大管径TiO_2纳米管的制备及其光解水性能研究

采用阳极氧化法制备小管径(20~300 nm)的TiO2纳米管已经有很多报道,但大管径的TiO2纳米管的制备还是一个挑战。为制备大管径的TiO2纳米管,研究了高水含量的电解液对纳米管管径的影响。结果表明,纳米管的管径随水含量的增加而增加(8%~12%(体积分数)),而水含量增加到13%(体积分数)时,无法得到规则的纳米管,进一步增加水含量到20%(体积分数),只能得到致密的TiO2薄膜。此外,在含有0.3%(质量分数)NH4F和12%(体积分数)H2O的乙二醇电解液中,研究了不同氧化电压对纳米管管径的影响。结果表明,在170 V氧化电压下制备的TiO2纳米管的管径可达到600 nm。纳米管的光解水性能测试结果表明,管径的增大有利于提高TiO2纳米管的光解水性能。     

HF酸电解液浓度对TiO2纳米阵列结构的影响

TiO2纳米阵列(纳米管、纳米棒)结构具有良好的力学性能、化学稳定性以及抗腐蚀性能,在许多技术领域具有广阔的应用前景。采用阳极氧化法在工业纯钛片表面制备出高度有序的TiO2纳米管阵列和纳米棒阵列,研究了电解液浓度和阳极氧化时间对TiO2纳米阵列结构的影响,并对其形成机理进行了初步探讨。结果表明,低浓度的HF酸电解液有利于制备纳米管阵列,高浓度的HF酸电解液有利于制备纳米棒阵列。     

甘油/DMF混合体系中TiO2纳米管阵列的制备及表征

采用电化学阳极氧化法,以甘油/DMF混合溶液为电解质,在纯钛表面制备了一层排列紧密、结构规整的TiO2纳米管阵列。讨论了氧化电压、电解液中DMF比例、电解液中水含量和电解液重复使用对TiO2纳米管阵列形貌的影响,并且从阳极氧化过程中电流-时间曲线出发分析了混合体系中阳极氧化的形成特征。研究表明,氧化电压越高所制备的纳米管管径越大,但是管长与氧化电压之间不呈线性关系;电解液中DMF比例增加不利于纳米管形成;电解液中水含量越高,纳米管管径越大,表面的覆盖物越多,最佳的水含量为1%(体积分数)。经450℃热处理2h后TiO2纳米管阵列的结构由无定形转变为锐钛矿型。     

V掺杂TiO2纳米管阵列的制备及光催化研究

以钒钛合金为原料,应用阳极氧化法制备出高度致密、有序的V掺杂TiO2纳米管阵列。应用扫描电镜(SEM)和粉末X光衍射仪(XRD)表征分析纳米管阵列的形貌和结构,结果表明在浓度不同的HF电解液下制备出径向不同的纳米管阵列,电解液浓度(0.5%～1.5%(质量分数)),管径变化(39.7～72.7nm)。在室温、可见光照射条件下,以10mg/L的亚甲基蓝溶液为模拟污染物进行光催化降解试验,研究了其光催化性能。结果显示V掺杂TiO2纳米管阵列光催化性能优于纯TiO2纳米管,且在HF电解液浓度为1.0%(质量分数)时制备出来的TiO2纳米管光催化降解有机毒物性能最佳。     

不同阳极氧化条件下TiO_2纳米管阵列的制备及表征

分别在三种不同的电解液中,以钛为基体采用阳极氧化的方法制备了TiO2纳米管阵列薄膜,用SEM观察纳米管阵列薄膜的形貌、测量纳米管管径大小;用XRD、拉曼光谱检测TiO2纳米管阵列薄膜热处理前后的晶型.结果表明:不同的电解液体系和氧化电压下得到的纳米管形貌各不相同.在0.24wt%HF水溶液中得到的TiO2纳米管排列整齐,管径为110nm;在0.5wt%NaF+2.7wt%Na2SO4水溶液和0.88wt%NH4F的丙三醇-水(体积比1:1)混合溶液中得到的纳米管排列不规整,管径为100nm;在0.24wt%HF条件下生成的TiO2纳米管管径与氧化电压成线性关系:d=k×U+b,其中,系数k=5.2nm/V,b=2.2nm,0≤U≤25V.经450℃热处理2h后TiO2纳米管结构由无定形态转变为锐钛矿.     

