铝基阳极氧化铝模板水热法制备TiO2纳米管阵列

在(NH4)2TiF6的水溶液中,以铝基阳极氧化铝为模板,采用水热法制备了TiO2纳米管阵列. 使用场发射扫描电镜和X射线衍射对水热合成产物进行了表征. 实验结果表明,水热处理所得TiO2纳米管阵列具有特殊的形貌,其表面为连续的多孔状,断面为不连续、相互分离的管状;管口和管壁分别由平均粒度约45和25 nm的微细TiO2颗粒紧密堆积而成. 采用本方法制备的TiO2纳米管阵列无需热处理便已具有明显的锐钛矿型晶相特征.     

Nanotube formation from a sodium titanate powder via low-temperature acid treatment

Through structure-monitoring of nanotube formation from a lamellar sodium titanate, the present work explicitly elucidated the structure of the titanate nanotubes obtained from hydrothermal treatment of TiO(2) with NaOH. A new compound of an orthorhombic lepidocrocite-type sodium titanate was synthesized from calcination of a solid-state mixture of TiO(2) anatase and Na(2)CO(3) powders followed by hydrothermal treatment with NaOH. By treating with acid at 25 degrees C for Na(+) exchange with H(3)O(+), the titanate compound exfoliated and then proceeded with sheet-scrolling to form nanotubes, which had a structure and morphology very close to those of the nanotubes derived from NaOH treatment on TiO(2). During the low-temperature acid treatment, the lepidocrocite-type titanate is transformed from the orthorhombic C-base-centered symmetry to the body-centered symmetry. This transformation, accompanied by a size-contraction of TiO(6)-octahedron units, was critical for the formation of nanotubes. The present work provides direct evidence, for the first time, that the widely reported TiO(2)-derived titanate nanotubes can be obtained at low temperatures by scrolling the sheets exfoliated from the orthorhombic lepidocrocite-type titanate.     

Ellipsoidal TiO2 hierarchitectures with enhanced photovoltaic performance

Hierarchical TiO(2) ellipsoids 250-500 nm in size have been synthesized on a large scale by a template-free hydrothermal route. The submicrometer-sized hierarchitectures are assembled from highly crystallized anatase nanorods about 17 nm in diameter with macroporous cavities on the outer shells. Based on the time-dependent morphological evolution under hydrothermal conditions, an oriented attachment process is proposed to explain formation of the hierarchical structures. Such hierarchical TiO(2) not only adsorbs large amounts of dye molecules due to high surface area, but also shows good light scattering caused by the submicrometer size. The TiO(2) hierarchitectures were deposited on top of a transparent TiO(2) nanocrystalline main layer to construct a double-layered photoanode for dye-sensitized solar cell (DSC) application, exhibiting enhanced light harvesting and power-conversion efficiency compared to a commercial TiO(2)-based electrode.     

Hydrothermal synthesis and characterization of nanorods of various titanates and titanium dioxide

The formation process of titania based nanorods during hydrothermal synthesis starting from an amorphous TiO2.nH2O gel has been investigated. Sodium tri-titanate (Na2Ti3O7) particles with a rodlike morphology were prepared by a simple hydrothermal process in the presence of a concentrated NaOH aqueous solution. The ion exchange reaction of the synthesized Na2Ti3O7 nanorods with HCl under ultrasonic treatment promotes a complete sodium substitution and the formation of H2Ti3O7 nanorods. Low-temperature annealing of the as-produced nanorods of Na2Ti3O7 and H2Ti3O7 leads to a loss of the layered crystal structure and the formation of nanorods of condensed framework phases-sodium hexa-titanate (Na2Ti6O13) and metastable TiO2-B phases, respectively. These transformations proceed without a significant change in particle morphology. The nanostructures were investigated by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, thermogravimetric analysis (TGA), and Raman spectroscopy. The structural defects of the synthesized nanorods were investigated by high-resolution electron microscopy. The presence of planar defects can be attributed to the exfoliation of the zigzag ribbon layers into two-dimensional titanates as well as to the condensation of the layers of TiO6 octahedra into three-dimensional frameworks.     

