Optimizing TiO2 nanotube morphology for enhanced photocatalytic H2 evolution using single-walled and highly ordered TiO2 nanotubes decorated with dewetted Au nanoparticles

In the present work we introduce the formation of highly ordered single-walled TiO₂ nanotubes based on anodizing nanoimprinted titanium substrates. In a first step, anodization on nanoimprinted substrates leads to the formation of highly ordered TiO₂ nanotubes. These as-formed TiO₂ nanotubes have a double-walled nature. After an optimized chemical treatment in piranha solution, the inner wall is removed and an array of single-walled TiO₂ nanotubes is obtained that has a high degree of hexagonal ordering. These single walled arrangements show an enhanced photocatalytic activity for H₂ evolution in comparison with classic self-ordered TiO₂ nanotubes.     

阳极氧化法制备二氧化钛纳米管及其荧光性质

室温下采用电化学阳极氧化法在NaF、Na₂SO₄和H₂SO₄的混合溶液中用化学处理后的纯Ti片表面组装了一层结构高度有序的高密度TiO₂纳米管阵列。考察了几种主要的实验参数(阳极氧化电压、温度、电解液浓度)对TiO₂纳米管阵列形貌和尺寸的影响，探讨了二次阳极氧化对纳米管形貌的改善。对TiO₂纳米管阵列进行扫描电子显微镜(SEM)和荧光(PL)分析，探讨其生长机理。结果表明，孔径随阳极氧化电压的升高而变大，温度、电解液浓度影响反应过程中电流密度的大小；二次阳极氧化得到的纳米管的有序性有所改善，孔径大小更为均一，并且发现TiO₂纳米管的荧光具有量子效应。     

二氧化钛反蛋白石薄膜的制备及其在化学传感器中的应用

用提拉成膜法将单分散295 nm聚甲基丙烯酸甲酯(PMMA)胶体微球自组装成蛋白石光子晶体膜. 在PMMA蛋白石光子晶体膜的空隙里填充15 nm二氧化钛纳米颗粒, 经500 ℃的处理除去PMMA膜板, 制备出大面积, 结构均一的二氧化钛反蛋白石光子晶体膜. 扫描电子显微镜(SEM)观察和X射线光电能谱(XPS)分析表明, 这种二氧化钛反蛋白石光子晶体薄膜是六方紧密堆积. 用这种二氧化钛反蛋白石光子晶体膜对溶液折射率的检测实验表明该传感膜分辨率可达0.01.     

Lithium-ion intercalation and electrochromism in ordered V2O5 nanoporous layers

Highly ordered V₂O₅ porous layers were fabricated from vanadium metal foils by self-organizing anodization. The defined porous structure of this material provides excellent lithium-ion transportation and intercalation/extraction properties. As a result the highly ordered porous structure shows a very good electrochromic performance with long term switching stability.     

Controlled self-assembly of nanoporous alumina for the self-templating synthesis of polyaniline nanowires

In this report, the self-templating synthesis of polyaniline nanowires on prestructured aluminum is described, emphasizing that anodization and electropolymerization can occur at the same time by a single electrochemical process. The method is based on the principle that the anodization of predefined aluminum in H₂SO₄ leads to the formation of highly ordered porous alumina and aniline monomer can be electrochemically polymerized in the formed porous alumina by the anodic reaction. XPS analysis reveals that polyaniline nanowires prepared in this work is protonated emeraldine.     

