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.     

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。     

TiO_2纳米管阵列电极染料敏化太阳能电池

采用电化学阳极氧化法在纯钛片表面制备了高度有序的TiO2纳米管阵列。利用SEM、XRD分别对TiO2纳米管阵列的形貌、晶型进行了表征,并通过线性扫描伏安法对N719染料敏化纳米管阵列电极的光电性能进行了研究。实验结果表明,纳米管阵列的管径和长度随着阳极氧化电压的升高和氧化时间的延长都分别相应增加。同时还发现,通过450℃热处理的TiO2纳米管阵列,具有较好的锐钛矿晶型结构,其光电转化效率为2.1%。     

玻璃基底TiO2纳米管阵列的制备及其光电性能研究

提高二氧化钛纳米管阵列电极的机械稳定性,改善电极的透光性能,有助于提高其光电催化性能,拓展电极的应用范围.通过室温射频溅射方法在玻璃基底上溅射一层金属钛膜,然后在含0.5%HF的电解液,10V阳极氧化电压下进行阳极氧化,得到玻璃基TiO2纳米管阵列电极.扫描电子显微镜和X射线衍射分析表明,玻璃基表面形成了孔径为20～30nm,管长约130nm排列有序的锐钛矿型TiO2纳米管阵列.光电性能测试表明,玻璃基TiO2纳米管阵列与金属钛基TiO2纳米管阵列表现出相似的光电催化性能,明显优于磁控溅射制备的TiO2薄膜.     

阳极氧化电压对TiO2纳米管阵列生长及场发射性能的影响

室温下在HF水溶液中,利用阳极氧化法在纯钛表面制备了规则有序的TiO2纳米管阵列,应用场致发射扫描电子显微镜、X射线光电子能谱对纳米管阵列表面形貌、断面结构及元素组成进行表征,并对所得样片的场发射性能进行测试,研究了阳极氧化电压对TiO2纳米管阵列形貌及场发射性能的影响.结果表明:在一定范围内增大氧化电压,可增大纳米管的管径、壁厚和管长,但壁厚变化比较小.随着氧化电压的增大,开启场强先降低后增大.当氧化电压为10 V时,所获得的TiO2纳米管阵列开启场强最低,为3.15 V/μm,在6h内8 V/μm电场下保持了稳定的场发射,电流密度为0.85 mA/cm2.     

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。     

不同制备条件对二氧化钛纳米管阵列及其结构的影响

采用阳极氧化法以NH4F/乙二醇为电解液制备高度有序的TiO2纳米管,研究了不同电解液浓度、电解电压、电解时间等参数对TiO2纳米管的影响.在不同温度下对TiO2纳米管进行退火处理.分别利用转靶X射线衍射仪(XRD)和场发射扫描电子显微镜(SEM)对TiO2纳米管阵列的物相结构和形貌变化进行表征.结合氧化过程电流密度变...     

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。     

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。     

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。     

Fabrication of highly ordered TiO2 nanotube arrays via anodization of Ti-6Al-4V alloy sheet

Uniform and highly ordered TiO2 nanotube arrays were fabricated by the electrochemical anodic oxidation on Ti-6Al-4V surface, using graphite plate as cathode and ethylene glycol (EG) with addition of a certain amount of H2O and NH4F as electrolyte, and the anodization voltage went up to a presetting voltage by stepwise increment. The morphology, structure and composition of TiO2 nanotube arrays were characterized by SEM, EDS, XRD and XPS. The formation process of TiO2 nanotubes was introduced in brief. The experiments were arranged by an orthogonal experiment method and the experimental results showed that the formation of TiO2 nanotube arrays was influenced by not only each factor (F- content, H2O content, external voltage and duration), but also cross correlation among the four factors. The optimal condition was F- content 0.2 wt%, H2O content 4 vol%, external voltage 40 V and duration 1 h in the studied electrochemical system, and the length of obtained nanotubes was 1.5 microm, the outer diameter was approximately 100 nm and the aspect ratio was 15. As-formed nanotube arrays were amorphous and changed to anatase TiO2 after annealed at 500 degrees C for 2 h in air ambience. XPS survey spectra revealed the surface of as-formed nanotube arrays containing Ti, O, C, F and N. The nanotube arrays on Ti-6Al-4V surface with better thermo-stability and crystallinity would have great potential in biomaterials.     

