TiO_2纳米管半导体特性与光电催化动力学研究

通过阳极氧化法在有机溶液中制备TiO2纳米管阵列,随着氧化时间的不同,TiO2纳米管阵列呈现各异的形貌。通过光电流测试,考察了不同氧化时间和施加不同电压下的Ti/TiO2纳米管阵列光电极的光电化学响应,阳极氧化6h表面规整纳米管阵列并施加偏压0.1V光电流响应最强。通过测试Mott-Schott-ky曲线,计算不同氧化时间的TiO2纳米管阵列的半导体载流子浓度、平带电位、空间电荷层宽度和能带弯曲量等特征参数,理论上提出了TiO2纳米管阵列生长机理。在光电催化降解无机氨氮的实验中,所得到的电化学阻抗谱(EIS)表明,外加偏压0.1V时,TiO2纳米管阵列电极的光电催化活性最强,同时通过拟合电路分析可知,光电催化降低了电极界面的反应阻抗,加速了光生载流子的转移,在TiO2纳米管阵列电极/溶液界面Helmholtz层中发生的氧化还原反应是整个光电催化反应的速率控制步骤。     

TiO2纳米管阵列催化降解甲基橙的性能研究

采用阳极氧化法制备了TiO2纳米管阵列电极,以甲基橙为目标降解物研究了TiO2纳米管阵列电极的光催化和光电催化性能.此外,还进行了超声辐射替代紫外光照探索性研究.结果表明,阳极氧化时间和热处理温度对TiO2纳米管阵列电极的光催化性能具有显著影响;在光催化过程中,施加一定外加电压可有效提高电极的光催化活性.尽管与紫外光照相比,超声辐射在TiO2纳米管阵列电极的催化氧化甲基橙分子过程中的促进作用具有一定的差距,但仍显示出替代紫外光照的可行性.     

CdS/TiO_2纳米管阵列的制备及其光电催化活性研究

利用阳极氧化法和电沉积法制备CdS修饰的TiO2纳米管阵列。应用FE-SEM、XRD、DRS和LSV(线性伏安扫描)对该阵列的形貌、晶型、光学性质和光电性能进行表征,并研究该阵列降解亚甲基蓝的光电催化活性。结果表明,CdS以颗粒形式存在于TiO2纳米管阵列表面,CdS/TiO2纳米管阵列在可见光处有较强吸收,有较大光响应电流,其光电催化活性优于纯TiO2纳米管阵列。     

TiO2纳米管的制备及光催化性能研究

以氟化铵水溶液为电解质,采用阳极氧化法,在钛片基体上制备出TiO2纳米管阵列.用FESEM、XRD等测试方法对样品进行表征,采用UV-1800型紫外-可见分光光度计检测TiO2纳米管对甲基橙的光催化性能.结果表明,氧化电压为50V,氧化时间为10h,煅烧温度为500℃时得到的TiO2纳米管对甲基橙的降解效果最好.     

形貌对锐钛矿型TiO_2纳米管薄膜光催化性能的影响

采用阳极氧化法在纯钛表面制备了5组平均内径不同以及5种管长不同的TiO2纳米管阵列薄膜,应用SEM对管径进行了表征.将之烧结成锐钛矿型后通过光催化降解甲基橙溶液研究管径与管长的大小对其光催化活性的影响,通过重复催化实验研究其重复使用的效果.结果表明:管径为100nm时催化剂催化降解甲基橙的效果最好,管长则基本不影响纳米管薄膜的催化活性.重复催化实验表明,TiO2纳米管薄膜有很好的重复使用效果.     

TiO2纳米管的结构特征对其光电催化性能的影响

研究了利用电化学阳极氧化法在不同的氧化电压和氧化时间条件下制备的TiO2纳米管(TNT)的结构特征对其光电催化性能的影响。运用场发射扫描电子显微镜,X射线衍射和X射线光电子能谱分析等手段对其进行表征,考察了其光电化学性质,研究了具有不同纳米结构特征的TiO2纳米管降解甲基橙染料废水的反应动力学性能。结果表明,TiO2纳米管的长径比对其光电催化性能影响最大。其管长和管径随着氧化电压和氧化时间的增大而增大,壁厚随着氧化电压的增大而减小。在其管长为25.85μm、壁厚为10.23nm、长径比为178、粗糙系数为175的条件下具有最大光电流密度4.8×10-2 mA/cm2,对甲基橙(MO)光电催化降解拟一级反应动力学常数达到最大值2.26×10-3/min。     

溶胶-凝胶法制备ZnFe2O4纳米薄膜及其光电催化性能研究

用溶胶-凝胶工艺在导电玻璃上制备出纳米ZnFe2O4薄膜,用X射线衍射仪、扫描电镜对膜的粒径、物相进行了表征,对不同层数的薄膜进行了光电催化性能测试.薄膜对甲基橙溶液的降解结果表明:随着ZnFe2O4薄膜层数的增多,对甲基橙的降解率先增大后减小,且以3层的ZnFe2O4膜片效果最好.当外加正向偏压时,薄膜的光催化性能有一定提高,且随着偏压增大而呈波动性增强.同时,薄膜与极板间的距离对薄膜的光电催化活性也有较大影响.     

