不对称变色酸双偶氮胂类试剂与铋—钪的共显色反应及分光光度测定铋的研究

本文研究了十种变色酸双偶氮胂类试剂与铋—钪的共显色反应,发现其中三溴偶氮胂等五种试剂与铋—钪有共显色反应。铋、钪与试剂生成的配合物的表现摩尔吸光系数为9.4×10~4L·mol~(-1)·cm~(-1)。大量的常见离子不干扰铋的测定,可不经分离直接测定合金中的微量铋。     

Ion-exchange chromatography of glycolatocomplexes of rare earths

Summary The ion-exchange behavior of glycolatocomplexes of the rare earths (Sc, Y and lanthanides) with 1-octanesulfonate as the hydrophobic ion has been investigated in aqueous glycolate media. The system is capable of separating adjacent light intra rare earths, La-Ce-Pr-Nd-Y-Sm, and heavy rare earths, Ho-Er-Tm-Yb-Lu-Sc, from each other with good resolution by gradient elution at room temperature. Intermediate rare earths, Dy-Tb-Gd-Eu-Sm, are difficult to separate from each other. The position of Y in the eluate is different from that found with most other eluent systems used for rare earth separations, being between Nd and Sm.     

Raman spectroscopic verification of fac-Sc(PMBP)3 by solid and solute spectra and density functional method calculation

Two kinds of solids were obtained for Sc(PMBP)₃ by precipitation from different solvents. They were light-yellow crystal and yellowish-white powder, and their melting points were 209 and 217 °C, respectively. Raman spectra of six anhydrous samples prepared from these materials were measured and classified into two types of spectral patterns. Raman solute spectra of these two materials were measured in a dilute solution of dichloromethane, in which the solute is a free molecule in a solvent cage. Their spectra were considerably similar to each other, but they indicated clear differences in some pairs of bands. One of these two molecules was concluded to be a facial form of Sc(PMBP)₃, because the other constituent has been established to be a meridional form of Sc(PMBP)₃ by X-ray analysis of a single crystal. Structural optimization for mer- and fac-Sc(PMBP)₃ and their vibrational calculation of frequencies and intensities were carried out with the density functional method of B3LYP/6-31G**. Their computed Raman spectra were well coincident with their observed spectra. The existence of fac-Sc(PMBP)₃ has been established by thermal analysis, Raman spectroscopy and ab initio calculation.     

团簇Sc_3B_2的结构与性质

利用密度泛函理论(DFT),在B3LYP/Lan12dz赝势基组水平下对团簇Sc_3B_2的二、四重态进行全参数优化计算和相关频率的计算验证,得出7种稳定构型。对这些稳定构型的能量、结构、成键情况和电荷进行分析,结果表明:团簇Sc_3B_2的优化构型以三角双锥型、戴帽三角锥型和四角锥型为主,仅一个平面五边形;所有优化构型中构型1~(2)的稳定性最好,二重态的稳定性均高于四重态的稳定性,多重度对结构稳定性影响较大;Sc-B键对团簇Sc_3B_2的稳定性起重要作用;金属原子Sc是团簇Sc_3B_2前线轨道的主要贡献者,是潜在的活性位点。     

Sc2O3: Nd,Sc2O3:Yb纳米粉体的制备和光致发光

以反滴定共沉淀方法制备了Sc2O3:Nd、Sc2O3 :Yb纳米粉体,用热重、差热分析、X射线衍射对前驱体相变及粉体结构进行了研究,并研究了其光致发光.Sc2O3:Nd、 Sc2O3:Yb前躯体的热重和差热曲线分别在73 ℃、77 ℃与434 ℃、436 ℃出现了明显的热失重和吸热峰,结合XRD表明约在450 ℃,前驱体粉体经γ-ScOOH相转变为立方Sc2O3相.Reitveld方法精修给出Sc、O的原子坐标.结果表明,掺杂离子导致了晶格畸变.在825 nm光激发下,粉体Sc2O3 :Nd的1084 nm主荧光峰为Nd3+的4F3/2→4I11/2跃迁;在937 nm光激发下,粉体Sc2O3:Yb的1044 nm主荧光峰为Yb3+的2F5/2→2F7/2跃迁.Sc2O3:Nd、Sc2O3:Yb的发光光谱表明激活离子处于较强晶场中,Stark能级分裂大,有利于降低Yb3+的激光阈值、提高激光热稳定性.     

