铕掺杂纳米二氧化钛透明光触媒乳液的制备及光催化性能研究

本文采用常温络合—控制水解法,以TiCl_4,有机羧酸,氨水,硝酸铕,D-山梨醇等为主要实验药品,制备了Eu掺杂纳米TiO_2光触媒乳液。以酸性红3R染料为待降解物,分别考察了不同条件下制备的TiO_2光触媒乳液在太阳光模拟器生成光照射下的光催化性能。此外,还考察了Eu掺杂纳米二氧化钛透明光触媒乳液对于不同浓度染料的光催化性能。通过酸性红3R染料的降解实验,研究了影响Eu掺杂纳米二氧化钛透明光触媒乳液光催化活性的因素。通过X射线衍射仪(XRD)、纳米激光粒度分析仪、紫外可见分光光度计(UV-Vis)等对样品进行表征。结果表明:样品的平均粒度为4.1 nm左右,晶型为锐钛矿,样品的吸收光谱可拓宽至可见光区。当Eu掺杂量为0.3%,pH值为6,回流时间是15 min时,制备的Eu掺杂纳米二氧化钛光触媒乳液的光催化性能最佳。该光触媒乳液经太阳光照射1 h之后,对浓度为25 mg/L的酸性红3R模型反应物的降解效率最高,达到97%以上。     

负载型二氧化钛光催化材料的制备及其光催化性能研究

以球形氧化铝为载体,采用溶胶-凝胶法和浸渍涂覆过程制备了负载型二氧化钛光催化材料。以扫描电子显微镜(SEM)和X-射线衍射仪(XRD)等手段对所合成的样品形貌及晶型进行了表征。结果表明,氧化铝载体经负载二氧化钛后,在球形氧化铝表面沉积了一层粒径为10~20nm的锐钛型二氧化钛纳米颗粒。通过能量色散X射线光谱(EDX)对氧化铝载体和所合成的样品进行进一步分析,表明样品中明显存在Ti元素。另外,提高氧化铝载体在二氧化钛溶胶中的浸渍次数能够有效提高二氧化钛的负载量。当浸渍次数增加到5次时,Ti元素的含量由3.8Wt.%提高至15.7Wt.%。另外,以亚甲基蓝为目标降解物,详细研究了不同浸渍次数获得的负载型二氧化钛催化材料的催化性能。结果表明:随着浸渍次数的增加,负载型二氧化钛催化材料的表面形貌不仅得到明显改善,而且显著提高了样品的光催化活性。当浸渍次数由1次提高至4次时,亚甲基蓝的降解率由40%上升至83.1%。然而,当二氧化钛负载量达到一定程度时,由于不断浸渍导致下层的二氧化钛受光照机会和光照强度减弱,导致其光催化活性提高缓慢。当浸渍次数提高至5次时,亚甲基蓝降解率仅为85.6%。所制备的负载型二氧化钛光催化材料重复使用5次,其光催化活性保持相对稳定。     

Photocatalysts of Cr Doped TiO2 Film Prepared by Micro Arc Oxidation

通过微弧氧化法在Na3PO4+K2Cr2O7电解液中制备了系列铬掺杂二氧化钛薄膜. X射线和扫描电镜显示薄膜的主要晶相为锐钛矿型二氧化钛,且表面为多孔结构. 在可见光照射下,薄膜对降解亚甲基蓝和分解水有着较好的光催化性能,这主要是由铬的掺杂引起的.由于铬的掺杂,一方面在二氧化钛中形成了Cr3+/Cr4+离子对,另一方面在带隙中形成了氧的空位能级. 前者降低了电子-空穴的复合几率,而后者在二氧化钛的禁带中形成了新的能级. 新能级的形成使得由二氧化钛价带跃迁至氧空位能级所需的光子能量减少. 另外探讨了微弧氧化形成掺杂二氧化钛薄膜的机制.     

二氧化钛薄膜的结构和光催化活性关系

用化学气相沉积法合成了具有不同晶体结构的二氧化钛薄膜，研究了二氧化钛薄膜的结构和光催化活性的关系．用XRD、AFM研究了薄膜的晶体组成和形貌，用亚硝酸根研究了薄膜的光催化活性．结果表明在制备温度低于573 K或高于773 K时，薄膜的结构分别为锐钛矿型或金红石型．而在上述温度之间生成的薄膜具有混合的晶型结构，特别是在623 K附近，制备的薄膜具有最高的光催化活性．进一步研究表明，当金红石与锐钛矿微晶体的比例在0.5?0.7时，催化剂薄膜具有高活性．     

原位核磁共振技术研究共催化剂类型以及光照波长对甲醇光催化重整产物的影响

本文采用原位核磁共振的方法研究了在真实固-液环境中共催化剂类型以及光照波长对甲醇光催化重整产物及光解水产氢产率的影响.结果发现,不同贵金属担载的锐钛矿型二氧化钛催化剂对甲醇光催化重整产物的产量和产率有着不同程度的影响,但是对其动力学特征影响不大.光照波长对甲醇光催化重整产物的产量也影响较大.通过对比甲醇氧化产率与产氢产率,发现共催化剂的种类对光催化反应速率及氧化还原能力起重要作用,且共催化剂的种类会影响体系氧化和还原能力之间的协同性.     