Template-assisted electrochemical synthesis of cuprous oxide nanowires

Nanowires of Cu₂O as well as Cu were synthesized within the anodic aluminum oxide templates in an aqueous acidic electrochemical cell. The content of Cu₂O in the copper nanowires was controlled by varying the anodic potential of the pulse-reverse electrolysis and the pH of the electrolyte within a range of 2.0–3.9. For the pH of 2.0, pure Cu nanowires were deposited regardless of the anodic potential. When the anodic potential became higher than the cathodic one, pure Cu₂O nanowires were produced at a pH of 3.9. The growth of Cu₂O nanowires in the acidic electrolyte was ascribed to the local increase of the pH at the pore base, as well as the capacitive barrier layer of the template.     

TC4钛合金表面阳极氧化制备TiO_2多孔膜的实验研究

以硫酸为电解液,钛合金(TC4)为阳极,不锈钢片为阴极,采用恒压的氧化方式在钛合金表面获得TiO2多孔膜。通过扫描电镜(SEM)观察了多孔膜的微观形貌并用X射线衍射(XRD)对覆在钛合金基体上的氧化膜进行了物相分析,研究了氧化工艺参数电压、阳极氧化时间和硫酸浓度对TiO2多孔膜相组成的影响。结果表明:TC4钛合金阳极氧化获得的氧化膜为非均一平面的TiO2多孔膜,且膜的孔径分布在90~240nm,XRD分析表明在不同的氧化工艺参数下氧化膜均由锐钛相和金红石相双相晶型组成。在0.5mol/L硫酸溶液中,电压高于100V或氧化时间长于5min即出现锐钛相和金红石相TiO2,随着电压的升高和时间的增长金红石相TiO2的含量逐渐增加;在恒压120V时,硫酸溶液浓度为0.3mol/L即出现锐钛相和金红石相TiO2,随着硫酸浓度的提高金红石相TiO2的含量先增加后减少。     

In-situ preparation of multi-layer TiO2 nanotube array thin films by anodic oxidation method

The multi-layer TiO₂ nanotube array thin films have been formed by anodic oxidation method via adjusting the outer voltage during oxidation process in glycerol electrolyte containing 0.3% NH₄HF₂. The diameter of the nanotube array increases with the outer voltage, and the length of nanotube in every layer increases with the anodic oxidation time. These multi-layers bring new possibilities to tailor the properties of the TiO₂ nanotube array thin films formed via anodic oxidation method. Further, such multi-layer structure provide a new approach to evaluate the growth rate of TiO₂ nanotube, which will help us to understand more deeply the formation mechanism of the TiO₂ nanotubes. The growth rate of TiO₂ nanotube array is respectively 1.2 and 3.6 μm/h under the anodic voltage of 30 V and 60 V. These multi-layer TiO₂ nanotube array thin films may exhibit lots of potential applications in photoelectrochemical fields.     

不同电解液组成对TiO2纳米管形成的影响

电解液在阳极氧化中发挥着重要作用,对TiO2纳米管的形成与否,形成后管的成分、形貌都有着很大的影响.本实验采用了恒压阳极氧化方式,分别以HF(0.5wt%),(NH4)2SO4 HF(0.5wt%),(NH4)H2PO4 HF(0.5wt%),NaNO3 HF(0.5wt%)为电解液,在钛箔表面获得多孔TiO2膜.用FESEM观察了多孔膜的形貌并用EDX和XPS能谱对膜表面成分和构成进行测试分析.实验结果表明:在单一的HF酸电解液中加入(NH4)2SO4或(NH4)H2PO4后,阳极氧化生成的膜孔径明显减小,并且膜表面形态较差.加入NaNO3后,对膜的形貌影响不是很大.由EDX和XPS能谱分析得出,阴离子中的大部分非金属元素较难进入膜表面,而氮元素却很容易掺杂进入膜的表面形成N-Ti-O结构,从而影响膜的成分构成.这表明本实验利用简单电化学方法实现了N的掺杂.通过XRD测试得出,含不同阴离子的电解液对TiO2膜的晶型转变温度影响不大.     

钛合金着色技术的研究

利用正交试验法研究了在磷酸-冰乙酸体系中磷酸、冰乙酸、添加剂、氧化电压、电解液温度、氧化时间等对钛阳极氧化膜的影响,确定了最佳工艺条件.结果表明,在采用以Ce作为添加剂的电解液中处理后所得到的钛合金着色膜呈蓝色、光亮美观,具有优良的耐蚀性、耐磨性和良好的附着力.     

