Photocatalytic effect of nature and modified V-bearing rutile

A natural rutile TiO2, which displays photocatalysis on degrading halohydrocarbon pollutants, was reported. The rutile contains up to 1.22% V2O5 (weight percent). Substitutions of Ti by V, as well as Fe, Cu and Zn, result in lattice distortions and defects. Grinding, heating and quenching modify the surface characteristics of ruffle, and consequently increase its photoactivity. It is found that the heating and quenching treatments enhance visible-light absorption of ruffle, especially at 1000 and 1100℃. Ground rutile is effective to degrade tetrachloroethylene and trichloroethylene. While, heating at 1000℃, and quenching at 1000 and 1100℃ distinctly improve degradation rate of samples. The special properties of the natural rutile have particular capabilities in photocatalytic oxidation, especially in degradation of halohydrocarbons.     

Al掺杂TiO_2的制备及酸化处理对其光催化活性的影响

锐钛矿相TiO2的光催化活性高于金红石相。采用化学溶液分解法制备了Al掺杂锐钛矿TiO2,并用硝酸对其进行酸化处理。利用TG-DTA、XRD、FTIR、BET和UV-vis等手段对样品进行了表征,通过对甲基橙的降解分析了酸化处理对Al掺杂TiO2光催化活性的影响。结果表明:掺杂Al能有效抑制TiO2由锐钛矿向金红石转变。酸化处理因能增大Al掺杂TiO2的比表面积而使其光催化活性提高。Al/Ti掺杂比为1∶4的样品在酸化处理后具有的光催化活性最高,60min后对甲基橙的降解达到100%。     

Effect of hydrolysis conditions on hydrous TiO2 polymorphs precipitated from a titanyl sulfate and sulfuric acid solution

The relationship between hydrolysis conditions and hydrous titania polymorphs obtained in a titanyl sulfate and sulfuric acid solution was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The results revealed that the feeding rate of the titanyl sulfate stock solution, the concentration of sulfuric acid, and the seed dosage of rutile crystal could significantly affect the hydrolysis rate, thus influencing the titania crystal phase. Hydrous TiO₂ in the form of rutile, anatase, or the mixture of both could be obtained in solutions of low titanium concentrations and 2.5wt% to 15wt% sulfuric acid at 100°C. When the hydrolysis rate of titanium expressed by TiO₂ was more than or equal to 0.04 g/(L·min), the hydrolysate was almost phase-pure anatase, while the main phase state was rutile when the hydrolysis rate was less than or equal to 0.01 g/(L·min). With the hydrolysis rate between 0.02 and 0.03 g/(L·min), the hydrolysate contained almost equal magnitude of rutile and anatase. It seems that although rutile phase is thermodynamically stable in very acidic solutions, anatase is a kinetically stable phase.     

High-pressure polymorph of TiO2-II from the Xiuyan crater of China

Abundant TiO2-II, a high-pressure polymorph of titanium dioxide, was found in the gneiss fragments of impact-produced breccias from the Xiuyan crater. Rutile in the gneiss was severely fragmented and fine-grained clasts less than 2 ~tm in size had been transformed to TiO2-II. Irregular thin layered TiO2-II is also observed in coarse-grained ruffle fragments, where the TiO2-II layers distributes along fractures and cracks in rutile, About 30 percent of rutile in the gneiss had been transformed to TiO2-II. Fine grains of TiO2-II display light bluish grey to light yellow brown in plane-polarized reflected light. Crystallographic investigation shows that TiO2-II has an orthorhombic structure with space group Pbcn. The cell parameters are a=4.543（1）/~, b=5.491（9）/~ and c=4.895（2） ,~. Its empirical formula calculated on the basis of two oxygen atoms can be written as （Tio.985Feo.oosNbo.oor- Si0.003Zr0.0Ol）l.0O302, or simply formula TiO2. According to the shock effects of quartz and feldspars, the peak shock pressure and post-shock temperature in the TiO2-II-bearing gneiss are estimated to be between 35 and 43 GPa and 300-900~C, respectively. The finding of TiO2-II in the shock-metamorphosed gneiss provides another mineral physics evidence for shock origin of the Xiuyan crater.     

Environmentally-friendly harvesting TiO2 nanospheres and V2O5 microrods from spent selective catalytic reduction catalysts

Spent selective catalytic reduction(SCR) catalysts are defined as hazardous wastes because of the toxicity of V₂O₅ to the ecological environment. Recycling of V₂O₅ and TiO₂ from the spent SCR catalysts has strikingly social and environmental benefits as well as economic values. In this work, a “NaOH + Na₂CO₃” system was employed to recycle 99.2% of anatase/rutile TiO₂ nanospheres with a nanospherical morpholo...     

