激光加热法制备TiO2和Pt/TiO2纳米颗粒

氧化钛(TiO2)纳米颗粒和金属／氧化钛(M／TiO2)复合纳米颗粒具有优异的物理和化学性质。实验用CO2连续激光直接加热法制备TiO2纳米颗粒和铂/氧化钛(Pt／TiO2)复台纳米颗粒．并用TEM．XRD．和HRTEM等技术对所制备的纳米颗粒进行了表征。用平均粒径为1．0μm的金红石相TiO2粉体压制成的细圆棒料为前驱物．制备的纳米TiO2颗粒呈球形，平均粒径约为30nm．96．2％为锐钛矿相。用TiO2/PtCl2混合物制成的细圆棒料为前驱物，制备的Pt／TiO2纳米复台颗粒平均粒径约为40nm，Pt颗粒被TiO2包裹，并和TiO2分离形成粒径为2～3nm的颗粒．复合粉体内的TiO2有95％以上属锐钛矿相。     

纳米TiO_2的合成及纳米TiO_2/Pt修饰电极的电化学催化性能

采用溶胶-凝胶法合成纳米TiO2粉体,通过正交实验优化了纳米TiO2的合成工艺条件,用透射电镜及X-射线衍射技术对纳米TiO2样品进行表征;进而采用涂膜法制备纳米TiO2/Pt修饰电极,通过循环伏安法研究其在葡萄糖体系中的电化学催化性能。结果表明:在钛酸丁酯与乙醇体积比为2∶3、烘干温度为80℃、焙烧温度为500℃时,合成的纳米TiO2具有最佳电化学催化性能;合成的纳米TiO2为锐钛矿型,颗粒粒径分布在5~20nm之间;纳米TiO2/Pt修饰电极对葡萄糖具有显著的电化学催化活性。     

TiO2纳米管阵列光催化降解苯酚

采用电化学阳极氧化法在钛基体上制得了高度致密的、有序的、均匀的TiO2纳米管阵列。用SEM、XRD等对其表面形貌和结构晶型进行了表征和分析。以TiO2纳米管阵列为光催化剂对废水中典型的有机污染物——苯酚进行了光催化降解,考察了影响光催化降解速率的因素。结果表明,在紫外光照下,苯酚水溶液的pH=3、ρ(苯酚)=10.0 mg/L时,具有锐钛矿相结构的TiO2纳米管阵列的光催化效果最好,相同条件下与溶胶凝胶法制备的纳米TiO2颗粒膜的光催化降解速率进行对比,前者比后者提高了近一倍。     

Au NPs修饰TiO2纳米片阵列的制备及光电化学性能研究

TiO_2吸光性能差和光电转化效率低,通过Au NPs修饰TiO_2纳米片来提高其吸光性能以及光电转化效率。修饰后的纳米复合物(Au-TiO_2-Ti)在可见光范围内的光吸收和光电流密度都明显增加,在200 mW/cm~2,0.5 V vs. Ag/AgCl的条件下,光电流密度可达到0.38 mA/cm~2,经过8 h光照后光电流保持稳定,表明材料具有优异的稳定性。因此,合成的Au-TiO_2-Ti电极在光电化学转化中有良好的应用前景。     

TiO2纳米管阵列的制备及其应用研究进展

TiO2纳米管阵列作为一种新型的纳米TiO2材料,由于独特的有序结构和优异的性能,引起了人们的极大关注。介绍了采用阳极氧化法制备TiO2纳米管的工艺条件、影响因素、形成机理,及其在光电解水制氢、光催化降解有机污染物、染料敏化太阳能电池、气敏传感等方面的研究进展,展望了其发展方向。     

热处理对TiO2纳米管阵列光解水性能的影响研究

采用两步阳极氧化法制备了TiO2纳米管阵列并探索了不同退火温度和冷却方式对其光解水性能的影响。研究发现较高的退火湿度和较快的冷却速率有助于光电流密度的提高。在650℃下退火并油冷的TiO2纳米管阵列表现出最大的能量转换效率。阳极氧化过程中的碳掺杂、较高的结晶度、纯的锐铁矿相和较薄的界面阻挡层是其性能较高的主要原因。     