MSn_（10）（M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni）团簇的稳定性和磁性研究

采用密度泛函理论（density functional theory,DFT）中的广义梯度近似（generalized gradient approximation,GGA）对Sn11团簇的4种同分异构体（对称性分别为D5h,D5d,D4h,D4d）的几何结构、电子结构计算研究,得出对称性为D5d的团簇最稳定.将Sn11团簇的中心原子替换成过渡金属原子成为MSn10（M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni）团簇,对其稳定性和磁性进行了分析.在Sn11团簇中将中心原子替换成过渡金属原子后,束缚能都变小了,说明过渡金属原子的替换提高了原锡团簇的稳定性,其中NiSn10团簇的束缚能最小,稳定性最强.过渡金属原子都具有一定的磁性,当把这些原子掺入锡团簇后,过渡金属原子的磁性都有所减弱,其中MSn10（M=Sc,Ti,V,Ni）团簇的磁性完全消失,其原因在于掺杂后,团簇中各原子的电荷分布发生了变化.     

Sc与Zr对Al-Mg-Mn合金力学性能和剥落腐蚀性能的影响

为了寻找Al-Mg-Mn合金力学性能和耐剥蚀性能的最佳组合,采用对比法探索Sc和Zr对Al-Mg-Mn合金力学性能和剥落腐蚀性能的影响,测定了含与不含微量Sc和Zr的Al-Mg-Mn合金板材在不同退火态的力学性能和剥落腐蚀性能,测量了它们的极化曲线.采用扫描电镜观察了合金的腐蚀微观形貌、用能谱仪分析了腐蚀产物的成分.采用光学显微镜和透射电子显微镜分析了合金的显微组织和力学性能、剥落腐蚀性能之间的关系.结果表明： 添加微量Sc和Zr能显著提高Al-Mg-Mn合金强度,改善合金强度和塑性的配合,而且Sc和Zr的添加没有引起合金耐剥蚀性能的明显下降.经过350 ℃/1 h退火的Al-Mg-Mn-Sc-Zr合金具有优良的力学性能和耐蚀性能组合.可通过添加微量Sc,Zr,减少Mg的含量,选择合理的退火工艺,使该类合金的力学性能和耐剥蚀性能达到理想组合.     

P204萃取Sc和Ti机理的研究

用分配比反应平衡常数直线斜率法测定出用二（２ 乙基已基） 磷酸（ 简称Ｐ２０４） 萃取Ｓｃ（ Ⅲ） ，Ｔｉ（ Ⅳ） 的萃取化合物的组成分别为ＳｃＡｓ ，ＨＡ 及ＴｉＡ４（ＨＡ 表示Ｐ２０４） ．用等摩尔系列法测定的结果进一步证实了斜率法测出的Ｓｃ 的萃取化合物组成的正确性．     

含钪Al-Zn-Cu-Mg-Zr合金的腐蚀行为和电化学阻抗谱特征

通过晶间腐蚀、剥落腐蚀和极化曲线试验,结合电化学阻抗谱(EIS)测量,研究不同时效处理对含钪超高强Al-Zn-Cu-Mg-Zr合金的晶间腐蚀和剥落腐蚀敏感性的影响。研究结果表明:在自然时效状态下,合金腐蚀敏感性最大;人工时效处理的合金,其腐蚀敏感性随时效时间的延长而降低,相应时效态合金在EXCO溶液中恒电位极化曲线分析,也得出相同的结论。晶界析出相和晶界无沉淀析出带(PFZ)是影响合金腐蚀性能的主要因素。随着时效时间的延长,η′和S′相逐渐向平衡的η和S相转变,晶界析出相粗化并呈链状分布,PFZ变宽等均有助于降低合金的腐蚀敏感性。合金的电化学阻抗谱(EIS)演变对腐蚀类型的转变具有规律的反映,可以用来对合金的腐蚀性能进行快速、无损的检测。     

First-principle studies of the magnetism and optical properties of (Sc,Y)-codoped anatase TiO2 (101) surface

We calculated the electronic structure, magnetism and optical properties of the Sc-doped, Y-doped, and (Sc, Y)-codoped anatase TiO₂ (101) surface using a projector augmented wave (PAW) method with GGA + U approximation. Sixteen doping systems were considered in the present work. The lattice distortion results in the generation of an internal local electric field. In addition, the difference between positive and negative spin charge densities leads to the generation of magnetism. With the exception of the [email protected] system, the width of band gap of the other doping systems increases to varying degrees, leading to a blueshift of the absorption edge. The photocatalytic activity of all the doping systems was improved to different degrees. The absorption intensity and absorption range of the [email protected]&[email protected] system in the visible-light region is the highest amongst all doping systems. This mainly attributed to the formation of hole states and the presence of impurity bands.