氧化钛纳米线阵列的溶胶凝胶模板合成与表征

采用二次阳极氧化工艺制备了高度规则排列的多孔氧化铝(PAA)模板,并利用模板法与溶胶-凝胶法结合的模板组装技术制备了氧化钛纳米线阵列,得到了直径在50nm左右,线间距约为50nm的纳米线阵列.研究了模板组装过程不同压力条件对溶胶向模板孔洞中填充度的影响,发现在一定的负压条件下,有利于PAA孔中气体的排出,得到高的溶胶填充度,进而制备出高质量的纳米线阵列.分别通过SEM及XRD技术表征了PAA模板及纳米线的形貌及相结构.SEM观察发现纳米线彼此平行,表面光洁,不存在龟裂,纳米线的长度和直径与所使用模板的厚度和直径一致,表明纳米线的生长受控于模板;XRD分析表明模板为单一的θ-Al2O3晶型,纳米线为锐钛矿型TiO2.

糖葫芦状氧化钛纳米线阵列的溶胶-电泳沉积及其形成机理

采用二次阳极氧化工艺制备了高度规则排列的多孔氧化铝(PAA)模板,并利用溶胶-电泳法在PAA模板中制备了糖葫芦状氧化钛纳米线阵列,对纳米线及PAA模板进行了SEM分析。结果表明,纳米线直径在75 nm左右,线间距约为100 nm,每根纳米线都具有周期性凹凸,形状与糖葫芦相似。结合胶体颗粒间的相互作用、胶体颗粒在电场作用下的运动、胶体聚沉理论及胶体颗粒的扩散行为等因素,建立了溶胶-电泳沉积的物理模型,阐明了糖葫芦状纳米线阵列的形成机理。

隧道结TiO_x线宽度对隧穿现象的影响

在新型超高速光导开关的研究中,采用AFM阳极氧化加工方法,加工利用磁控溅射方法在GaAs衬底得到的厚约3nm的钛膜,形成纳米级氧化钛线.该Ti-TiOx-Ti形成MIM隧道结作为光导开关的基本结构,并且TiOx作为电子的能量势垒.为说明氧化线的宽度对隧穿现象的影响,确定加工超高速光导开关时不引起隧穿的最窄线宽及其实验条件,通过控制空气中的相对湿度,在加工速度、氧气浓度和偏置电压不变的条件下,加工出宽度分别为15·6,34·2和46·9nm的钛氧化线,测试了不同宽度氧化线隧道结的I-V特性.结果表明,在两电极的偏压为6V时不引起隧穿的前提下,可以在超高速光导开关两电极间加工最小宽度大约为10nm的氧化钛线.

Distance-Dependent Long-Range Electron Transfer in Protein:a Case Study of Photosynthetic Bacterial Light-Harvesting Antenna Complex LH2 Assembled on TiO 2 Nanoparticle by Femto-Second Time-Resolved Spectroscopy

The function of protein in long-range biological electron transfer is a question of debate. We report some preliminary results in femtosecond spectroscopic study of photosynthetic bacterial light-harvesting antenna complex assembled onto TiO2 nanoparticle with an average size of 8 nm in diameter. Crystal structure shows that photosynthetic bacterial antenna complex LH2 has a ring-like structure composed by alpha- and beta-apoprotein helices. The alpha- and beta-transmembrance helices construct two concentric cylinders with pigments bacteriochlorophyll a (Bchl a) and carotenoid (Car) buried inside the protein. We attempt to insert TiO2 nanoparticle into the cavity of the inner cylindrical hollow of LH2 to investigate the nature of the electron transfer between the excited-state Bchl a and the TiO2 nanoparticle. A significant decrease in the ground state bleaching recovery time constant for Bchl a at 850 run (B850) in respect to that of the Bchl a in free LH2 has been observed. By using the relation of distance-dependent long-range electron transfer rate in protein, the distance between the donor B850 and the acceptor TiO2 nanoparticle has been estimated, which is about 0.6 nm. The proposed method of assembling proteins onto wide-gap semiconductor nanoparticle can be a promising way to determine the role of the protein playing in biological electron transfer processes.