Facile fabrication of anatase TiO2 microspheres on solid substrates and surface crystal facet transformation from {001} to {101}

Anatase TiO(2) microspheres with controlled surface morphologies and exposed crystal facets were directly synthesized on metal titanium foil substrates by means of a facile, one-pot hydrothermal method without use of any templating reagent. The obtained products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelecron spectroscopy (XPS), and the focused ion beam (FIB) technique. The sizes of the resultant microspheres ranged from 1.1 to 2.1 μm. The transformation of anatase TiO(2) microspheres with exposed {001} facets surface to nanosheets surface with {101} facets was achieved by simply controlling the hydrothermal reaction time. The anatase TiO(2) microspheres with exposed square-shaped plane {001} facets were obtained by controlling the reaction time at 1 h. The prolonged reaction time transforms the anatase TiO(2) microspheres with exposed square-shaped plane {001} facets to eroded {001} facets then to a nanosheet surface with exposed {101} facets. With hydrothermal synthesis, the surface morphological structure and crystal facets formation are highly dependent on dissolution/deposition processes, which can be strongly influenced by attributes, such as pH of the reaction media, the total concentration of dissolved and suspended titanium species, and the concentration of fluoride in the reaction solution. The changes of these attributes during the hydrothermal process were therefore measured and used to illustrate the morphology and crystal-facet transformation processes of anatase TiO(2) microspheres. The surface morphologies and crystal-facet transformations during hydrothermal processes were found to be governed by the compositional changes of the reaction media, driven by dynamically shifted dissolution/deposition equilibria. The photocatalytic activities of the photoanodes made of anatase TiO(2) microspheres were evaluated. The experimental results demonstrated that the photocatalytic activity of anatase TiO(2) microspheres with exposed {001} facets was found to be 1.5 times higher than that of the anatase TiO(2) microspheres with exposed {101} facets.     

Sol-gel synthesis and morphological control of nanocrystalline TiO(2) via urea treatment

Nanocrystalline TiO(2) rods and hollow tubes with an engraved pattern on the surface have been prepared by a novel anionic template-assisted sol-gel synthesis via urea treatment and under hydrothermal condition. X-ray diffractometry (XRD) results indicate that these nanocrystallines consist predominantly of anatase TiO(2), with minor amounts of rutile and brookite. Scanning and transmission electron microscopy (SEM and TEM) analyses reveal these rods and hollow tubes may result from the aggregates of nanorods of approximately 10 nm in diameter. The crystallographic faceting found from TEM further reveals the polymorphic nature of the nanocrystalline TiO(2) thus prepared. A "reverse micelle" formation mechanism taking into account the hydrothermal temperature, the pH effect of the sol-gel system, the isoelectric point, the formation of micelles, and the electrostatic interaction between the anionic surfactant and the growing TiO(2) particulates is proposed to illustrate the competition between the physical micelle assembly of the ionic surfactants and the chemical hydrolysis and condensation reactions of the Ti precursors.     

Simultaneous phase- and size-controlled synthesis of TiO(2) nanorods via non-hydrolytic sol-gel reaction of syringe pump delivered precursors

The simultaneous phase- and size-controlled synthesis of TiO(2) nanorods was achieved via the non-hydrolytic sol-gel reaction of continuously delivered two titanium precursors using two separate syringe pumps. As the injection rate was decreased, the length of the TiO(2) nanorods was increased and their crystalline phase was simultaneously transformed from anatase to rutile. When the reaction was performed by injecting titanium precursors contained in two separate syringes into a hot oleylamine surfactant solution with an injection rate of 30 mL/h, anatase TiO(2) nanorods with dimensions of 6 nm (thickness) x 50 nm (length) were produced. When the injection rate was decreased to 2.5 mL/h, star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 200 nm and a small fraction of rod-shaped anatase TiO(2) nanorods with dimensions of 9 nm x 100 nm were synthesized. Pure star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 450 nm were synthesized when the injection rate was further decreased to 1.25 mL/h. The simultaneous phase transformation and length elongation of the TiO(2) nanorods were achieved. Under optimized reaction conditions, as much as 3.5 g of TiO(2) nanorods were produced. The TiO(2) nanorods were used to produce dye-sensitized solar cells, and the photoconversion efficiency of the mixture composed of star-shaped rutile TiO(2) nanorods and a small fraction of anatase nanorods were comparable to that of Degussa P-25.     

TiO2-MoO3复合纳米管阵列薄膜的制备及其可见光活性

通过阳极氧化的方法制备TiO₂纳米管薄膜, 在MoO₃存在的条件下对该薄膜进行热处理得到TiO₂-MoO₃复合纳米管阵列薄膜. 利用X射线衍射(XRD), 扫描电子显微镜(SEM), X射线光电子能谱(XPS), 电化学阻抗谱(EIS), Mott-Schottky 及光电化学方法对得到的薄膜进行了表征. XRD结果表明, TiO₂-MoO₃复合纳米管薄膜中的TiO₂主要为锐钛矿晶型. SEM实验证实了薄膜纳米管结构的存在, 样品中的MoO₃均匀地分散在TiO₂纳米管表面. 利用XPS方法分析了TiO₂-MoO₃复合纳米管薄膜元素的组成, 结果表明, MoO₃在TiO₂表面形成TiO₂-MoO₃复合纳米管薄膜. 研究了热处理温度以及热处理时间对样品的光电化学性能的影响, 相对于单纯TiO₂纳米管薄膜, 适量引入MoO₃提高了样品在可见光区的光电响应能力, 样品的平带电位负移. 在450 °C热处理60 min制得的TiO₂-MoO₃复合半导体纳米管阵列薄膜光电响应活性最高.     