TiO2/Ti光电催化体系中羟自由基的测定

为探索TiO2光电催化氧化体系中·OH的产生规律并加速该技术的实用化,根据光激发TiO2体系的特点,借助阴离子交换膜,建立了采用邻二氮菲-Fe(Ⅱ)分光光度法测定TiO2/Ti光电催化体系中羟自由基累积浓度的方法,研究了体系pH值,外加偏压等对产生羟自由基累积浓度的影响.结果表明:pH值和外加偏压对TiO2/Ti光电催化体系中·OH的生成率具有重要影响,当溶液的初始pH值在TiO2等电点(pH为6.3)附近,外加偏压为O.6 V时,光激发TiO2所产生·OH的累积浓度达到最大;光激发后体系的pH值朝着靠近等电点的方向变化.     

用乳酸溶液为电解质制备TiO2纳米管阵列

为了开发自组织阳极氧化制备TiO2纳米管阵列的新体系,以乳酸/NH4F混合溶液为电解质,研究了阳极氧化制备TiO2纳米管阵列的影响因素及形成机理.采用X射线衍射(XRD)和扫描电子显微镜(SEM)对样品进行检测,并通过观察阳极氧化过程中的电流-时间变化曲线,探讨TiO2纳米管阵列的形成机理.结果表明:阳极氧化电压、时间及电解质溶液的黏度是影响TiO2纳米管阵列结构和形貌的主要因素,在40 v阳极氧化电压下,制备出平均管径高达180 nm的纳米管,所获得的TiO2纳米管阵列为无定型结构,300℃热处理以后转变为锐钛矿型TiO2.     

TiO2纳米管阵列的制备工艺对其光催化性能的影响

采用阳极氧化法,在醇(丙三醇、乙二醇)-水-NH4F电解液体系中制备高度有序的TiO2纳米管阵列。采用场发射扫描电子显微镜(SEM)、X射线衍射仪(XRD)对TiO2纳米管阵列的形貌和晶型结构进行表征,讨论了阳极氧化法制备工艺(阳极氧化电压、氧化时间、电解液)对TiO2纳米管的形貌、结构及其甲基橙光催化降解性能的影响;分析了退火温度对TiO2阵列的物相及其光催化性能的影响。研究结果表明,采用高电压、增加氧化时间有利于TiO2纳米管阵列光催化的提高,在其它参数相同的情况下,采用丙三醇作为电解液制备获得的TiO2纳米管阵列较乙二醇体系具有更加优异的光催化性能。     

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。     

CeO2修饰的透明TiO2纳米管电极的电致变色器件

采用电化学沉积法在阳极氧化制备的TiO2纳米管阵列管壁上沉积一层CeO2纳米颗粒,再将CeO2修饰的透明TiO2纳米管阵列薄膜对电极与聚三甲基噻吩变色电极组装成透过型电致变色器件.实验结果表明:CeO2修饰的TiO2纳米管阵列薄膜仍保持良好的光透过性,其电荷存储能力比纯TiO2纳米管电极提高了30%.经CeO2修饰的TiO2纳米管改善了器件的性能,与对电极为单一TiO2纳米管阵列的器件相比,其对比度仍保持在38%左右,其褪色时间由1.3 s缩短为0.8 s.电致变色器件快速响应得益于纳米管与纳米颗粒组成的复合结构的高比表面积和快速的电荷传输过程.     

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.     

Nitrogen-doped TiO2 nanotube array films with enhanced photocatalytic activity under various light sources

Highly ordered nitrogen-doped titanium dioxide (N-doped TiO(2)) nanotube array films with enhanced photocatalytic activity were fabricated by electrochemical anodization, followed by a wet immersion and annealing post-treatment. The morphology, structure and composition of the N-doped TiO(2) nanotube array films were investigated by FESEM, XPS, UV-vis and XRD. The effect of annealing temperature on the morphology, structures, photoelectrochemical property and photo-absorption of the N-doped TiO(2) nanotube array films was investigated. Liquid chromatography and mass spectrometry were applied to the analysis of the intermediates coming from the photocatalytic degradation of MO. The experimental results showed that there were four primary intermediates existing in the photocatalytic reaction. Compared with the pure TiO(2) nanotube array film, the N-doped TiO(2) nanotubes exhibited higher photocatalytic activity in degradating methyl orange into non-toxic inorganic products under both UV and simulated sunlight irradiation.     