新型有序纳米碳管阵列的合成、表征及电化学性能

用模板法合成纳米碳管阵列（ordered carbon nanotubes arrays，OCNT）。利用XRD、氮气吸附、电镜、循环伏安技术对样品的结构和电化学性能进行表征。样品孔结构具有典型的二维六角（p6mm）有序分布，比表面积高达1703m^2／g，中孔分布集中，最可儿直径3．5nm。OCNT由纳米碳管规整有序排列构成。OCNT具有很好的电容特性，在高的电压扫描速度下比电容值不发生明显衰减，50mV／s的高电压扫描速度下，比电容为181．2F／g；高频下仍能保持优异的电容特性，频率1Hz时样品的比电容大约100F／g。OCNT大的孔尺寸和规整有序的孔结构是其优异电容性能的主要原因。     

TiO2纳米管阵列孔径调控葡萄糖氧化酶生物传感器性能

采用电化学阳极氧化法制备出不同孔径（21、62、83、102 nm）的TiO₂纳米管阵列（TNA）,研究了孔径对固定化葡萄糖氧化酶（GOx）的传感器性能的影响。循环伏安测试结果表明固定在不同孔径大小的TNA上的GOx在葡萄糖溶液中均具有良好的酶活性。计时电流法和交流阻抗法测试发现,当孔径是83 nm时,灵敏度达到最大值27.2 μA·（mmol·L^-1）^-1·cm^-2。调控TNA的孔径可改变固定化GOx的活性及溶液扩散阻抗,从而显著提高生物传感器性能。     

TiO2纳米管阵列电合成的扩散-反应耦合强化机制研究

研究针对TiO₂纳米管材料批量电合成过程的结构有序性耗失问题,考察了TiO₂纳米管阵列生长过程中的非线性动力学机制,及其随电解时间等的演变机制。结合扫描电镜（SEM）及电化学分析表明,TiO₂纳米管阵列形成是低聚羟基钛中间体扩散-反应耦合过程中的自组织行为。研究建立了电合成体系的反应-扩散动力学方程组,并对其进行了线性稳定性分析,阐释了TiO₂纳米管阵列有序结构形成,乃至出现周期性电化学振荡的参数阈值空间,在此基础上提出了TiO₂纳米管阵列电合成过程的扩散-反应耦合强化机制。研究提出的非线性动力学机制广泛存在于各种金属的电溶过程中,并对产物结构及过程电耗有深刻影响。这也为新型纳米材料的批量电合成过程强化提供了理论依据。     

有序TiO_2纳米管阵列光催化性能研究进展

高度有序TiO₂纳米管阵列由于具有结构的有序性及尺寸的可控性,已成为近年来光催化材料领域的研究热点之一。本文针对有序TiO₂纳米管阵列特殊的结构形貌特点,阐述了管壁粗糙度、管长、管壁厚度、管径及表面积对其光催化性能的影响。在不同的催化剂载体（透明玻璃基底、无基底、钛丝网基底、非平面钛片基底）生长TiO₂纳米管阵列是有效地提高其光催化性能的途径之一,介绍了这些新型结构的TiO₂纳米管阵列的研究进展。最后总结了现阶段主要掺杂改性TiO₂纳米管阵列的方法及掺杂效果。在此基础上,指出了当前研究中存在的主要问题,并展望今后的研究方向。     

Morphology and Microstructure of As-Synthesized Anodic TiO2 Nanotube Arrays

The as-grown structure of electrochemically synthesized titania nanotube arrays is investigated by scanning electron microscope (SEM) in combination with transmission electron microscope (TEM) as well as X-ray diffraction (XRD). The analysis reveals a preferred growth direction of the nanotubes relative to the substrate surface and the well control on the nanotube arrays morphology. The crystal structure of the anatase phase is detected and exists in the tube walls without any thermal treatment, which makes it possible to realize the application of as-formed TiO₂ nanotubes avoiding the degradation of the nanotube structures when sintering. In addition, a new growth, layered model of the anodic TiO₂ nanotubes is presented to obtain further understanding of the growth mechanism.     