Electrochemical capacitance performance of polypyrrole–titania nanotube hybrid

In this study, the polypyrrole–titania nanotube hybrid has been synthesized for an electrochemical supercapacitor application. The highly ordered and independent titania nanotube array is fabricated by an electro-oxidation of titanium sheet through an electrochemical anodization process in an aqueous solution containing ammonium fluoride, phosphoric acid and ethylene glycol. The polypyrrole–titania nanotube hybrid is then prepared by electrodepositing the conducting polypyrrole into well-aligned titania nanotubes through a normal pulse voltammetry deposition process in an organic acetonitrile solution containing pyrrole monomer and lithium perchlorate. The morphology and microstructure of polypyrrole–titania nanotube hybrid are characterized by scanning electron microscopy, infrared spectroscopy and Raman spectroscopy. The electrochemical capacitance performance is determined by cyclic voltammetry and charge/discharge measurement. It indicates that the polypyrrole film can been uniformly deposited on both surfaces of titania nanotube walls, demonstrating a heterogeneous coaxial nanotube structure. The specific capacitance of polypyrrole–titania nanotube hybrid is determined to be 179?F?g^?1 based on the polypyrrole mass. The specific energy and specific power are 7.8?Wh?kg^?1 and 2.8?kW?kg^?1 at a constant charge/discharge current of 1.85?mA?cm^?2, respectively. The retained specific capacitance still keeps 85% of the initial capacity even after 200 cycle numbers. This result demonstrates the satisfying stability and durability of PPy–TiO₂ nanotube hybrid electrode in a cyclic charge/discharge process. Such a composite electrode material with highly ordered and coaxial nanotube hybrid structure can contribute high energy storage for supercapacitor applications.     

多孔氧化铝有序膜的制备研究

本文用阳极氧化法分别在硫酸和草酸电解液中成功制备出高度有序、具有纳米级孔洞的氧化铝有序阵列模板。采用饱和HgCl₂去除Al基体后,得到典型六方形结构的多孔Al₂O₃有序膜。通过改变氧化电压、氧化时间等条件使模板的孔径、孔深可调、膜厚度可控,并系统研究了对模板有序性、孔径、膜厚度等的影响因素,总结出制备Al₂O₃有序膜的最佳工艺。     

钴离子（Co（2＋））掺杂TiO2纳米管阵列的光生阴极保护行为

应用电化学阳极氧化法在纯钛箔表面构筑TiO2纳米管阵列膜,借助离子交换法对纳米管阵列膜作钴离子（Co2＋）掺杂.扫描电子显微镜（SEM）、X-射线衍射（XRD）观察膜层的形貌和晶型,紫外-可见吸收光谱（UV-Vis）、光电化学分别测试Co2＋掺杂TiO2纳米管阵列在不同波长范围内的光电响应特性和光生阴极保护行为,考察C...     

单分散聚苯乙烯乳胶有序膜在二氧化硅多孔材料制备中的模板作用

自然界中许多物质经千万年发展进化,具有特殊结构,决定了它们具有奇异特性.人们对此过程非常关注,试图了解其结构性能关系,从而实现人工合成,仿生学应此而产生.比如天然蛋白石能呈现出鲜艳颜色,其原因在于单分散二氧化硅微球与具有选择性吸收光的某些金属氧化物微粒形成了有序的超晶格结构[1].为了模拟此过程,人们以单分散二氧化硅或聚苯乙烯微粒形成的胶体晶作为模板,实现蛋白石的人工合成[2].可以说,模板合成技术是制备有序材料的有效手段.本文以单分散聚苯乙烯乳胶室温形成的有序膜为模板,采用快速溶胶凝胶方法,制备了聚苯乙烯/二氧化硅…     

TiO2 nanotubes fabricated by electrochemical anodization in molten o-H3PO4-based electrolyte: Properties and applications

Self-organized TiO₂ nanotubes (NTs) can be formed by electrochemical anodization. Anodization is generally performed in aqueous or organic electrolytes containing halogen ions, such as Cl⁻ and F⁻. However, these electrolytes lead to less ordered structures or carbon remnants, thus suppressing the electrical properties and limiting the applications. To overcome these limitations, new anodization approaches were performed in carbon-free electrolyte-based electrolyte. In this review, we summarizes the short history of TiO₂ NTs, general mechanisms of growing NTs, properties, and applications of classic TiO₂ NTs. Then, a new-generation of anodization approach conducted in molten orhto-phosphoric acid is elucidated based on anodization parameters, concluding the optimized condition to form highly ordered TiO₂ NT arrays. Finally, the review addresses further modifications such as heat-treatment, noble metal deposition, thermal dewetting, and double anodization to enhance the optical and electrical properties for use in various applications.     

Photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant on highly smooth and ordered TiO2 nanotube arrays

The photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant were achieved on TiO₂ nanotube electrodes with double purposes of environmental protection and renewable energy production under illumination of simulated solar light. The TiO₂ nanotube arrays (TiO₂ NTs) were fabricated by a two-step anodization method. The TiO₂ NTs prepared in two-step anodization process (2-step TiO₂ NTs) showed much better surface smoothness and tube orderliness than TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). In the photoelectrochemical water splitting and simultaneous photoelectrocatalytic decomposition process, the 2-step TiO₂ NTs electrode showed both highest photo-conversion efficiency of 1.25% and effective photodecomposition efficiency with existing of methylene blue (MB) as sacrificial agent and as pollutant target. Those results implied that the highly ordered nanostructures provided direct pathway and uniform electric field distribution for effective charges transfer, as well as superior capabilities of light harvesting.     

Fabrication of highly ordered TiO2 nanotube arrays using an organic electrolyte

Anodization of titanium in a fluorinated dimethyl sulfoxide (DMSO) and ethanol mixture electrolyte is investigated. The prepared anodic film has a highly ordered nanotube-array surface architecture. Using a 20 V anodization potential (vs Pt) nanotube arrays having an inner diameter of 60 nm and 40 nm wall thickness are formed. The overall length of the nanotube arrays is controlled by the duration of the anodization, with nanotubes appearing only after approximately 48 h; a 72 h anodization results in a nanotube array approximately 2.3 mum in length. The photoelectrochemical response of the nanotube-array photoelectrodes is studied using a 1 M KOH solution under both UV and visible (AM 1.5) illumination. Enhanced photocurrent density is observed for samples obtained in the organic electrolyte, with an UV photoconversion efficiency of 10.7%.     

高度有序的二氧化钛纳米管阵列的制备及其光催化活性的研究

采用电化学阳极氧化法在钛表面构筑了一种结构有序、微米级的TiO₂纳米管阵列膜层. 考察了制备电压、氧化时间、溶液搅拌等实验参数对TiO₂纳米管阵列形貌和尺寸的影响. 应用SEM和XRD对膜层的形貌和晶型进行了分析和表征, 并通过TiO₂纳米管阵列膜对甲基橙的光催化降解, 研究了TiO₂纳米管阵列膜层结构与光催化活性的关系. 结果表明: 阳极电压和溶液搅拌对制备TiO₂纳米管阵列的结构起到关键的作用. 控制20 V电压制备的TiO₂纳米管阵列膜, 管长达2.6～3.3 μm, 经500 ℃热处理后具有最高的光催化活性, 其光催化性能明显优于一般的TiO₂纳米颗粒膜.     

低频交流电沉积金纳米线阵列的AFM研究

迄今,人们已采用许多方法制备纳米材料,如刻蚀技术、化学法和模板法等［1]．其中,引起科学界广泛兴趣的模板法,在合成有序纳米材料上占有极其重要的地位．常用的模板有两种,一种是有序孔洞阳极氧化铝（Anodic Aluminum Oxide,AAO）模板[2],另一种是含有孔洞无序分布的高分子模板．AAO模板具有耐高温,绝缘性好,孔洞分布均匀有序,而且大小可控等特点［3]．可以利用 AAO模板来制备各种纳米纤维和纳米管,如导电聚合物［4]、金属［5]、半导体［6]、碳［7]和其它一些材料．由于纳米材料的应用具有广阔的前景,如光催化、电化学、酶固定等方面,因而不同材料纳米线的制备备受关     

Characterization of TiO2 nanotube arrays prepared via anodization of titanium films deposited by DC magnetron sputtering

Highly ordered TiO₂ nanotube arrays were fabricated on a conducting glass substrate in NH₄HF₂/glycol electrolyte via anodization of titanium film which was deposited by direct current magnetron sputtering (DCMS) at different temperatures. The results showed that Ti films with good homogeneity and high denseness could be formed under the conditions Ar pressure 0.35 Pa, direct current 3.5 A, and 2 h at 300 °C. Characterization of the TiO₂ nanotube arrays was investigated comparatively, by altering anodization time. The surface morphology of the samples changed as the anodization time was prolonged from 10 to 150 min at 30 V. The TiO₂ thin film was amorphous and could be transformed into anatase by annealing at 450 °C. On the basis of UV?Cvisible transmission spectra the bandgap of the thin film was calculated to be 3.12 eV, and its tail extended to 2.6 eV.     

