Ti2(OMe)4/SiO2催化剂的制备及其合成碳酸二甲酯的反应性能

采用表面改性和离子交换法制备了SiO2负载的Ti2(OMe)4双核桥联配合物催化剂，用IR、TPD和微反技术考察了催化剂的表面构造及CO2和CH3OH在催化剂表面上的化学吸附和反应性能。结果表明：双核桥联配合物Ti2(OMe)4以Ti-O-Si键锚定在SiO2表面上；CO2在催化剂表面存在桥式和甲氧碳酸酯基两种吸附态，其中甲氧碳酸酯基吸附态是生成DMC的关键物种；CH3OH在催化剂上只有一种分子吸附态。在150℃以下，CO2和CH3OH在Ti2(OMe)4/SiO2催化剂表面上高选择地生成碳酸二甲酯。     

稀土在低硫铌钛钢中的作用

在实验条件下采用50kg真空感应炉炼和两段控制轧制工艺，并采用WE－60型万能拉伸试验机，JB－30B型冲击试验机，MM6型及OLYMPUS－PME3型光学金相显微镜，IBAS－2000图相分析等手段研究了稀土对低硫铌钛钢性能，组织及夹杂物的影响。在低硫铌钛钢中的试验结果表明，稀土元素的加入使力学性能变化各异，它使钢的横向屈服点和抗拉强度先下降而后上升；延伸率则无下降而后上升；稀土对钢的横向冲击功则表现为先上升而后下降，并且在－20℃以上，适量的稀土加入可以明显改善其冲击功的各向异性；稀土的加入并不能改变钢的显微组织类型，钢的组织为铁素体＋珠光体，但稀土会使钢中珠光体数量增加，铁素体数量减少，在钢中夹杂物方面，稀土加入则表现为它一方面 化钢液，使钢中夹杂物数量减少，另一方面是使钢中夹杂物的颗粒球化，细化和弥散化，从而改善夹杂物的分布。     

激发态Ti＋(3d14s2)与丙炔醇气相反应理论研究

用量子化学密度泛函(DFT)方法研究了激发态Ti^＋(3d¹4s²)与丙炔醇(PPA)气相反应的机理. 在B3LYP/DZVP水平上, 优化了反应的两个通道的反应物、中间体、过渡态和产物的几何构型, 并在MP4/[6-311＋G**(C,H,O)＋Lanl2dz (Ti)]水平上计算了各驻点的单点能量. 为了确证过渡态的真实性, 在B3LYP/DZVP水平上进行了内禀坐标(IRC)计算和频率分析, 获得了二重态反应势能面, 确定了反应机理. 研究结果表明生成产物为[C₃H₃O]^＋和Ti—H的通道是主要反应途径.     

稀土掺杂对锂离子电池正极材料LiMn2O4结构及电性能的影响

利用微波加热技术合成稀土掺杂基锂离子电池正极材料LiMn2-xRExO4(RE=Y，Nd，Gd，Ce)，通过XRD、循环伏安及恒电漉充放电测试研究了稀土掺杂离子对合成正极材料结构及电化学性能的影响。XRD测试结果表明，合适的掺杂量可以起到扩展锂离子脱嵌通道和稳定骨架结构的作用，稀土离子的引入可以部分取代原有的三价锰离子，由于稀土离子的离子半径较三价锰离子大，因此稀土掺杂锰酸锂材料的晶胞参数比未掺杂材料大，在一定程度上扩充了锂离子迁移的三维通道，更有利于锂离子的嵌入与脱嵌；循环伏安及恒电漉充放电测试结果表明稀土掺杂有效提高了LiMn2O4材料的电化学循环可逆性及循环稳定性。     

Characterization and electrochemical investigation of boron-doped mesocarbon microbead anode materials for lithium ion batteries

The structure and anodic performance of boron-doped and undoped mesocarbon microbeads (MCMBs) have been comparatively studied and the results obtained by XPS, XRD, SEM, Raman spectroscopy and electrochemical measurements are discussed. It is found that boron doping introduces a depressed d ₀₀₂ spacing and the larger amount of "unorganized carbon", which induces vacancy formation in the graphite planes and leads to a quite different morphology from that of the undoped material. Electrochemical charge/discharge cycle tests indicated that after boron doping the lithium intercalation was carried through at a somewhat higher potential, being attended by greater irreversible capacity loss. Electronic Publication     

金属离子掺杂对TiO2光催化性能的影响

TiO₂光催化反应过程涉及光生电荷、电荷迁移、电荷在TiO₂表面的反应和溶液体相反应4个顺序相接并相互影响的步骤.在TiO₂中掺杂金属离子对以上4个步骤均有重要影响,合理的掺杂可有效地提高其光催化性能.本文综合了国内外此方面的最新研究成果,从提高TiO₂光催化性能和优化光催化反应的角度出发,在材料吸光能力、电荷扩散、表面反应、粒径和晶型等方面,全面地分析总结了金属离子掺杂的影响效果和规律性认识,并对TiO₂基光催化材料的金属离子掺杂改性研究的未来发展方向提出了建议.文中还简要介绍了相关的掺杂方法和材料表征手段.     