Au@SiO2 core/shell nanoparticle-decorated TiO2 nanorod arrays for enhanced photoelectrochemical water splitting

To improve the separation efficiency of photoinduced charge carries,Au@SiO2nanoparticles(NPs)with core–shell structure were loaded onto the surface of TiO2nanorods grown on fluorine-doped tin oxide substrate by a facile two-step process.The resulted Au@SiO2/TiO2photoanodes were characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,as well as photoelectrochemical measurements.Compared with pristine TiO2nanorod film,the Au@SiO2/TiO2films showed remarkable enhancement in photoelectrochemical water splitting,with incident photonto-current conversion efficiency increasing from 31%to37%at 380 nm at 0.7 V versus saturated calomel electrode.This could be interpreted by the effect of metallic surface plasmon resonance of Au@SiO2NPs,which would generate an intense electromagnetic field with spatially nonhomogenous distributed intensity.As a result,the charge carriers generated in the near-surface region of TiO2nanorods could be easily separated.This modification method based on the effect of metallic surface plasmon resonance for promoted charge carrier separation provides a promising way to develop semiconductor photoelectrodes with high solar water-splitting performance.     

TiO2/SiO2/GQDs双层增透膜的制备及其在太阳能板中的应用

采用溶胶-凝胶法制备了SiO₂ 和TiO₂ 纳米溶胶,采用水热法制备了石墨烯量子点（graphene quantum dots,GQDs）。为进一步提高光伏太阳能板的透光率,设计了一种TiO₂/SiO₂/GQDs双层增透膜结构。探究了薄膜的结构、自清洁性能和增透性能,并进一步讨论了GQDs在增透性中的作用。结果表明,SiO₂-TiO₂/TiO₂-GQDs结构的双层薄膜厚度为120 nm时,太阳能板上的光透过率由未涂敷的85%增加至95%。接触角实验和室外耐环境性能实验测试表明,复合膜层接触角为10°,并具有良好的亲水性和耐环境性能。此外,户外实验结果表明,涂覆该薄膜的太阳能电板发电效率提高6%。由此说明双层增透膜可有效地提高太阳能电池板的光能利用率和使用寿命,可高效地利用太阳能。     

Improved and excellent CO sensing properties of Cu-doped TiO<Subscript>2</Subscript> nanofibers

Cu-doped TiO2 nanofibers with an average diameter of about 80 nm are synthesized through an electrospinning method. Both anatase and rutile crystallographic structures are found in the fibers based on XRD results. Compared with pure TiO2 nanofibers, the Cu-doped TiO2 nanofibers exhibit improved CO sensing properties at 300°C. The sensitivity of Cu-doped TiO2 nanofibers is up to 3 when the sensor is exposed to 5 ppm CO, and the response and recovery times are about 4 and 8 s, respectively. Good selectivity i...     

金红石相纳米二氧化钛的制备

报道了一种制备金红石相纳米二氧化钛的新方法.即以四氯化钛作为原料,通过加入特殊的有机添加剂,利用简单的水解法,在较低温度下制备了金红石相纳米二氧化钛粒子.利用X-射线衍射(XRD)、场发射扫描电镜(FE SEM)及热重 差热(TG DTA)分析等方法对产物的形貌以及添加剂的用量和煅烧温度对产物晶相和粒径的影响进行了研究.结果表明,添加剂的用量对二氧化钛产物中金红石相的含量有显著影响,当添加剂的用量为0.5 g/mL水时可直接水解得到完全的金红石相;经过400 ℃的煅烧,即可得到结晶良好的金红石相纳米二氧化钛球形粒子,晶粒径约为40~50 nm.     

自由基抑制剂对不同晶型TiO2光催化反应的影响

以荧光光谱法研究了不同晶型 TiO₂ 的光催化反应体系中羟基自由基(·OH)的产生情况,表明在H₂O₂存在条件下,金红石型 TiO₂ 经可见光激发可持续稳定产生·OH,而以锐钛矿型 TiO₂ 作光催化剂时,则检测不到·OH的生成。光催化结果表明,在H₂O₂存在条件下,苯酚可被 TiO₂ 可见光催化降解;往反应体系加入自由基抑制剂(叔丁醇或甲醇)时,明显降低了金红石型 TiO₂ 的降解效率,但对锐钛矿型 TiO₂ 的影响较弱。以金红石型 TiO₂ 作光催化剂时,苯酚的降解反应主要发生在溶液中;而以锐钛矿型 TiO₂ 作光催化剂时,则苯酚的降解反应主要发生在催化剂的表面。     