Dye-sensitized solar cells based on a single-crystalline TiO2 nanorod film

Highly crystalline TiO2 nanorods with lengths of 100-300 nm and diameters of 20-30 nm have been synthesized by a hydrothermal process in a cetyltrimethylammonium bromide surfactant solution. The microstructure measured by X-ray diffraction and high-resolution transmission electron microscopy was a pure highly crystalline anatase phase with a long nanorod shape. The addition of a triblock copolymer poly(ethylene oxide)100-poly(propylene oxide) 65-poly(ethylene oxide)100 (F127) decreased the length of the nanorods and kept the rod shape of the particles even after sintering at high temperatures. The rod shape kept under high calcination temperatures contributed to the achievement of the high conversion efficiency of light-to-electricity as discussed in the paper. A high conversion efficiency of light-to-electricity of 7.29% was obtained with the TiO2 single-crystalline anatase nanorod cell.     

Single nanocrystals of anatase-type TiO2 prepared from layered titanate nanosheets: formation mechanism and characterization of surface properties

Anatase-type TiO2 single nanocrystals with boatlike, comblike, sheetlike, leaflike, quadrate, rhombic, and wirelike particle morphologies were prepared by hydrothermal treatment of a layered titanate nanosheet colloidal solution. The formation reactions and surface properties of the TiO2 nanocrystals were investigated using XRD, TEM, TG-DTA analyses, and measurements of BET specific surface area, photocatalytic activity, and ruthenium dye (N719) adsorption. The crystal morphology can be controlled by reaction temperature, pH value of reaction solution, and exfoliating agent. The titanate nanosheets were transformed to the TiO2 nanocrystals by two types of reactions. One is an in situ topotactic structural transformation reaction, and the other is a dissolution-deposition reaction on the surface. The anatase nanocrystals formed by the in situ topotactic structural transformation reaction retain the sheetlike particle morphology of the precursor, and they preferentially expose the (010) plane of anatase structure. The crystal surface of anatase nanocrystals prepared in this study showed higher photocatalytic activity and higher ruthenium dye adsorption capacity than did the Ishihara ST-01 sample, a standard anatase nanocrystal sample. The results indicated the (010) plane of the anatase structure has high photocatalytic activity and high ruthenium dye adsorption ability.     

Synthesis of uniform anatase TiO2 nanoparticles by the gel-sol method 2. Adsorption of OH- Ions to Ti(OH)4 gel and TiO2 particles

The pH value in the gel-sol system for the preparation of uniform anatase TiO2 nanoparticles, as a decisive factor for controlling the size and shape of the final product, was found to be significantly changed during the formation process of the anatase TiO2 particles from a condensed Ti(OH)4 gel. The dramatic evolution of pH with the progress of the synthetic process has clearly been explained in terms of the adsorption and desorption of a hydroxide ion (OH-) ora proton (H+) on the solids transforming with time. The adsorption and desorption of OH- or H+ were enhanced by the presence of an inert electrolyte such as NaClO4, as explained by its shielding effect on the electrical interactions between the electrically charged precipitates and free OH- and H+ ions. The electrolyte also hampered the phase transformation of Ti(OH)4 precipitate to anatase TiO2. This effect of electrolytes was explained in terms of the inhibited nucleation of anatase TiO2 by enhanced adsorption of OH- ions toTiO2 embryos. The points of zero charge (PZC) of the amorphous Ti(OH)4 precipitate and the anatase TiO2 particles at 25 degrees C were obtained from the change in pH associated with the adsorption and desorption of OH- or H+, i.e., 4.6 for Ti(OH)4 precipitate and 6.0 for anatase TiO2 in the presence of 0.1 mol dm(-3) NaClO4. The PZCof the Ti(OH)4 precipitate measured at 25 degrees C after additional aging at 100 degrees C for 30 min was shifted to 4.1, owing to the promoted adsorption of OH-.     