Synthesis and Morphology of TiO2 Nanotube Arrays by Anodic Oxidation Using Modified Glycerol-Based Electrolytes

Titanium dioxide (TiO₂) nanotube arrays were prepared by electrochemical anodization of titanium sheets in the glycerol 176 mL/H₂O 44 mL/NH₄F 0.5 wt% electrolytes modified with H₂SO₄ and NaAc addition. The surface morphologies, average inner diameter, and the length of the nanotube arrays changed with the solution pH in the range from 5.6 to 4.0 by adding H₂SO₄. A uniform surface morphology of the nanotubes with average inner diameter of ∼80 nm and a length of ∼1000 nm was obtained when the solution pH was 5.0. The growth rates of the nanotubes were remarkably enhanced by NaAc addition in the range of 0.04–0.14 M . With NaAc addition of 0.10 M , the length of the nanotube arrays reached 4.16 μm after an 8-h anodization, increasing 3.23 μm compared with no NaAc addition. The relationship between solution pH and growth of TiO₂ nanotubes was analyzed by current–time curves, solution electrical conductivities, and scanning electron microscopy (SEM), and the role of NaAc was also discussed based on SEM and solution electrical conductivities.     

Photoelectrochemical properties of thermally oxidized TiO2

The photoelectrochemical properties of polycrystalline TiO₂ prepared at high temperature and doped polycrystalline TiO₂ with noble metals have been investigated. The polycrystalline TiO₂ prepared at high temperature give a cathodic photocurrent as well as a visible light response. These phenomena can be explained by a model based on the d-band formed by the interstitial Ti ion in TiO₂ lattice. The doped polycrystalline TiO₂ with noble metals (Rh, Ru, Pt, Au) prepared at low temperature also show a cathodic photocurrent and a visible light response. These are based on the impurity band formed by the doping metals. It is judged that the impurity band is near the π* conduction band for the doped TiO₂ with Rh, Ru and Pt, but is near the π valence band for the Au doped TiO₂ in energy position. It is found that there exist overlap potentials of the anodic and cathodic photocurrents at the doped TiO₂ with noble metals. This will provide evidence on the mechanism of the enhancement of the photocatalysis on TiO₂ owing to the doping of noble metals.     

Anodic TiO2 Nanotube Arrays for Dye-Sensitized Solar Cells Characterized by Electrochemical Impedance Spectroscopy

This paper reports on the microstructure of anodic titanium oxide (TiO₂) and its use in a dye-sensitized solar cell (DSSC) device. When voltages of 60 V were applied to titanium foil for 2 hr under 0.25 wt% NH₄F+ 2 vol% H₂O+C₂H₄(OH)₂, TiO₂ with a nanotube structure was formed. The film, which had a large surface area, was used as an electron transport film in the DSSC. The DSSC device had a short-circuit current density (J_sc) of 12.52 mA cm⁻², a fill factor (FF) of 0.65, an open-voltage (V_oc) of 0.77 V, and a photocurrent efficiency of 6.3% under 100% AM 1.5 light. The internal impedance values under 100%, 64%, 11%, and 0% (dark) AM 1.5 light intensities were measured and simulated using the electrical impedance spectroscopy (EIS) technique. The impedance characteristics of the DSSC device were simulated using inductors, resistors, and capacitors. The Ti/TiO₂, TiO₂/Electrolyte, electrolyte, and electrolyte/(Pt/ITO) interfaces were simulated using an RC parallel circuit, and the bulk materials, such as the Ti, ITO and conducting wire, were simulated using a series of resistors and inductors. The impedance of the bulk materials was simulated using L₀+R₀+R_b, the impedance of the working electrode was simulated using (C₁//R₁)//(R_a+(C₂//R₂), the electrolyte was simulated using C₃//R₃, and the counter electrode was simulated using C₄//R₄.     