三电极体系制备TiO2纳米管

利用电化学阳极氧化法在乙二醇和氟化铵溶液三电极体系中阳极氧化纯钛箔,制备出具有双面结构的TiO2阵列纳米管。研究了不同电压和电解液含水量对纳米管形貌的影响,通过扫描电子显微镜(SEM)和X射线衍射仪(XRD)分析了TiO2纳米管阵列的微观形貌及物相。     

阳极氧化法制备TiO2纳米管的pH值参数研究

采用电化学阳极氧化法在HF水溶液体系中对钛金属进行表面处理,得到高度规整的TiO2纳米管阵列.主要研究了电解液pH值大小对TiO2纳米管阵列形貌(管径及管长)的影响;用扫描电子显微镜(SEM)对其表面形貌进行表征.结果表明:酸性条件下能形成TiO2纳米管;强碱性环境不利于TiO2纳米管的制备;在可制备TiO2纳米管的pH值范围内,管径和管长随pH值升高而减小.采用微孔模型对pH值的影响机理进行了阐述.     

阳极氧化TiO2纳米管阵列的制备及场发射性能

采用阳极氧化法以HF水溶液为电解液制备二氧化钛(TiO2)纳米管阵列,用场致发射扫描电子显微镜和X射线光电子能谱对纳米管阵列的表面形貌、断面结构及元素组成进行表征,并使用场发射测试系统测试其场发射性能,研究了HF水溶液的pH值对TiO2纳米管阵列形貌(管径及管长)的影响。结果表明:调节电解液的pH值可改变TiO2纳米管阵列的形貌,从而提高其场发射性能。当电解液pH值为2.0时TiO2纳米管阵列的场发射开启场强降为2.52 V/μm,且具有较好的电流稳定性。     

阳极氧化工艺参数对TiO_2纳米管形貌和性能的影响

采用阳极氧化法制备TiO2纳米管阵列,研究电解液成分、阳极氧化电压、阳极氧化时间、电解液温度及氧化次数对纳米管阵列微观结构及形貌的影响,探讨了TiO2纳米管阵列生长机理,并采用SEM、表面粗糙度仪、接触角测量仪对所得TiO2纳米管阵列的形貌、粗糙度、亲水性及表面能进行了表征和分析。结果表明,阳极氧化后Ti表面活性增加,相比于其他阳极氧化工艺参数,电解液成分对样品表面粗糙度、接触角及表面能的影响更大。     

电解液组分对阳极氧化法制备TiO_2纳米管的影响

在不同电解液组分中采用阳极氧化法制备了不同结构参数的TiO2纳米管,考察了不同电解液组分对TiO2纳米管形貌和尺寸参数的影响.采用场发射扫描电子显微镜(SEM)和X射线衍射仪(XRD)对纳米管的形貌和结构进行了表征,并分析了电解液组分对纳米管生长的影响机制.结果表明,降低电解液中H+浓度以及减少电解液中H2O的含量可有效提高纳米管的长度.     

TiO_2纳米管的制备及光电性能研究

以NH4F-乙二醇为电解液阳极氧化制备Ti基TiO2纳米管,利用扫描电镜(SEM)图像分析TiO2纳米管阵列的退火前后的形貌结构变化,研究退火温度对TiO2纳米管光电性能的影响。分别用CdS、曙红对TiO2纳米管进行敏化,并研究了其敏化后的光电性能和电极稳定性。结果表明:退火并未改变TiO2纳米管结构,经CdS敏化后的TiO2纳米管光电性能最好,且电极稳定性也较好。     

TiO2 nanotube membranes on transparent conducting glass for high efficiency dye-sensitized solar cells