Performance of V_2O_5-WO_3-MoO_3/TiO_2 Catalyst for Selective Catalytic Reduction of NO_x by NH_3

The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM） and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V ： W ： Mo ： TiO2 ： fiber glass = 1 ： 4.5 ： 4.5 ： 72 ： 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.

TiO_2 Thin Film UV Detectors Deposited by DC Reactive Magnetron Sputtering

Crystalline TiO2 thin films were prepared by DC reactive magnetron sputtering on indium-tin oxide（ITO） thin film deposited on quartz substrate, the photoconductive UV detector on TiO2 thin films was based on a sandwich structure of C/ TiO2/ITO. The measurement of the I-V characteristics for these devices shows good ohmic contact. The photoresponse of TiO2 thin films was analyzed at different bias voltage. The detector shows a good photoresponse with a rise time of 2 s and a fall time of 40 s, the photocurrent is linearly increased with the bias voltage.

Fabrication of SPES/Nano-TiO_2 Composite Ultrafiltration Membrane and Its Anti-fouling Mechanism

Membrane fouling is one of the major obstacles for reaching a high flux over a prolonged period of ultrafiltration（UF）process.In this study,a sulfonated-polyethersulfone（SPES）/nano-TiO2 composite UF membrane with good anti-fouling performance was fabricated by phase inversion and self-assembly methods.The TiO2 nanoparticle self-assembly on the SPES membrane surface was confirmed by X-ray photoelectron spectroscopy （XPS）and FT-IR spectrometer.The morphology and hydrophilicity were characterized by scanning electron microscopy（SEM）,atomic force microscopy（AFM）and contact angle goniometer,respectively.The anti-fouling mechanism of composite UF membrane was discussed through the analysis of the micro-structure and component of UF membrane surface.The results showed that the TiO2 content and the micro-structure of the composite UF membrane surface had great influence on the separation and anti-fouling performance.

Preparation of titanium powders by calciothermic reduction of titanium dioxide

To develop an effective process for titanium powders production, a calciothermic reduction process of pigment titanium dioxide （w（TiO2）〉98%）, based on the preform reduction process （PRP）, was investigated by means of XRD, SEM and EDS. In this process, the mixture of TiO2 powder and CaC12 was pressed into pieces as feed preform and was reduced by calcium vapor. Titanium powders was recovered after leaching from the reduced preform with hydrochloric acid and deionized water. The results indicate when the mass ratio of CaC12 to TiO2 is about 1：4 and at a constant temperature of 1 273 K for 6 h in vacuum furnace, titanium powders with 99.55% purity by EDS analysis and irregular shape （8-15 μm in particle size） are obtained.

Synthesis and electrochemical performance of TiO_2-B as anode material

TiO2-B was synthesized by solid-state reaction. The structures, surface morphologies and electrochemical performances of TiO2-B were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement, respectively. The effects of calcining temperature, molar ratio of K2O to TiO2 and calcining time on the characteristics of TiO2-B were investigated. The results show that the calcining time exerts a significant influence on the electrochemical performances of TiO2-B. The TiO2-B is obtained with good crystal structure and suitable size by using K2Ti4O9, which is prepared at 950 ℃for 24 h under the condition of x（K2O）/x（TiO2）=1：3.5. The TiO2-B delivers all initial discharge capacity of 231.6 mA.h/g. And the rate caoacitv is 73.2 mA-h/g at 1 675 mA/g, which suggests that TiO2-B is a promising anode material for the lithium ion batteries.

