高压导致纳米TiO2形变的电子显微研究

α-PbO₂相TiO₂高压相具有适宜的带隙能和可见光范围的光催化能力,是一种适用于可见光、高效且环保的光催化材料.本文使用金刚石对顶压砧对锐钛矿纳米球进行加压-卸压处理得到了α-PbO₂相TiO₂高压相.利用透射电子显微镜对比初始样品和卸压样品,观察结果表明晶粒发生了明显形变,高分辨图显示其晶粒中存在大量[100]方向层错和形变孪晶,其中亚微米级晶粒中形成了透镜形片层结构的形变孪晶带;纳米级晶粒中形成了扇形多重形变孪晶.研究表明高压下锐钛矿TiO₂可以发生明显的形变,其形变的微观机制与金属类似,主要为形变孪晶和层错滑移,形变孪晶的形成存在明显的尺寸效应.这些结果为TiO₂高压相变的尺寸效应研究提供了一个新的切入点,同时还为制备孪晶α-PbO₂相TiO₂高压相提供了方法.     

ZnS:Eu纳米晶的高压相变研究

采用同步辐射能量色散X射线衍射技术和金刚石对顶砧高压装置,对ZnS:Eu纳米晶进行了原位高压X光衍射实验.最高压力为30.8Pa.当压力为11.5GPa时,ZnS:Eu发生了一次从纤锌矿到闪锌矿的结构相变.在压力为16.0GPa时,又发生了明显的结构相变,相变后的结构为岩盐矿,其相变压力较体材料高.得到了Birch-Murnaghan状态方程、ZnS:Eu纳米晶的体模量和压力导数.ZnS:Eu纳米晶的体模量高于体材料的值,表明纳米材料较体材料的硬度高.     

Ca5N4高压新相的第一性原理研究

通过在氮中引入杂质离子,利用高压手段获得具有新奇结构的多氮化合物是目前被广泛应用的研究方法.钙氮材料在催化、光电方面有着广泛的应用.具有较低电离能的钙(Ca)元素很容易和氮原子形成离子键钙氮化物.高压为寻找新型钙氮化合物提供了全新的技术途径.因此,利用高压方法,通过改变配比的方式,寻找具有新奇特性的钙氮高压结构,是一项非常有意义的工作.本文利用基于密度泛函理论的结构搜索方法,在100 GPa条件下,通过预测得到了一个稳定的Ca5N4相.该结构内部氮原子之间以N-N共价单键键合,氮原子和钙原子之间是离子键相互作用,且钙氮之间的电荷转移量为1.26 e/N atom.能带结构计算表明P 21/c-Ca5N4是一个直接带隙为1.447 eV的半导体结构.最后,系统地给出了该结构的拉曼振动光谱,并指认了拉曼振动模式,为实验合成该结构提供了理论指导.     

自由涡尾迹方法中涡核尺寸对风力机气动计算的影响

涡核模型中的涡核尺寸对自由涡尾迹(free vortex wake,FVW)方法准确预估风力机气动特性至关重要,涡核尺寸包括初始涡核半径和由于耗散效应涡核半径在尾迹中的增长.FVW方法中涡线控制方程离散采用三步三阶预估校正格式,涡核模型采用经典Lamb-Oseen模型,并考虑了涡耗散效应和拉伸效应.首先,通过气动载荷和叶尖涡涡量平均值的分析得到初始涡核半径的取值范围;然后,根据叶尖涡耗散特性的分析,确定体现涡黏性耗散效应涡核半径增长的经验常数的取值;最后,分析了涡核尺寸对叶尖涡结构的影响,进一步验证初始涡核半径和涡黏性耗散经验常数的取值对风力机气动计算的影响.结果表明:当初始涡核半径大于50%弦长时,FVW方法收敛稳定且能准确预估风轮气动载荷;综合风轮气动载荷和叶尖涡耗散特性,初始涡核半径取60%到70%弦长为宜,且对应的涡黏性耗散经验常数取值也不同;风轮气动载荷和叶尖涡结构的准确预估主要受初始涡核半径影响,经验常数对其影响不大,而经验常数主要影响风轮下游尾流场叶尖涡的耗散特性.      