Crack-free TiO(2) nanotube (NT) membranes were obtained by short time re-anodization of a sintered TiO(2) NT array on Ti foil, followed by dilute HF etching at room temperature. The resulting freestanding TiO(2) membranes were opaque with a slight yellow color having one end open and another end closed. The membranes were then fixed on transparent fluorine-tin-oxide glass using a thin layer of screen-printed TiO(2) nanoparticles (NPs) as a binding medium. It was found that low temperature treatment of the resulting NT/NP film under appropriate pressure before sintering at 450?°C was critical for successful fixation of the NT membrane on the NP layer. The resulting films with open-ends of NT membranes facing the NP layer (open-ends down, OED, configuration) exhibited better interfacial contact between NTs and NPs than those with closed-ends facing the NP layer (closed-ends down, CED, configuration). The cells with an OED configuration exhibit higher external quantum efficiency, greater charge transfer resistance from FTO/TiO(2) to electrolyte, and better dye loading compared to CED configurations. The solar cells with the OED configuration gave 6.1% energy conversion efficiency under AM1.5G condition when the commercial N719 was used as a dye and I(-)/I(3)(-) as a redox couple, showing the promise of this method for high efficiency solar cells.     

Hyaluronic acid immobilization on the poly-allylamine coated nano-network TiO2 surface

Recently, biocompatibility report revealed that the TiO2 nano-network (TiO2 NT) structure has much higher cells colonization than the native TiO2 on Ti surface. In this study, we prepared the hyaluronic acid (HA) immobilized TiO2 NT layer by plasma surface modification and then evaluated biological behavior of MC3T3-E1 on the Ti, TiO2 NT and TiO2 NT/NH2/HA surface. The cell viability tests revealed slightly enhanced viability on the TiO2 NT/NH2/HA surfaces than on the untreated Ti surfaces.     

Electrochemiluminescence cell fabrication using TiO2 nanotube produced by anodic oxidation

Electrochemiluminescence (ECL) cell using the electrode of TiO2 nanotube (NT) and Ru(ll) complex Ru(bpy)3(PF6)2 as a luminacence substance was fabricated. TiO2 NT were produced from the membrane of TiO2 NT arrays fabricated by anodic oxidation of approximately 100 microm thick Ti-plate. TiO2 NT arrays inject increasing number of electrons to the Ru(II) complex at the interface of TiO2 NTs. It allows the increasing exergonic oxidation/reduction reaction of Ru(II) complex. The ECL cell emits approximately 600 nm light in orange color. The cell structure is composed of a glass/F-doped SnO2(FTO)/TiO2 NT/Ru(II) complex in propylene carbonate/FTO/glass. The ECL efficiency of the cell consisting of the layer of TiO2 NT was approximately 255 cd/m2 at a bias of 4 V. The use of TiO2 NT increases ECL intensities by 5 times compared to the typical ECL cell without the use of TiO2 NT.     

Self-organized TiO2 nanotube arrays: synthesis by anodization in an ionic liquid and assessment of photocatalytic properties

Self-organized TiO(2) nanotube (NT) arrays were produced by anodization in ethylene glycol (EG) electrolytes containing 1-n-butyl-3-methyl-imidazolium tetrafluoroborate (BMI.BF(4)) ionic liquid and water. The morphology of the as-formed NTs was considerably affected by changing the anodization time, voltage, and water and ionic liquid electrolyte concentrations. In general, a nanoporous layer was formed on the top surface of the TiO(2) NTs, except for anodization at 100 V with 1 vol % of BMI.BF(4), where the NT's mouth was revealed. The length and bottom diameter of the NTs as well as the pore diameter of the top layer showed a linear relationship with increased anodization voltage. These TiO(2) NTs were tested as photocatalysts for methyl orange photodegradation and hydrogen evolution from water/methanol solutions by UV light irradiation. The results show that the TiO(2) NTs obtained by anodization in EG/H(2)O/BMI.BF(4) electrolytes are active and efficient for both applications.     