Preparation of hierarchical CuO@TiO_2 nanowire film and its application in photoelectrochemical water splitting

A new kind of self-standing CuO@TiO2 nanowires (NWs) film with hierarchical feature was prepared by a three-step protocol consisting of hydrothermal reaction, electroless plating, and branched growth processes. This heterostructured CuO@TiO2 NWs film demonstrates the favorable physical properties in the photoelectrochemical cell (PEC) water splitting, such as the hierarchical surface, the extended optical absorption range, and the rapid interface charge transfer kinetics. Under the illumination of the simulated solar light, the pristine TiO2 NWs film only attains a photocurrent density of 0.12 mA/cm2 at 1.0 V versus reversible hydrogen electrode (RHE). Significantly, the CuO@TiO2 NWs film can yield a dramatically increased photocurrent density of 0.56 mA/cm2 at the same applied voltage. Furthermore, amperometric I?t tests of the CuO@TiO2 NWs film reveal satisfactory stability. All the above characteristics of this heterostructured CuO@TiO2 NWs film indicate its great potential in the water splitting applications with solar visible light.

Optical and Structural Properties of Carbon Nanotube-Rutile Heterostructures

The paper presents a study of the growth and characterization of carbon nanotube-rutile nanocomposites. The heterostructures were obtained with a chemical mixing method. Scanning electron microscope images show that the samples appear as a homogeneous powder of rutile with carbon nanotubes intercalated in interspaces between the TiO2 grains. Characterization by both X-ray photoelectron spectroscopy and cathodo-luminescence analysis show the formation of CO-Ti chemical bonds with a decrease of 0.8 eV in the band gap compared to pure rutile. The consequence of this band gap modification is a strong change in optical properties. Luminescence emission is drastically reduced and absorption in the visible range is increased of about 6% at very low concentration （1%） of carbon nanotubes.

Reduction of Panzhihua titanium-bearing oxidized pellets by CO-N_2-H_2 gas

The effect of H_2 gas content on the reduction of Panzhihua titanomagnetite concentrate pellets by carbon monoxide was investigated by isothermal reduction experiment using CO-N_2-H_2 gas mixtures in a vertical electric resistance furnace.The morphology and phase transformation of reduced samples obtained were detected by scanning electron microscopy,energy disperse spectroscopy analysis and X-ray diffractometry respectively.The results show that increasing H_2 content will enhance the initial stage of reduction rate apparently.There are two reasons responsible for this effect,one is that H_2 accelerates the chemical reaction,and the other is that the addition of H_2 gas can improve the porosity of pellet intensively.It is noteworthy that this effect is more obvious when the reduction temperature reaches 1473 K with sticking phenomenon happening.There are no crystalline phases which can be found such as ulvospinle,ilmenite,ferrous-pseudobrookite and any titanium oxide except titanomagnetite(TTM).The reduction progress is suggested as follows:1) Fe_2O_3→Fe_3O_4→FeO→Fe;2) Fe_2TiO_5→Fe_2TiO_4+Fe_3O_4→TTM.Element Al migrates and gets enriched in high titanium content iron ores,and eventually Al to Ti molar ratio is 1:3.Al is likely to dissolve in titanium iron oxides to form a kind of composite iron compound,which results in the restrain of reduction.

Study of Properties of Lead Selenide （PbSe） Thin Films Deposited on TiO2

The study of nano properties of PbSe （lead selenide） thin films deposited on TiO2 semi conductor film prepared by sol gel method was a new work destined to perfect the nano materials used in photovoltaic energy. The growth of the first group of the fihns （Set 1： P（9）） ＆ P（14）） was based on the decomposition of lead citrate and sodium selenosulphite in the presence of sodium citrate and sodium hydroxide with ammonia and triethalamine （TEA） acting as the complexing agents and P.H stabilizers; while in the second group （Set 2： Pc15~）, the reaction bath was made up of solutions of lead nitrate Pb（NO3）2, PVA （polyvinyl alcohol）, H20 （distilled water）, NH3 （ammonia）, sodium selenosulphite （Na2SeSO3） and Triethalamine [N（CH2CH2OH）], which was used as the complexing agent. The deposited materials were identified by X-ray diffraction. In addition, nano optical and morphological investigations were also performed. The sample P9 has the lowest absorbance of about 0.3 nm in the ultra-violet region. It was found that there was a reduction in the optical absorbance as the wavelength increases. The optical band gap shows a range of 1.26-2.00 eV with sample PcIs~ having the lowest direct band gap.