TiO2及其掺Fe材料的制备和EPR谱的研究

以钛酸四丁酯、无水乙醇、冰醋酸为原料,在室温下用溶胶-凝胶法制备得到二氧化钛及其掺Fe样品的湿凝胶,室温放置2天后,100 ℃干燥得到干凝胶,在500 ℃下焙烧得到二氧化钛及其掺Fe的粉末状样品. 利用X射线衍射、电子顺磁共振等测试手段对样品进行分析,结果显示所得样品均为锐钛矿,Fe被引入了二氧化钛晶格中,Ti³⁺氧化中心信号强度随Fe掺杂量的增加而增强,峰值向磁场减小方向小幅偏移. 在不同测试温度下, 含Fe量为0.1%的Fe-TiO₂样品中Ti³⁺氧化中心信号强度随温度升高而增强,峰值也向磁场减小方向小幅偏移. 根据电子顺磁共振理论以及二氧化钛在空气中与O₂的反应解释了这些现象.     

介孔二氧化钛光催化降解乙醛及其影响因素

"应用溶剂蒸发自组装的方法合成了具有蠕虫状孔道的介孔二氧化钛粉末和薄膜．考察了不同焙烧温度对材料介孔结构和光催化性能的影响．乙醛光催化降解实验用来表征不同焙烧温度下介孔材料的光催化性能．结果表明实验中合成的介孔二氧化钛材料的光催化活性明显高于颗粒二氧化钛(Degussa P25)．其中400 oC焙烧的样品具有平均孔径为6.0 nm的窄的孔径分布和117 m2/g的大的比表面积．通过对光催化活性结果的分析,发现介孔二氧化钛的活性主要受其比表面积和结晶性的共同影响．对介孔二氧化钛薄膜材料进行了同样的光催化表     

纳米TiO2薄膜的结构及光催化特性

利用磁控溅射方法在单晶硅和石英衬底表面沉积TiO2薄膜. 通过调节实验参量,制备出不同结构的TiO2薄膜. 通过X射线衍射、扫描电镜、拉曼光谱、吸收光谱等对样品进行表征,同时对不同结构的TiO2薄膜的光催化特性进行分析,发现具有网络状结构锐钛矿相的TiO2薄膜具有更高的光催化能力. 本文对不同薄膜的表面形貌和生长机理进行分析,并讨论TiO2结构和表面形貌对其光催化特性的影响.     

水热法制备二氧化钛纳米管-石墨烯复合光催化剂及其光催化性能

采用水热法制备了二氧化钛纳米管-石墨烯的复合光催化剂。利用X射线衍射仪、扫描电镜、透射电镜和拉曼光谱仪对复合材料进行了表征与分析,并对其光催化性能进行了测试。结果显示,同纯二氧化钛纳米管相比,二氧化钛纳米管-石墨烯的光催化性能较高。石墨烯与二氧化钛纳米管复合,充当电子受体,载流子迁移率得到提高,从而提升了光催化性能。     

光催化二氧化钛(TiO2)活性炭再生控制系统

对光催化二氧化钛(TiO2)活性炭进行了分析,利用光催化二氧化钛(TiO2)活性炭的再生机理,提出了光催化二氧化钛(TiO2)活性炭的制备方法及光催化二氧化钛(TiO2)活性炭再生控制系统的设计实现过程,论述了控制系统硬件原理,对TGS2600空气质量传感器电路、活性炭换层控制单元、再生用TL-D 15W/10紫外灯控制单元进行了描述和方案设计,对软件设计流程进行了讨论和说明; 在光催化二氧化钛(TiO2)活性炭再生控制系统,利用再生过程紫外灯光照强度连续监测及动态在线调整,结合程序计算反馈调整,运用碳层连续换层设计,使得 光催化二氧化钛(TiO2)活性炭的再生效率好,光催化二氧化钛(TiO2)活性炭再生控制系统对其它的类似设计提供了借鉴。     

Structural characterizations of sol–gel synthesized TiO2 and Ce/TiO2 nanostructures

Mixed phase TiO₂ and Ce/TiO₂ samples were synthesized by a sol–gel method using different hydrolysis conditions. In pure TiO₂ samples, traditional X-ray diffraction (XRD) and Ti K-edge synchrotron X-ray absorption near edge structures (XANES) independently revealed their anatase/rutile phase ratios. XANES results further revealed a substantial amount of Ti atoms existed in other forms beside anatase and rutile TiO₂ in the sample synthesized by the low hydrolysis condition. An increase in the extent of the hydrolysis during the synthesis leads to an increased rutile ratio and a reduction in other forms. In Ce/TiO₂ samples, the crystal sizes were too small for XRD characterization. Only XANES could be used to characterize their phase ratios. It is found that adding Ce impedes rutile formation; leading to increased anatase ratio. The difference in the fundamental aspects of XRD and XANES techniques in providing the phase ratios is discussed.     