Macro,micro and nanostructure of TiO<Subscript>2</Subscript> anodised films prepared in a fluorine-containing electrolyte

The paper presents an electron microscopy study of the macro, micro and nanostructure of titania nano-tubes formed by electrochemical anodisation of titanium in a fluorine containing electrolyte. Scanning electron microscopy (SEM) is used to examine the overall structure of the nano-tubes formed under potentiostatic conditions. Transmission electron microscopy (TEM) has been used to examine the structure of the oxide layer of a sample anodised for a relatively short period (30 min) and provides a new insight into the formation of titania nano-tubes. The fluorine ions are able to nucleate sites on the titanium metal and generate a series of interconnected cavities or pores in the oxide complex formed, allowing current to flow within this film. Under specific conditions the cavities and randomly dispersed pores can align in the direction of the applied electric field and link up to generate an array of tubes, where the passage of ions and water is optimised. We also suggest that oxygen evolution at the anode may play a role in the development of the nano-tubes.     

通过聚吡咯-聚苯胺共聚物修饰TiO_2纳米管阵列来增强其可见光光催化性能（英文）

纳米管阵列结构的光催化半导体设计一直以来是研究热点,因为纳米管结构有益于对光的吸收和减少载流子的迁移距离。然而,这些材料往往受限于比较差的电荷传输。因此,我们研究了一个易于重复利用的PPy-PANI/TiO2NT光催化剂,其中聚吡咯-聚苯胺共聚物充当光敏剂和电子导体介体。实验所制备的PPy-PANI/TiO2NT复合材料有更高的可见光吸收,更高的电荷分离效率以及在可见光下有156μA的光电流。所有的样品通过XRD,FTIR,SEM,光电流进行表征。通过降解4-NP也证明由聚吡咯-聚苯胺共聚物修饰后的二氧化钛有很好的光催化效果。     

暴露高活性晶面的TiO2纳米管的制备及生物活性

采用多次阳极氧化技术,在金属钛表面制备(001)晶面族择优生长的TiO_2纳米管阵列,研究电解液成分对锐钛矿TiO_2不同晶面相对比例的影响并考察其生物学活性。采用扫描电镜(SEM)、X射线衍射(XRD)等方法分析纳米管阵列的形貌特征和晶体结构,通过生物矿化CaP盐的沉积和蛋白吸附实验评价样品晶面对生物活性的影响。结果表明:通过改变电解液中H_2O的含量,能够便捷调控锐钛矿TiO_2纳米管中不同晶面的相对比例。当H_2O含量为2%(体积分数)时,制备得到的TiO_2纳米管阵列(004)晶面的织构系数T_c(004)可达4.76。而具有(001)优势晶面族的TiO_2纳米管,在类人体环境中能够为生物矿化和蛋白吸附提供更多的活性位点,加速羟基磷灰石的沉积并增加蛋白吸附量,表现出更优异的生物学活性。     

Capillary effects, wetting behavior and photo-induced tube filling of TiO(2) nanotube layers

The present work addresses effects associated with the electrolyte penetration kinetics into TiO(2) nanotube layers. In particular, it is shown that the electrolyte uptake kinetics affects the magnitude of the measured photoresponse. We demonstrate that for aqueous electrolytes the penetration of the electrolyte into a TiO(2) nanotubular layer is comparably slow and may take up to several hours. The electrolyte uptake kinetics can significantly be accelerated by UV illumination. We ascribe this to a light-induced change in the wetting properties on the inside of the TiO(2) nanotube surface. This effect can be exploited to achieve photo-induced filling of the nanotubes by a secondary material.     

Enhancement of ionic conductivity of PEO based polymer electrolyte by the addition of nanosize ceramic powders

The ionic conductivity of polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) has been improved by the addition of nanosize ceramic powders (TiO2 and AL2O3). The PEO based solid polymer electrolytes were prepared by the solution-casting method. Electrochemical measurement shows that the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte has the best ionic conductivity (about 10(-4) S cm(-1) at 40-60 degrees C). The lithium transference number of the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte was measured to be 0.47, which is much higher than that of bare PEO polymer electrolyte. Ac impedance testing shows that the interface resistance of ceramic-added PEO polymer electrolyte is stable. Linear sweep voltammetry measurement shows that the PEO polymer electrolytes are electrochemically stable in the voltage range of 2.0-5.0 V versus a Li/Li+ reference electrode.