阳极氧化时间对二氧化钛纳米管阵列形貌的影响

采用电化学阳极氧化法,以乙二醇体系作为电解液,在60V的直流电压下,在纯钛基底表面制备高度有序的TiO2纳米管阵列,通过改变氧化时间来探究其对TiO2纳米管阵列形貌的影响。运用XRD、SEM分别对TiO2纳米管阵列的结构、形貌特征进行表征。结果表明,氧化时间对TiO2纳米管的管壁厚度、管径以及管长均有影响;氧化时间为2～2.5h时,所得到的二氧化钛纳米管管壁约为10nm、管径约为200nm、管长为2～3μm。     

Dye-sensitized solar cells based on thick highly ordered TiO(2) nanotubes produced by controlled anodic oxidation in non-aqueous electrolytic media

Dye-sensitized solar cells (DSSCs) were prepared using TiO(2) nanotubes, grown by controlled Ti anodic oxidation in non-aqueous media. Smooth, vertically oriented TiO(2) nanotube arrays, presenting a high degree of self-organization and a length of 20 μm, have been grown using ethylene glycol electrolyte containing HF. As-grown nanotubes exhibit an amorphous structure, which transforms to the anatase TiO(2) crystalline phase upon post-annealing in air at 450?°C. Atomic force microscopy (AFM) revealed the porous morphology together with high roughness and fractality of the surface. The annealed tubes were sensitized by the standard N719 ruthenium dye and the adsorption was characterized using resonance micro-Raman spectroscopy and adsorption-desorption measurements. The sensitized tubes were further used as active photoelectrodes after incorporation in sandwich-type DSSCs using both liquid and solidified electrolytes. The efficiencies obtained under air mass (AM) 1.5 conditions, using a back-side illumination geometry, were very promising: 0.85% using a composite polymer redox electrolyte, while the efficiency was further increased up to 1.65% using a liquid electrolyte.     

An innovative approach to synthesize highly-ordered TiO2 nanotubes

An innovative route to prepare highly-ordered and dimensionally controlled TiO2 nanotubes has been proposed using a mild sonication method. The nanotube arrays were prepared by the anodization of titanium in an electrolyte containing 3% NH4F and 5% H2O in glycerol. It is demonstrated that the TiO2 nanostructures has two layers: the top layer is TiO2 nanowire and underneath is well-ordered TiO2 nanotubes. The top layer can easily fall off and form nanowires bundles by implementing a mild sonication after a short annealing time. We found that the dimensions of the TiO2 nanotubes were only dependent on the anodizing condition. The proposed technique may be extended to fabricate reproducible well-ordered TiO2 nanotubes with large area on other metals.     

Conversion of potassium titanate nanowires into titanium oxynitride nanotubes

Tunnel-structured potassium titanate with a K(3)Ti(8)O(17) phase was synthesized by direct oxidation of titanium powder mixed with KF(aq) in water vapor at 923 K. The reaction conditions were adjusted so that uniform single crystalline potassium titanate nanowires with [010] growth direction (length: 5-30 μm, diameter: 80-100 nm) were obtained. Nitridation of the nanowires by NH(3)(g) at 973-1073 K converted the titanate nanowires into rock-salt structured cubic phase single crystalline titanium oxynitride TiN(x)O(y) nanotubes (x = 0.88, y = 0.12, length = 1-10 μm, diameter = 150-250 nm, wall thickness = 30 - 50 nm) and nanorods (x = 0.5, y = 0.5, length = 1-5 μm, diameter = 100-200 nm) with rough surfaces and [200] growth direction. The overall conversion of the titanate nanowires into the nanotubes and the nanorods can be rationalized by Ostwald ripening mechanism. We fabricated an electrode by adhering TiN(x)O(y) nanotubes (0.2 mg) on a screen-printed carbon electrode (geometric area: 0.2 cm(2)). Electrochemical impedance spectroscopy demonstrated its charge transfer resistance to be 20Ω. The electrochemical surface area of the nanotubes on the electrode was characterized by cyclic voltammetry to be 0.32 cm(2). This property suggests that the TiN(x)O(y) nanostructures can be employed as potential electrode materials for electrochemical applications.