Enhanced ferromagnetic properties of Fe+N codoped TiO2 anatase

The undoped, Fe-doped, N-doped and Fe+N codoped titanium dioxide (TiO₂) samples were synthesized. Detailed analysis shows that all the samples are pure anatase with the shape of a nanorod, and N and Fe ions are incorporated into the TiO₂ lattice. For all the samples, the saturation magnetization at room temperature is in the order of the Fe+N codoped TiO₂>N-doped TiO₂>Fe-doped TiO₂>undoped TiO₂. Upon N doping, enhanced ferromagnetic properties were observed. The N content in Fe+N codoped TiO₂ is about two times as large as that in the N-doped TiO₂, which may account for the largest saturation magnetization observed in Fe+N codoped TiO₂. It is suggested that metal ion and N codoping may provide a new approach for increasing the saturation magnetization in TiO₂-based dilute magnetic semiconductors.     

Preparation and tribological properties of stearic acid-modified hierarchical anatase TiO2 microcrystals

Hierarchical TiO₂ microcrystals were synthesized through a facile solvothermal method. X-ray diffraction (XRD) and scanning electron microscope (SEM) measurements were used to characterize the structure of the as-prepared samples. The results indicated that the synthesized hierarchical titania (TiO₂) microspheres were composed of numerous anatase phase TiO₂ particles. The as-prepared samples were chemically modified with stearic acid to improve their dispersion in oil. Fourier transmission infrared spectroscopy (FT-IR) and thermogravimetry analysis (TGA) were carried out to evaluate the characteristics of the modified TiO₂ microcrystals. The tribological properties of the modified TiO₂ microcrystals as additives of liquid paraffin were studied by a four-ball tester, and the results showed that they could significantly improve anti-wear performance, friction-reduction property and load-carrying capacity of liquid paraffin. These advantages make the modified TiO₂ microcrystals promising for green lubricating oil additives.     

Effect of post heat treatment on microstructure and photocatalytic activities of TiO2 nanoribbons

Low-dimensional TiO₂ nanoribbons were synthesized by a simple one-step hydrothermal method. The TiO₂ nanoribbons were calcined over the temperature range 200-800 °C in order to enhance their photocatalytic properties by altering their crystal phase and increasing crystallization. Effects of hydrothermal temperature, calcinated temperature and calcination time on the formation of nanostructures have been observed and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The (BET) specific surface area of the samples which with different post treatments were determined by N₂ absorption-desorption experiment. In addition, photocatalytic activities of the nanoribbons were evaluated by photodegradation of organic dyes methyl orange under the radiation of UV light. The results reveal that the post-treatments have great effects on the microstructures and the photocatalytic activities of TiO₂ nanoribbons.     

Nitrogen doped TiO2 nanoparticles decorated on graphene sheets for photocatalysis applications

Nitrogen doped TiO₂ nanoparticles decorated on graphene sheets are successfully synthesized by a low-temperature hydrothermal method. The resulting GR-N/TiO₂ composites are characterized by X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-Ray photoelectron spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The optical properties are studied using UV–visible diffuse reflectance spectroscopy (DRS), which confirms that the spectral responses of the composite catalysts are extended to the visible-light region and show a significant reduction in band gap energy from 3.18 to 2.64 eV. Photoluminescence emission spectra verify that GR-N/TiO₂ composites possess better charge separation capability than pure TiO₂. The photocatalytic activity is tested by degradation of methyl orange (MO) dye under visible light irradiation. The results demonstrate that GR-N/TiO₂ composites can effectively photodegrade MO, showing an impressive photocatalytic enhancement over pure TiO₂. The dramatically enhanced activity of composite photocatalysts can be attributed to great adsorption of dyes, enhanced visible light absorption and efficient charge separation and transfer processes. This work may provide new insights into the design of novel composite photocatalysts system with efficient visible light activity.     