Photoelectrochemical behaviour of TiO2 and formation of hydrogen peroxide

Electrochemical and photoelectrochemical behaviour of anodized titanium sheets has been investigated.It has been shown that, on a TiO₂ electrode, reduction of oxygen into hydrogen peroxide can take place.Under illumination at rest potential, we have simultaneously the photo-induced anodic oxidation of water into oxygen and the reduction of oxygen into hydrogen peroxide.This H₂O₂ formation is a real photosynthesis reaction on a semi-conductor electrode.     

Synthesis and electrochemiluminescence of the CeO2/TiO2 composite

CeO₂/TiO₂ composite with kernel–shell structure was synthesized by a sol–gel process. The characterization results show that the composite is made up of anatase phase TiO₂ and cubic system CeO₂. The electrochemiluminescence (ECL) behavior of the CeO₂/TiO₂ composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO₂/TiO₂ composite resulted from the benefit ECL effect of interface heterojunction in composite.     

TiO2改性煤气化粗渣基地质聚合物的微观结构与性能

煤气化渣可分为粗渣和细渣,其有在碱激发领域应用的潜力。本文对煤气化粗渣的理化性能进行了研究,使用煤气化粗渣制备了地质聚合物,并对其进行了TiO₂的改性研究。结果表明,在煤气化粗渣基地质聚合物中掺入一定量的TiO₂可明显改善其力学性能。当掺入质量分数为10.0%的TiO₂时,样品28 d的抗压强度可从23.4 MPa提高到42.9 MPa。此外,通过对样品进行物相分析与微观结构分析, TiO₂的掺入明显改善了地质聚合物的微观结构,促进了碱激发反应,提高了材料的力学性能。     

Cr3+掺杂TiO2粉末的水热制备及光催化活性

以钛酸四丁酯为钛源,采用水热法制备了铬离子掺杂的TiO2纳米粉末光催化剂。通过X射线衍射(XRD),扫描电子显微镜(SEM)、透射电子显微镜(TEM),高分辨透射电子显微镜(HRTEM)和比表面积(BET)等方法对新制备的二氧化钛粉末进行表征。新制二氧化钛的光催化活性通过在紫外光照射下光催化降解室温下空气中的丙酮来表征。研究并探讨了Cr3+掺杂浓度对二氧化钛粉末的微结构和光催化活性的影响。实验结果表明,制备的掺杂浓度0.5%的Cr3+-TiO2纳米粉末具有最好的光催化活性。     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Ce-Zn共掺杂改性TiO2纳米管阵列的制备及其光催化性能

采用阳极氧化法在钛网上制得TiO₂纳米管阵列(TNTA),并利用操作简单的微溶剂燃烧合成法将稀土元素Ce和过渡金属元素Zn共掺杂修饰TiO₂纳米管阵列得到复合光催化材料Ce-Zn/TiO₂纳米管阵列(CeZn/TNTA),并对CeZn/TNTA的形貌、组成结构和光催化性能等进行测试。结果表明:阳极氧化时间会影响TNTA的形貌,氧化时间为2 h的TNTA管状结构分布均匀且高度有序,纳米管内径约为50 nm,管壁厚约为25 nm,管长约为1μm。CeZn/TNTA样品中的Ce以CeO₂和Ce₂O₃混合态、Zn以ZnO形式呈簇状不均匀分布在TiO₂纳米管阵列表面。与裸TNTA相比,CeZn/TNTA复合催化剂的光响应范围拓宽至可见光区域,电荷转移阻力减小,光生电子-空穴的分离效率提高,载流子的传输速率较快,且表现出较高的光催化活性,其在1 h内对亚甲基蓝光催化降解率可达85.27%。