电感耦合等离子体-原子发射光谱法测定地下水及矿泉水中二氧化硅含量的研究

地下水及矿泉水中二氧化硅的传统分析方法过程皆比较繁冗,采用电感耦合等离子体-原子发射光谱法(ICP-AES)测定地下水及矿泉水中的二氧化硅。在选定了较灵敏的硅分析线后,探讨了ICP光谱仪工作条件对分析结果的影响,同时研究并消除共存离子对SiO2测定结果的影响。通过条件实验,选择仪器的发射功率为1 350 W,观测高度为12mm,雾化器压力为0.20 MPa,泵速为75r·min-1。在光谱仪最佳分析条件下,利用该方法测定地下水及矿泉水中二氧化硅的含量,其检出限为0.017mg·L-1,加标回收率在94.10%~103.8%之间,相对标准偏差(RSD)≤3.06%,同时与硅钼黄分光光度法进行对比实验,结果基本吻合,相对偏差≤3.00%,本方法简便快捷,精密度和准确度较高,可以用于科研及日常生产中。     

Study of high pressure structural stability of CeO2 nanoparticles

In situ high pressure XRD diffraction and Raman spectroscopy have been performed on 12 nm CeO₂ nanoparticles. Surprisingly, under quasihydrostatic conditions, 12 nm CeO₂ nanoparticles maintain the fluorite-type structure in the whole pressure range (0-51 GPa) during the experiments, much more stable than the bulk counterpart (P_T～31 GPa). In contrast, they experienced phase transition at pressure as low as 26 GPa under non-hydrostatic conditions (adopting CsCl as pressure medium). Additionally, 32-36 nm CeO₂ nanoparticles exhibit an onset pressure of phase transition at 35 GPa under quasihydrostatic conditions, and this onset pressure is much lower than our result. Further analysis shows both the experimental condition (i.e., quasihydrostatic or non-hydrostatic) and grain size effect have a significant impact on the high pressure behaviors of CeO₂ nanomaterials.     

Preferred orientations of encapsulated C60 molecules inside single wall carbon nanotubes

A systematical study of the orientational behavior of C60 molecules in single wall carbon nanotubes (SWCNTs) with different chirality and diameter has been performed by using a model of an infinite long nanotube filled with two C60 (denoted as C60-1 and C60-2) molecules. We studied the preferred orientation of the C60-1 molecule when the neighboring C60-2 molecule was fixed at the pentagon, double-bond, and hexagon orientations respectively. Our results showed that the C60-1 molecule prefers the pentagon (hexagon) orientation when the tube diameter is smaller (larger) than 1.31nm (1.36nm). For the tube diameter in between, the preferred molecular orientation of C60-1 changes from pentagon to hexagon with the increasing tube diameter when the neighboring C60-2 molecule is fixed at the pentagon or double-bond orientation. A novel vertex orientation for the C60-1 molecule has been found when the C60-2 molecule is fixed at the hexagon orientation.     

含镧金属富勒烯不同溶剂的高温高压提取

将金属原子或离子置于以Ｃ６０、Ｃ８２为代表的富勒烯笼内形成金属富勒烯包合物是目前富勒烯研究的热点课题［１～３］．合成的金属富勒烯常伴随生成较难分离的空心富勒烯,传统的索氏提取法效率又较低,使得金属富勒烯的深入研究受到限制［１,２］．本文采用改进的高温...     

金属富勒烯La@C2的合成,提取及其ESR和MS表征

采用对掺入Ｌａ２Ｏ３的石墨棒原位活化并结合交换电极回放方法制备了产率较高的金属富勒烯，并用甲苯温热提取的方法有效地提取的Ｌａ＠Ｃ２ｎ，其中Ｌａ＠Ｃ７１为可溶性金属富勒烯增加了新成员，同时，首次采用解吸电子轰击质谱对提取物进行了表征，讨论了提取物的ＥＳＲ谱。     

Local microstructural analysis for Y_2O_3/Eu~(3+)/Mg~(2+) nanorods by Raman and photoluminescence spectra under high pressure

In this paper, we investigate the Raman and photoluminescence spectra of Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods under high pressures using 514-nm and 532-nm laser light excitation. We observe transitions from the initial cubic phase to amorphous at pressures higher than 24 GPa for both Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods. In addition, Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods exhibit different distorted states after the pressure has been raised to 8 GPa. The analyses of intensity ratios, I_(0-2)/I_(0-1) from ~5D_(0–)~7F2_to~5D_(0–)~7F_1and I_(0-2)A/B of ~5D_(0–)7F_2 transitions indicate that Y_2O_3/Eu~(3+)/Mg~(2+) nanorods exhibit stronger local micro-surrounding characteristics for Eu~(3+) ions in a pressuremodulated crystal field. The doped Mg2+ion results in reducing the crystal ionicity in the distorted lattice state under high pressures. The use of doped ions as an ion modifier can be applied to the study of small local microstructural changes through Eu~(3+) luminescence.