In situ preparation of weakly flocculated aqueous anatase suspensions by a hydrothermal technique

Weakly flocculated aqueous anatase suspensions were prepared in situ by hydrothermally treating amorphous titania particles peptized with different amounts of tetraethylammonium hydroxide (TENOH). The simultaneous formation of hydrous TiO2 polyanions in the presence of OH- and tetraethylammonium cations are two essential conditions for the peptization process to occur. The absence of either of these conditions will cause reprecipitation. Transmission electron microscopy (TEM) revealed that the morphology of the particles formed at low TENOH concentrations consisted of well-dispersed anatase crystals, changing to asterisk-like structured particles with increasing concentrations of TENOH. Because of the extremely high absolute zeta potential (over -70 mV in all the samples) and ionic strength values, nontouching particle networks may be formed in situ in the mother solution in all samples, as predicted by DLVO theory. A trend to coagulation was observed in the suspensions with increasing concentrations of TENOH due to a more pronounced secondary minimum in the particle pair potential curves. Assuming the particles remained in the secondary minimum throughout the hydrothermal treatment may lead to the formation of the asterisk-like hard agglomerates. This may arise from the condensation of the -OH-rich TiO2 particles or from the deposition of material in the interparticle gap during the particle growth process. The green packing density of slip-cast bodies from a suspension containing 20 wt% solids was around 46%.     

TiO2纳米薄片的合成及其光催化降解苯酚性能

以钛酸纳米管为前驱体,通过添加NaF高温水热合成了(001)面暴露的TiO₂纳米薄片,并对其催化苯酚光降解行为进行了研究。结果表明经水热反应后,钛酸型TiO₂纳米管(NT)转晶成锐钛矿型TiO₂纳米薄片(NS),且具有高(001)暴露面。和NT相比,NS对苯酚的光催化降解活性显著提高,其活性随水热温度升高而增加。NS光催化去除苯酚符合一级动力学,其中200 ℃合成的NS反应速率常数k最高,为0.083 min^-1。同时,苯酚的光催化反应初活性与其初浓度的关系符合Langmuir-Hinshelwood模型,表明苯酚的光催化降解受吸附控制。     

钛酸纳米管前驱体水热制备TiO2：水热媒介对结晶度及光催化活性的影响

以钛酸纳米管为先驱体,180℃24 h同一水热条件下,利用H2O、HNO3、KBF4以及HNO3+KBF4的4种水热媒介溶液,制备了高结晶度高光催化活性的TiO2,并研究了水热媒介对TiO2结晶度、表面羟基和光催化活性的影响。通过扫描电镜(SEM)、X射线衍射(XRD)、红外测试(FTIR)、X射线光电子能谱(XPS)、紫外可见漫反射吸收光谱(UV-Vis)进行了结构表征。光催化活性通过降解甲基橙溶液进行了评价。结果表明,与其他3种媒介相比,HNO3+KBF4溶液为水热媒介制备的锐钛矿晶型TiO2,结晶度高,表面羟基含量高,因此,呈现高的光催化活性。     

水热处理锐钛矿TiO2纳米管阵列及其增强的光电催化活性

在含氟溶液中,通过电化学阳极氧化钛片成功制备了高度有序的TiO2纳米管阵列,先在450℃下煅烧使其晶化为锐钛矿相,再在不同温度下水热处理了这些锐钛矿阵列。用XRD、SEM和XPS表征了所制备的样品。通过在氙灯光照下光电催化降解对氯苯酚水溶液来检测样品的活性。以对苯二甲酸作为探测分子,用荧光光谱检测了在氙灯光光照下样品表面产生的羟基自由基(.OH)。通过线性伏安扫描的间隙光照实验,测定了样品的光电流响应。结果表明后水热处理对锐钛矿TiO2纳米管阵列的结晶度和形貌没有影响,但光电催化活性明显增强,而不同温度处理的样品的活性差别不大。水热处理后的TiO2纳米管阵列的光电催化活性增强的原因是,水热后TiO2纳米管阵列表面羟基含量明显增加,使得其在光电催化过程中生成的.OH增加。     

TiO2纳米棒载Pd催化剂的制备及其对甲酸的电催化氧化

利用水热合成和无机溶胶法,分别制备了具有棒状(TiO2-R)和无规则结构(TiO2-I)的锐钛矿相TiO2,并以之为载体制备得到Pd/TiO2电催化剂.循环伏安测试显示,与无规则TiO2相比,具有棒状结构的TiO2载Pd催化剂对甲酸氧化的电催化性能提高了70%;计时电流测试显示,运行3000 s后,甲酸在棒状TiO2载Pd催化剂上的氧化电流是无规则TiO2载Pd催化剂的16倍.其原因可能与TiO2纳米棒拥有更好的电子传导性且表面拥有较多的活性含氧基团有关,从而能够有效提高催化剂对甲酸氧化的电催化活性和抗毒化性能.     

