有序Ti02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5I)0℃退火后,HF水溶液中制备的样品出现单一锐钛矿相,页在含NH4F和H2O的乙二醇有机溶液中氧化得到的样品则出现锐钛矿和金红石的混合相.前者在氧气氛中退火后锐钛矿晶化程度较高;后者在真空中退火后混合相的品化程度也较高.初步分析了TiO2纳米管阵列的形成机理.这些结果对基于TiO2,纳米管阵列的传感器及有机一无机异质结太阳电池的应用研究是非常有益的.     

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)。     

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     

锐钛矿相纳米TiO2晶体生长动力学及生长过程控制

研究了采用溶胶-凝胶法经由前驱物钛酸四异丙酯水解制备纳米TiO₂结构相变及锐钛矿晶体生长动力学过程. 研究结果表明,在酸性条件下水解,由于高压热处理温度的变化导致锐钛矿向金红石相的结构相变,锐钛矿相纳米TiO₂生长活化能在250℃以下和以上分别为(15.8±4.5)kJ/mol和(80.2±1.0)kJ/mol;而在碱性条件下水解的活化能值为(3.5±0.4)kJ/mol. 在不发生结构相变的条件下,酸性水解条件下锐钛矿相纳米TiO₂生长速 关键词： 2')" href="#">纳米TiO₂ 锐钛矿 生长动力学 溶胶-凝胶法     

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     

高度有序TiO2纳米管阵列的制备及其生长机制

采用金属钛片和石墨分别作为阳极和阴极,氢氟酸和醋酸的混合溶液为电解液,通过阳极氧化法制备高度有序的TiO2 纳米管阵列. 经过场发射扫描电子显微镜(FESEM), X-射线电子衍射仪分别对样品的形貌,结构进行了研究. 结果表明,TiO2 纳米管的尺寸,形貌都随着外加电压、反应时间的变化而变化;随着退火温度的提高,TiO2 纳米管的结构逐渐由锐钛矿相向金红石相转变. 另外,我们讨论了TiO2 纳米管阵列形成机制.     

TiO2纳米线阵列干涉传感器

开发一种新型TiO₂纳米线阵列干涉传感器。首先,通过水热合成法在FTO导电玻璃表面制备了TiO₂纳米线阵列薄膜。然后,以此复合结构作为传感芯片,利用Kretschmann 棱镜耦合结构,构建了基于Kretschmann结构的波长调制型薄膜干涉传感器。最后,以氯化钠水溶液为待测液体介质研究了该传感器对环境介质折射率的灵敏性能。结果表明：该传感器对1.333 5~1.360 4范围内的折射率有很好的响应。TM模式下,在0~3%与3~15%浓度范围内,氯化钠浓度与该传感器的反射光强度分别呈现了良好的线性关系。TE模式下,在0~3%浓度范围内,氯化钠浓度与吸收强度存在良好的线性关系,而波长基本不变;而在3~15%浓度范围内,随着氯化钠浓度的增加,波长逐渐红移,氯化钠浓度与波长也具有良好的线性关系。     

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     

含水量对TiO2纳米管形貌控制参数的影响

以不同含水量的乙二醇溶液为电解液,采用阳极氧化法制备TiO2纳米管阵列。通过记录反应过程中电导率、粘度及回路电流随时间的变化曲线,研究含水量对电解液粘度、电导率及电流等过程参数的影响,分析了纳米管形貌尺寸与TiO2溶蚀所耗电荷量的关系。粘度初始值和初始电导率均与含水量呈三次关系,相关系数分别为0.992 5和0.977 8。在反应过程中,溶液粘度值有缓慢增加的趋势。由于不同含水量的电解液粘度的不同,H+和OH-数量不同,F-迁移速率不同,电导率-时间曲线及电流-时间曲线具有不同的变化趋势,并对其进行了理论分析。当水体积分数为4%,5%,6%和10%时,纳米管的形貌较为有序并且TiO2纳米管阵列表面的碎片较少,纳米管直径变化范围为50 nm至72 nm,长度变化范围为0.85~1.90 m。F-腐蚀氧化膜时所消耗电量与TiO2氧化膜被腐蚀掉的体积呈一次函数关系,即腐蚀电量越大,腐蚀掉的体积越大,为制备一定形貌尺寸的纳米管提供了一定的控制方法。     

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%.     

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.     

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.     

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.     

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     

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.     

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.