制备TiO₂纳米管阵列电极,然后通过控制计时电流沉积时间来控制负载在TiO₂纳米管上Zn纳米颗粒的沉积量和 沉积尺寸．SEM和XRD分析结果显示,沉积时间为3～5 s时,负载在TiO₂纳米管上的Zn粒子的直径为15～25 nm．UV漫反射光谱发现负载Zn的TiO₂纳米管阵列电极比没有负载的样品吸收487～780 nm的光更强;在高压汞灯照射下,前者比后者的光电流响应提高了50%．     

特定位点上CO2与(TiO2)n团簇相互作用的第一性原理研究

本文基于密度泛函理论系统地研究了(TiO₂)_n团簇上二氧化碳(CO₂)的吸附和活化性质. 计算结果表明,CO₂更倾向于吸附在(TiO₂)_n团簇的桥氧原子上,形成“化学吸附”碳酸盐络合物. 而CO更倾向于吸附到末端Ti-O的Ti原子上. 发现计算得到的碳酸盐振动频率值与实验获得的结果非常吻合,这表明配合物中CO₂的几何构型与其线性型相比,有微小的弯转. 通过对电子结构、电荷密度、电离势、HOMO-LUMO以及态密度的分析,证实了CO₂与团簇之间的电荷转移以及相互作用. 从预测的能量分布图来看,(TiO₂)_n团簇上的CO₂活化与结构密切有关,相比于块体的TiO₂,CO₂在团簇结构上更易于吸附和活化.     

Photocatalytic Activity of N-doped TiO2 Photocatalysts Prepared from the Molecular Precursor (NH4)2TiO(C2O4)2

用不同温度控制分解草酸氧钛铵制备N掺杂TiO₂光催化剂．利用XRD、IR、热分析、N₂吸-脱附等温线、XPS、紫外可见漫反射光谱和SEM表征了N-TiO₂光催化剂的结构．400～600 oC焙烧的N-TiO₂光催化剂为纯锐钛矿相,而700 oC焙烧的N-TiO₂光催化剂为锐钛矿和金红石混合相．N掺杂在TiO₂的间隙位使锐钛矿相TiO₂带隙变窄．在光降解甲基橙的反应中,600和400 oC焙烧的N-TiO₂催化剂分别在紫外光和全波长光照射下有最好活性;700 oC焙烧的N-TiO₂催化剂无论在紫外光和全波长光下都表现出最好的比活性,即最高的光量子效率,这可以归因于700 oC焙烧的N-TiO₂光催化剂良好的结晶程度和锐钛矿-金红石异相结的存在．