Preparation and performance of dye-sensitized solar cells based on ZnO-modified TiO<Subscript>2</Subscript> electrodes

The ZnO-modified TiO₂ electrode was prepared by adding Zn(CH₃COO)₂·2H₂O to the TiO₂ colloid during the sol-gel production process, and was used in dye-sensitized solar cells (DSCs). The open circuit voltage (V _OC) and fill factor (ff) of the cells were improved significantly. The performances of the ZnO-modified TiO₂ electrode such as dark current, transient photocurrent, impedance, absorption spectra, and flat band potential (V _fb) were investigated. It is found that the interface charge recombination impedance increases and V _fb shifts about 200 mV toward the cathodic potential. The effect mechanism of ZnO modification on the performance of DSCs may be that ZnO occupies the surface states of the TiO₂ film.     

Effect of thermal oxidation on the surface characteristics and corrosion behavior of a Ta-implanted Ti-50.6Ni shape memory alloy

A NiTi shape memory alloy (SMA) modified by Ta ion implantation was subjected to oxidation treatment in air at 723 and 873 K. Atomic force microscopy (AFM), Auger electron spectroscopy (AES), and grazing incidence X-ray diffraction (GIXRD) measurements were conducted to investigate the surface characteristics, including surface topography, elemental depth profiles, and surface phase structures. The surface roughness of the Ta-implanted NiTi increases after oxidation, and the higher the oxidation temperature is, the larger the value is. The surface of the Ta-implanted NiTi oxidized at 723 K is a nanolayer mainly composed of TiO₂/Ta₂O₅ and TiO with depressed Ni content. The Ta-implanted NiTi oxidized at 873 K is mainly covered by rutile TiO₂ in several micrometers of thickness. Potentiodynamic polarization tests indicated that the corrosion resistance of the Ta-implanted NiTi was improved after thermal oxidation at 723 K, but a negative impact was found for the Ta-implanted NiTi oxidized at 873 K.     

Synthesis of dandelion-like TiO2 microspheres as anode materials for lithium ion batteries with enhanced rate capacity and cyclic performances

Dandelion-like TiO₂ microspheres consisting of numerous rutile single-crystalline nanorods were synthesized for the first time by a hydrothermal method. Their crystal structure, morphology and electrochemical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and galvanostatic charge and discharge tests. The results show that the synthesized TiO₂ microspheres exhibit good rate and cycle performances as anode materials of lithium ion batteries. It can be found that the dandelion-like structure provides a larger specific surface area and the single-crystalline nanorod provides a stable structure and fast pathways for electron and lithium ion transport, which contribute to the rate and cycle performances of the battery.     

Biodegradable starch/poly (vinyl alcohol) film reinforced with titanium dioxide nanoparticles

Biodegradable starch/poly (vinyl alcohol)/nano-titanium dioxide (ST/PVA/nano-TiO₂) nanocomposite films were prepared via a solution casting method. Their biodegradability, mechanical properties, and thermal properties were also studied in this paper. A general full factorial experimental approach was used to determine effective parameters on the mechanical properties of the prepared films. ST/PVA/TiO₂ nanocomposites were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results of mechanical analysis show that ST/PVA films with higher contents of PVA have much better mechanical properties. In thermal analysis, it is found that the addition of TiO₂ nanoparticles improves the thermal stability of the films. SEM micrographs, taken from the fracture surface of samples, illustrate that the addition of PVA makes the film softer and more flexible. The results of soil burial biodegradation indicate that the biodegradability of ST/PVA/TiO₂ films strongly depends on the starch proportion in the film matrix. The degradation rate is increased by the addition of starch in the films.     

处理频率对TC4钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化膜的制备系统对TC4钛合金进行表面处理, 通过扫描电镜(SEM)和X射线衍射仪(XRD)研究脉冲频率(f)对氧化膜生长特性、 表面形貌和相组成的影响. 结果表明, 当f≤2 000 Hz时, 成膜速率随f增加迅速减小; 当2 000 Hz＜f＜4 000 Hz时, 成膜速率随f增加而减小的趋势变缓; 当f≥4 000 Hz时, 成膜速率不随f发生变化. 该氧化膜表面多孔, 随f的增加, 膜表面微孔尺寸逐渐减少, 微孔密度逐渐增加. 膜层主要由锐钛矿和金红石相TiO2及少量不饱和氧化物TiO2-x（0.02＜x＜0.07）相组成, 其中锐钛矿和金红石相TiO₂的相对含量随f的变化不明显, 而TiO_2-x的相对含量当f≤2 000 Hz时较高, 当f＞2 000 Hz时, TiO_2-x的相含量明显减少.      