TiO2纳米管阵列光电催化氧化处理氨氮废水

用电化学阳极氧化法制备了高度有序的钛基二氧化钛纳米管阵列薄膜。用场发射扫描电镜(FE-SEM)、X射线衍射(XRD)表征样品的形貌与晶型特征。以二氧化钛纳米管阵列为光阳极,石墨为对电极,测试了不同pH值和外加偏压条件下的光电流响应和光电催化氧化降解NH4Cl水溶液(以N计,100 mg·L-1)的效率。结果表明:所制备的TiO2纳米管阵列具有锐钛矿和金红石的混晶结构,且主要晶型为锐钛矿。光电流响应的强弱与光电催化氧化效率的高低相对应,降解氨氮废水的最佳条件为pH=11,偏压为1.0 V。     

Ideally ordered porous TiO2 prepared by anodization of pretextured Ti by nanoimprinting process

Ideally ordered anodic porous TiO₂ was fabricated through the pretexturing of Ti by nanoimprinting using a metal mold with an ordered array of convexes. The shallow concaves prepared by nanoimprinting acted as initiation sites for hole development during the subsequent anodization and generated ideally hexagonally ordered porous or nanotubular TiO₂. The hole interval of the ideally ordered TiO₂ could be controlled by changing the pretexturing pattern. This process is a key step towards the preparation of various types of functional devices requiring ideally ordered defect-free hole or pore arrangements.     

高钛含量钛硅中孔材料的合成及理化性质研究

通过单独水解混合成胶在静态条件下采用水热晶化及水热后处理,在模版剂用量较低和n(Ti)/n(Si)高达1/4的条件下合成了钛硅中孔材料.XRD、FT-IR、UV-Vis DRS和催化选择氧化反应表征结果表明,新合成方法有效防止了成胶过程在高钛含量下产生不溶性钛硅物种,合成产物呈高度有序的MCM-41六方结构,并具有较高的热稳定性和催化选择氧化反应活性.四丁基氢氧化铵在成胶过程不仅有利于钛形成稳定的可溶性物种从而提高其利用率,同时还促进孔墙内基本结构单元的交联和有序化.     

复合模板剂下有序介孔TiO2的制备研究

在复合模板剂聚氧乙烯十二烷基醚(Brij35）和聚乙二醇（PEG)下，制备出有序介孔TiO2.用XRD、HRTEM、SEM、FT-IR和N2吸附脱附等方法进行表征；并通过对反应过程中电导率和粘度的连续监测，分析有序介孔TiO2形成过程.研究表明,介孔TiO2为规整的六方排列结构，在低于400 ℃焙烧，有序结构稳定性高，比表面积达252 m2•g－1，孔径3.4 nm，晶型为锐钛矿；经500 ℃焙烧，有序介孔结构破坏，并开始出现金红石型晶相.有序介孔TiO2形成过程是基于在高极性介质中非极性的碳氢链聚集成为胶束，同时钛酸丁酯（TBOT）在已形成的胶束上聚集，在酸作用下不断水解缩聚而形成有序介孔结构，有效控制水解和聚合过程是控制介孔材料结构形成的关键.     

含氯离子电解液中二氧化钛纳米管的阳极氧化形成机理及应用

采用电化学阳极氧化的方法,以氯化铵(NH₄Cl)水溶液为电解液,在纯钛表面制备了二氧化钛(TiO₂)纳米管。考察了制备电压、氧化时间、Cl^-浓度和钛基体的退火处理对阳极氧化过程的影响规律,探讨了在含氯离子电解液中纳米管的形成机理,并基于上述含氯离子电解液中纳米管形成机制,通过两步阳极氧化法得到无支撑纳米管薄膜。