Modification of TiO2 for enhanced surface properties: finite Ostwald ripening by a microwave hydrothermal process

The effect of microwave modification of colloidal TiO2 suspensions under extended periods of treatment is presented. The nanoparticulate TiO2 is compared and contrasted to similar convection hydrothermally treated TiO2 and a commercial titania product, namely Degussa P25. Microwave-treated samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy to determine their physicochemical characteristics. Comparative surface area analyses were performed by N2 adsorption and calculated from a Brunauer-Emmett-Teller (BET) isotherm. The complementary techniques of XRD and TEM showed good correlation between observed and calculated particle sizes (by application of the Scherrer equation), with the material being highly crystalline anatase TiO2, as identified by XRD and Raman. This investigation identified that extended periods of microwave hydrothermal treatment do not greatly enhance the crystallinity and primary grain size. Treatment of >180 min has a negative effect on crystallite growth; however, treatment up to this time had a significant effect on the material's surface area. The limiting regime of Ostwald ripening for hydrothermal treatment is discussed in relation to the mechanism of microwave treatment, that is, rapid heating to temperature and extremely rapid rates of crystallization. The effect of these property modifications are further discussed in relation to photocatalytic and photoelectrochemical applications of TiO2 nanoparticles.     

Control over the hierarchical structure of titanate nanotube agglomerates

An alkaline hydrothermal treatment of several types of ordered macroporous TiO(2) structures, namely, microtubes, sea urchin shapes, and anodic nanotube arrays, has been investigated under stationary conditions. The effect of the size and geometry of these structures on the morphology of the forming hierarchical agglomerates of titanate nanotubes has been systematically studied. It has been revealed that, at sizes larger than the critical value (ca. 1 μm), the whole geometry of the initial ordered TiO(2) structure is maintained under reaction conditions leading to formation of hierarchical structures, in which bulk TiO(2) is replaced with titanate nanotube agglomerates. This principle provides a convenient route for the preparation of multiscale micro- and nanostructures of TiO(2) based materials. The analysis of critical size suggests that, under reaction conditions, due to the limited transport of dissolved Ti(IV) species, the growth of nanotubes occurs locally.     

氧化钛纳米管阵列制备及形成机理

采用电化学阳极氧化法在HF水溶液体系使纯钛表面形成一层结构规整有序的高密度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、时间、电解液浓度）对TiO2纳米管阵列形貌和尺寸的影响.结果表明,阳极氧化电压是影响氧化钛形貌和纳米管尺寸的最主要因素,而温度和电解液浓度只影响TiO2纳米管阵列形成的时间.对TiO2纳米管阵列进行X射线衍射（XRD）和扫描电子显微镜（SEM）的分析,初步表征了TiO2纳米管阵列的电学性质.并讨论了TiO2纳米管的形成机理.     

Real time observation of the hydrothermal crystallization of barium titanate using in situ neutron powder diffraction.

The hydrothermal crystallization of barium titanate, BaTiO3, has been studied in situ by time-resolved powder neutron diffraction methods using the recently developed Oxford/ISIS hydrothermal cell. This technique has allowed the formation of the ferroelectric ceramic to be followed in a noninvasive manner in real time and under genuine reaction conditions. In a first set of experiments, Ba(OD)2-8D2O was reacted with two different titanium sources, either crystalline TiO2 (anatase) or amorphous TiO2-H2O in D2O, at 100-140 degrees C and the reaction studied using the POLARIS time-of-flight neutron powder diffractometer, at the ISIS Facility. In a second series of experiments, the reaction between barium chloride and crystalline TiO2 (anatase) in NaOD/D2O was studied at temperatures between 100 and 200 degrees C and at different deuterioxide concentrations using the constant-wavelength D20 neutron powder diffractometer at the Institut Laue Langevin. Quantitative growth and decay curves were determined from analysis of the integrated intensities of Bragg reflections of starting materials and product phases. In both sets of experiments the rapid dissolution of the barium source was observed, followed by dissolution of the titanium source before the onset of crystallization of barium titanate. Using a nucleation-growth model we are able to simulate the growth curve of barium titanate at three temperatures. Our results indicate the predominance of a homogeneous dissolution-precipitation mechanism for the hydrothermal formation of barium titanate, rather than other possible mechanisms that have been discussed in the literature. Analysis of the line widths of the Bragg reflections in the neutron diffraction data indicates that the particle size of the BaTiO3 product phase prepared from the amorphous TiO2-H2O is smaller than that prepared from crystalline TiO2 (anatase).