A kinetic model for describing effect of the external surface concentration of TiO2 on the reactivity of eggshell activated carbon supported TiO2 photocatalyst

The porous support supported TiO2 is considered to be the promising photocatalyst due to the fact that it is easily recovered from water and has high capacity to mineralize pollutants. Obviously, the expected structure of this kind of photocatalyst is egg-shell, that is, TiO2 is mainly on the external surface of the porous support. The reactivity of the supported photocatalyst strongly depends on the concentration of TiO2 on the external surface of the porous support. In this study, a kinetic model was developed to describe the effect of the external surface concentration of TiO2 （CESC） on the reactivity of egg-shell activated carbon （AC） supported TiO2 photocatalysts. It was found that the obtained model precisely described the effect of CESC, on the reactivity of TiO2/AC photocatalysts. This study can be used to deeply understand the performance of TiO2/AC catalysts and to provide valuable information on designing efficient supported TiO2 photocatalysts.     

Fabrication and character ization of electrospun TiO2/CuS micro–nano-scaled composite fibers

A process to fabricate a kind of novel micro–nano scaled TiO2/CuS composite fibers by electrospinning technique and chemical precipitation method was developed in the present study. The microstructures and photoelectronic properties of the fibers were characterize d using SEM, FT-IR, UV–vis and fluorescence spectroscopy. The results revealed that the TiO2 portion in the composite fibers was a mixture rutile and anatase phases while TiO2 and CuS had been fully composite. The fibers had smooth surface with a diameter of 50–300 nm. Comparing with pure TiO2 fiber, the TiO2/CuS micro–nano-scaled composite fibers exhibited a strong absorption in the visible light region and the efficiency of photo-induced charge separation were enhanced. This composite system is of widely potential applications in the areas such as solar cells, supercapacity, photocatalysis, etc.     

Removal of zirconium from hydrous titanium dioxide

A method was proposed for removing zirconium (Zr) from hydrous titanium dioxide (HTD) by the NaF solution. The effects of main parameters, i.e. pH values, NaF dosage, temperature and retention time, on the removal of zirconium were studied. The optimal conditions were found as the following: pH value, <5.5; molar ratio of NaF to TiO₂, 0.6; retention time, 80 min; and temperature, 80℃. The removal rate of Zr under the optimized conditions was above 87.7%. The adsorption energy of the preferential absorption of hydrofluoric acid for Zr(OH)₂SO₄(OH₂) on the (001) crystal surface of HTD was determined by theoretical calculation. The possible mechanism of the removal process was also discussed.     

一步法合成耐久性水基超疏水TiO2/DTMS涂层

为制备具有优异自清洁功能的耐久性水基超疏水涂层,以十二烷基三甲氧基硅烷(n-dodecyltrimethoxysilane, DTMS)为有机改性物,通过一步法在纳米TiO₂表面嫁接长链烷基官能团得到超疏水TiO₂/DTMS涂层。分析了TiO₂涂层及TiO₂/DTMS涂层的表面润湿性、形貌和化学组成,并对所得超疏水TiO₂/DTMS涂层的自清洁性能、机械及化学稳定性进行了测试。结果表明：超疏水TiO₂/DTMS涂层表面水接触角(water contact angle, WCA)达到159°;以亚甲基蓝粉末作模拟污染物,涂覆有超疏水TiO₂/DTMS涂层的玻璃具有优异的自清洁性能;经机械磨损(10 min)、酸碱液(pH=1、3、5、7、9、11、13)浸泡、高低温(−20、30、60、90、120、150 ℃)处理后超疏水TiO₂/DTMS涂层的WCA仍大于150°,表明其具有优异的机械和化学稳定性,可用于室外防污,如建筑物外墙、玻璃、太阳能电池板等。     

Photoelectrical performance of nanocrystalline TiO2 film electrode sensitized by Ru(II)-bipyridine complexes

Two kinds of Ru(II)-bipyridine complexes,cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(II) andcis-di(thiocyanate)bis(2, 2′-bipyridyl-3, 3′-dicarboxylate) ruthenium(II), were utilized as the sensitizers to the nanocrystalline TiO₂ film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO₂ film electrodes with TiCl₄ was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO₂ electrodes.