N-TiO2/ZnO复合纳米管阵列的掺杂机理及其光催化活性

以ZnO纳米柱阵列为模板, 采用溶胶-凝胶法制备出TiO2/ZnO和N掺杂TiO2/ZnO的复合纳米管阵列. 扫描电镜(SEM)、X射线光电子能谱(XPS)和紫外-可见漫反射吸收光谱(UV-Vis)的结果表明: 两种阵列的纳米管均为六角形结构, 直径约为100 nm, 壁厚约为20 nm; 在N-TiO2/ZnO复合纳米管阵列中, 掺入的N离子主要是以N-Ox、N-C和N-N的形式化学吸附在纳米管表面, 仅有少量的N离子以取代式掺杂的方式占据TiO2晶格O的位置; 表面N物种形成的表面态能级和取代式掺杂导致带隙的窄化, 增强了纳米管阵列的光吸收效率, 促进了光生载流子的分离. 光催化实验结果表明, N离子的掺杂有利于N-TiO2/ZnO复合纳米管阵列光催化活性的提高.     

Fe3+掺杂TiO2光催化降解聚乙烯薄膜的研究

以快速溶胶-凝胶法制备了纳米TiO₂光催化剂，并用Fe³⁺对其掺杂改性，在室温条件下, 用于固相光催化降解聚乙烯(PE)包装薄膜的研究. 对催化剂和薄膜进行了X衍射分析(XRD)、傅立叶红外光谱分析(FT-IR)、扫描电子显微镜(SEM)形貌观察. 结果表明， 60 W紫外光辐射240 h后， PE失重为8.43%, 锐钛矿型纳米TiO₂光催化剂使PE失重30.66%；用Fe³⁺掺杂后，0.5%Fe₂O3/TiO₂、1.0%Fe₂O₃/TiO₂和2.0%Fe₂O3/TiO₂分别使PE失重35.91%、20.72%和13.30%. 光催化剂加速了PE的失重，碳链的断裂和光氧化腐蚀，在薄膜表面形成大量的坑洞，降解产物中的小分子量的石蜡含量明显增高. Fe³⁺掺杂有一个最佳量， 0.5%Fe₂O3/TiO₂光催化降解PE的活性最高.     

Fabrication of PbTiO3 Ceramic Fibers by Sol-Gel Processing

The sol-gel processing was applied to the fabrication of PbTiO₃ fibers. Pb(CH₃COO)₂·3H₂O and Ti(OC₃H ₇ ⁱ )₄ were refluxed with stirring in 2-methoxyethanol to form Pb-methoxyethoxide and Ti-methoxyethoxide, respectively, followed by mixing with stirring in 2-methoxyethanol to form Pb−Ti double alkoxide. The hydrolysis and polycondensation reaction of this double alkoxide gave polymerized products, and as a result the viscosity of the solution increased, suggesting that linear polymers were produced through the hydrolysis and polycondensation reaction. Homogeneous PbTiO₃ gel fibers were drawn from the spinnable viscous solutions, which were wellcrystallized into perovskite type PbTiO₃ at 650°C. The heat-treated fibers were a few centimeters long and from 10 to 100 μm in diameter. The fiber was made up of extremely uniform grains. Electron diffraction revealed a preferred growth of (101) planes along the fiber axis, which might be due to the linear molecular characteristics of the alkoxide.     

Fast screening of anabolic steroids and other banned doping substances in human urine by gas chromatography/tandem mass spectrometry

A fast and sensitive method for the comprehensive screening of anabolic agents and other banned doping substances using gas chromatography/tandem mass spectrometry (GC/MS/MS) with an external ionization ion trap mass spectrometer is presented. The method takes advantage of the resolving power of MS/MS to eliminate background interferences, thus speeding up the chromatographic analysis. For each compound, different fragmentation reactions were studied and their collision energies optimized to obtain the best sensitivity in terms of their signal-to-noise ratio (S/N). A dramatic reduction in overall analysis time was achieved compared with other common approaches. More than 50 substances could finally be monitored in less than 7.4 min with detection limits (S/N >3) lower than 0.5 ng ml(-1) for most of the compounds with special sensitivity requirements according to the International Olympic Committee (IOC). A validation procedure for qualitative analysis was performed. The selectivity of the method showed that no interfering peaks were observed at the retention time of the analytes. Good intermediate precision, below 25% for most of the compounds, and robustness were observed. The optimized method was successfully applied to analyse more than 100 real human urine samples with optimum sensitivity and specificity rates.