纳米隧道结的制备和特性研究

结合对向靶直流磁控溅射技术、微电子光刻方法和原子力显微镜阳极氧化加工方法制备了实用的纳米钛-钛氧化线-钛隧道结,钛膜的厚度为3·02nm.钛氧化线的宽度为60·5nm,在室温下此隧道结的I-V曲线表现出明显的库仑阻塞效应.

Thermal expansion behaviors of Mn(Ⅱ)-pyridylbenzoate frameworks based on metal-carboxylate chains

Solvothermal reactions of MnCl2with pyridylbenzoic acids gave three-dimensional metal-carboxylate frameworks(MCFs),named MCF-34,MCF-43,and MCF-44,based on one-dimensional Mn-carboxylate chains.The crystal structure,stability,porosity,and framework flexibility of the new compound MCF-44 were studied in detail and compared with its analogs.Depending on their shapes and the bridging angles of the ligands,these compounds possess different network connectivities and porosities.Considering the pyridylbenzote ligands and Mn(II)ions as,respectively,3-and 6-connected nodes,they resemble either the anatase(ant)or rutile(rtl)polymorph of TiO2.Variable-temperature single-crystal X-ray diffraction studies revealed large thermal expansion coefficients for these compounds,which are probably related to the relatively flexible edge-sharing polyhedral structure of their Mn-carboxylate chains.Interestingly,the new compound MCF-44,with its highly porous rtl structure exhibits the largest thermal expansion coefficienct among the coordination polymers reported so far.

Sensitization of Hydrothermally Grown Single Crystalline TiO2 Nanowire Array with CdSeS Nanocrystals for Photovoltaic Applications

An oriented array of electron transporting nanowires, grown directly on a transparent conductor constitutes an optimal architecture for efficient photovoltaic applications. In addition, semiconductor nanocrystals can work as efficient light absorbers because of their tunable optical properties. In this paper, we use an oriented array of TiO2 nanowires grown directly on a transparent conductive electrode and subsequently sensitized with colloidally grown CdSeS nanocrystal quantum dots （QDs）, using an efficient bi-linker assisted methodology, to demonstrate photovoltaic cells. Upon excitation with light, exciton dissociation takes place at the nanowire-nanocrystal interface, after which, electrons are transported to the fluorine-doped tin oxide （FTO） electrode via single-crystalline TiO2 nanowire channels. We demonstrate that an ex situ ligand exchange of QDs followed by sensitization on oxygen-plasma treated TiO2 nanowires results in enhanced loading of QDs, as compared to the in situ ligand exchange approach. An array of 1μm long TiO2 nanowire sensitized with CdSeS nanocrystals exhibits photovoltaic effects with a short-circuit current of 2-3 mA/cm2, an open circuit voltage of 0.6-0.7 V and a fill factor of 52-5%, resulting in devices with efficiencies of up to 0.6%.

Preparation of dye-sensitized solar cells with high photocurrent and photovoltage by using mesoporous titanium dioxide particles as photoanode material

Several mesoporous TiO2 （MT） materials were synthesized under different conditions following a hydrothermal procedure using poly（ethylene-glycol）- block-poly（propylene-glycol）-block-poly（ethylene-glycol） （P123） as the template and titanium isopropoxide as the titanium source. The molar ratios of Ti/P123, and the pH values of the reaction solution in an autoclave were investigated. Various techniques such as Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, laser Raman spectrometry （LRS）, scanning electron microscopy （SEM）, and high-resolution transmission electron microscopy （HRTEM） were used to characterize the products. Then, these materials were assembled into dye-sensitized solar cells （DSSCs）. Analysis of the J-V curves and electrochemical impedance spectroscopy （EIS） were applied to characterize the cells. The results indicated that the specific surface area and crystalline structure of these materials provide the possibility of high photocurrent for the cells, and that the structural characteristics of the specimens led to increased electron transfer resistance of the cells, which was beneficial for the improvement of the photovoltage of the DSSCs. The highest photoelectric conversion efficiency of the cells involving MT materials reached 8.33%, which, compared with that of P25- based solar cell （5.88%）, increased by 41.7%.