Photocatalytic degradation of methyl orange using a TiO2/Ti mesh electrode with 3D nanotube arrays

To further improve the photocatalytic techniques for water purification and wastewater treatment, we successfully prepared a new type of TiO(2)/Ti mesh photoelectrode, by anodization in ethylene glycol solution. The three-dimensional arrays of nanotubes formed on Ti mesh show a significant improvement in photocatalytic activity, compared to the nanotube arrays formed on foil. This can be demonstrated by about 22 and 38% enhancement in the degradation efficiency per mass and per area, respectively, when TiO(2)/Ti mesh electrode was used to photocatalyze methyl orange (MO). Furthermore, the effects of different parameters on MO photodegradation were investigated, such as different photoelectrode calcination temperature, the initial pH value of MO solution, and the present of hydrogen peroxide. The superior photocatalytic activity could be achieved by the TiO(2)/Ti mesh photoelectrode calcinated at 550 °C, due to the appearance of mixed crystal phases of anatase and rutile. In strong acidic or caustic conditions, such as pH 1 or 13, a high degradation efficiency can be both obtained. The presence of H(2)O(2) in photocatalytic reactions can promote photocatalytic degradation efficiencies. Moreover, the experimental results demonstrated the excellent stability and reliability of the TiO(2)/Ti mesh electrode.     

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.     

MoS_2与TiO_2一维纳米复合材料的制备与表征

本文采用气相还原法制备了MoS2包覆TiO2的一维纳米复合材料,首先用水热法制备TiO2纳米管,并制备前驱体(NH42)MoS4;用浸渍法将(NH4)2MoS4附着于TiO2纳米管表面;然后利用氢气还原前驱体得到MoS2包覆层。用X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)表征所得产物的结构及微观形貌。结果表明当还原反应温度较高(≥600℃)时,产物呈烧结状态,而当反应温度为500℃时,可以得到表面均匀包覆MoS2的TiO2纳米管复合材料,其中包覆层MoS2的结晶程度较低。在此基础上,本文提出了该产物的生长模型,并对包覆前后的样品做荧光性能分析。     

Simple fabrication of carbon/TiO2 composite nanotubes showing dual functions with adsorption and photocatalytic decomposition of Rhodamine B

Carbon/TiO2 composite nanotubes were fabricated via a very simple electrospinning process and their dual functionalities of adsorptivity and photocatalytic activity were evaluated using Rhodamine B (RhB) as a model organic pollutant. A poly(vinyl alcohol) (PVA) aqueous solution was directly electrospun into a coagulation bath containing titanium (IV) tetraisopropoxide (TTIP) solution so that PVA-core/TiO2-shell composite nanofibers were formed through the in situ sol-gel reaction of TTIP. The carbon/TiO2 composite nanotubes were then fabricated by heat treatment of composite nanofibers under nitrogen atmosphere. By using several characterization methods, we confirmed that the resultant nanotubes consisted of anatase TiO2 nanocrystallites embedded in a carbonaceous matrix. The prepared nanotubes exhibited fast adsorption of RhB with high capacity compared with a commercial porous carbon, and they also showed the photocatalytic decomposition activity for the dye molecules under UV irradiation comparable to the degradation by P-25 and ST-01 (commercial TiO2). Finally, the carbon/TiO2 composite nanotubes exhibited several cycle performances of adsorption-photodegradation for RhB. This indicates that the composite nanotubes can adsorb and photodecompose organic pollutants repeatedly without additional activating processes.     

氮掺杂二氧化钛纳米管制备与光催化性能

以多孔氧化铝为模板,采用溶胶凝胶法制备出二氧化钛纳米管,在氨气气氛下进行了氮掺杂。用TEM、XRD、DRS等对其进行了表征,并通过降解碱性藏花红溶液研究了其光催化的性能。结果表明,用模板法制备的二氧化钛纳米管管径均匀、可控且排向一致,从DRS光谱可以推测出氮掺杂后的二氧化钛纳米管在可见光区有较强的吸收,并且与二氧化钛纳米管相比氮掺杂的二氧化钛纳米管的降解碱性藏花红溶液的效率更高。     

Fabrication of mesoporous titanium oxide nanotubes based on layer-by-layer assembly

Titanium oxide (TiO2)/polyacrylic acid (PAA) composite nanotubes were firstly fabricated through the sol-gel process of titanium alkoxide in the inner pores of alumina template followed layer-by-layer assembly with polyacrylic acid (PAA). Mesoporous TiO2 nanotubes could be obtained after the removal of PAA component by calcination and etching of the template with concentrated sodium hydroxide aqueous solution. The surface area of as-prepared porous TiO2 nanotubes was measured as twice larger than that of the conventional TiO2 nanotubes and the pore diameter in the wall of the tubes is several nanometers. Such assembled mesoporous nanotubes can serve as carriers for catalysis release and biomolecules.