Synthesis, structure and optical properties of Eu/TiO2 nanocrystals at room temperature

The nanocrystal samples of titanium dioxide doped with europium ion (Eu³⁺/TiO₂ nanocrystal) are synthesized by the sol-gel method with hydrothermal treatment. The Eu³⁺ contents (molar ratio) in the samples are 0, 0.5%, 1%, 2%, 3% and 4%. The X-ray diffraction, UV-Vis spectroscopy data and scanning electron microscope image show that crystallite size is reduced by the doping of Eu³⁺ into TiO₂. Comparing the Raman spectra of TiO₂ with Eu³⁺/TiO₂ (molar ratio Eu³⁺/TiO₂=1%, 2% and 4%) nanocrystals at different annealing temperatures indicates that the anatase-to-rutile phase transformation temperatures of Eu³⁺/TiO₂ nanocrystals are higher than that of TiO₂. This is due to the formation of Eu-O-Ti bonds on the surface of the TiO₂ crystallite, as characterized by the X-ray photoelectron spectroscopy. The photoluminescence spectra of TiO₂ in Eu³⁺/TiO₂ nanocrystals are interpreted by the surface self-trapped and defect-trapped exciton relaxation. The photoluminescence of Eu³⁺ in Eu³⁺/TiO₂ nanocrystals has the strongest emission intensity at 2% of Eu³⁺ concentration.     

在不同的退火温度下钴注入二氧化钛结构与磁性

选用能量为180 keV,温度为623 K,注入4×10¹⁶ cm^-2剂量的钴离子束注入TiO₂样品.在不同的退火温度下,用高分辨的扫描电镜、同步辐射X射线衍射、卢瑟福背散射/沟道实验和超导量子干涉仪,分别对样品进行结构与磁性的测试. SR-XRD和HRTEM测试结果表明: 在Co注入TiO₂后,形成了钴的体心立方(hcp)相和面心立方(fcc)相,且在TiO₂中,钴-纳米粒子也已经形成. 随着退     

<Superscript>119</Superscript>Sn Mössbauer studies on ferromagnetic and photocatalytic Sn–TiO<Subscript>2</Subscript> nanocrystals

Diluted Sn doped TiO₂ nanocrystals (Sn/Ti ratio: x ≤ 1.37 %) were synthesized by a simple hydrothermal method using pure reagents without any surfactant and dispersant material. The XRD of these samples showed an anatase phase, anatase and rutile mixed phases, and a rutile phase of TiO₂ and SnO₂ with the increase of Sn dopant concentrations. ¹¹⁹Sn Mössbauer spectra gave the broad peaks, which were decomposed into doublets and sextets because almost all these samples showed magnetic hysteresis even at room temperature. The titanium oxides doped with x ≤ 0.12 % showed the relatively large magnetic hysteresis and high photocatalytic activity. Mössbauer spectra of samples doped with x > 0.3 % were analyzed by one doublet and two sextets although the samples showed weak ferromagnetism. Three kinds of Sn species may be distinguished as Sn ⁴⁺ substituted TiO₂ and two different magnetic arrangements of Sn doped TiO₂: one with more oxygen defects and other at the interface of TiO₂ and precipitated SnO₂ containing Ti atoms. The correlation between various amounts of Sn sites and photocatalytic activity and/ or magnetic property was discussed.     

Monodispersed 3D MnWO4–TiO2 composite nanoflowers photocatalysts for environmental remediation

Pollutants from textile industries into water-bodies have caused huge environmental hazards. The semiconductor mediated photocatalytic purification of polluted water is a promising environmental remediation technology. In the present study MnWO₄–TiO₂ composite nanoflowers endowed with efficient photocatalytic activity have been successfully synthesized by facile hydrothermal approach. XRD, SEM, TEM, EDX spectroscopy and UV-DRS were used to characterize the as-synthesized samples. The average size of composite nanoflower is ∼2 μm while the nanorods constructing the nanoflowers had the average diameters of 90 nm. The photocatalytic activity of the MnWO₄–TiO₂ nanoflowers for the degradation of methyl orange (MO) in visible light was much higher than of pristine TiO₂ nanorods and MnWO₄ nanoflowers respectively. The superior photocatalytic activity could be attributed to the formation of a MnWO₄–TiO₂ heterojunction in the MnWO₄–TiO₂ nanoflowers.     

Preparation and photoelectrochemical performance of Ag/graphene/TiO2 composite film

By dipping-lifting in sol-gel solution and reducing process, the graphene/TiO₂ composite film on the glass plate was first prepared. Then, the Ag/graphene/TiO₂ composite film was fabricated by interface reaction with AgNO₃ and N₂H₄·H₂O on the surface of graphene/TiO₂ composite film. The characterization results show that the uniform porous TiO₂ film is made up of the anatase crystal, and the Ag/graphene/TiO₂ composite film is constructed by doping or depositing graphene sheets and Ag nanoparticles on the surface of TiO₂ film. The photoelectrochemical measurement results indicate that the Ag/graphene/TiO₂ composite film has an excellent photoelectrochemical conversion property.