Synthesis and Characterization of Novel Lanthanocene Complexes with Dichalcogenolate o-Carboranyl Ligands

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Quantum confinement effect in β-SiC nanowires

The quantum confinement effect is important in nanoelectronics and optoelectronics applications; however, there is a discrepancy between the theory of quantum confinement, which indicates that band-gap widening occurs only at small sizes, and experimental observations of band-gap widening in large-diameter nanowires (NWs). This paper reports an obvious blue shift of the absorption edge in the UV-visible absorption spectra of SiC NWs with diameters of 50–300 nm. On the basis of quantum confinement theory and high-resolution transmission electron microscopy images of SiC NWs, band-gap widening in SiC NWs with diameters of up to hundreds of nanometers is fully explained; the results could help to explain similar band-gap widening in other NWs with large diameters.     

含半夹心结构铑的1,1'-二硫(硒、碲)二茂铁化合物

以半夹心结构铑的化合物Cp*Rh(CN^tBu)Cl2(1)(Cp*=η^5-C5Me5)与Fe(C5H4ELi)2.2THF反应,合成出异双核二茂铁化合物Cp*Rh(CN^tBu)(EC5H4)2Fe[E=S(2),Se(3),Te(4)]。通过AgBF4氧化2和3得到二茂铁离子型化合物[Cp*Rh(CN^tBu)(EC5H4)2Fe]BF4[E=S(5),Se(6)]。采用元素分析、红外光谱、^1H和13CNMR谱以及EI-MS表征了所合成的化合物。     

Preparation of core-shell structured polyacrylic modifiers and effects of the core-shell weight ratio on toughening of poly(butylene terephthalate)

Core-shell structured polyacrylic(named CSSP) impact modifiers consisting of a rubbery poly(n-butyl acrylate) core and a rigid poly(methyl methacrylate) shell with a size of about 353 nm were prepared by seed emulsion polymerization. The CSSP modifiers with different core-shell weight ratios(90/10, 85/15, 80/20, 75/25, 70/30, 65/35 and 60/40) were used to modify the toughness of poly(butylene terephthalate)(PBT) by melt blending. It was found that the polymerization had a very high instantaneous conversion(> 95.7%) and overall conversion(99.7%). The morphology of the core-shell structure was confirmed by means of transmission electron microscopy. Scanning electron microscopy was used to observe the morphology of the fractured surfaces. Differential scanning calorimeter was used to study the crystallization behaviors of PBT/CSSP blends. The dynamic mechanical analyses of PBT/CSSP blends showed two merged transition peaks of PBT matrix, with the presence of CSSP core-shell structured modifier, that were responsible for the improvement of PBT toughness. The results indicated that the notch impact strength of PBT/CSSP blends with a core-shell weight ratio of 75/25 was almost 8.64 times greater than that of pure PBT, and the mechanical properties agreed well with the SEM observation.     

氧化钴溶胶复合酚醛树脂的热解碳结构变化

以乙醇为介质将制备的氧化钴溶胶与酚醛树脂进行复合,经固化后在埋炭条件下炭化处理,制备热解碳。借助场发射扫描电镜、高分辨率透射电镜、X射线衍射仪等手段对热解碳的晶体结构、显微结构进行了分析表征。结果表明：氧化钴溶胶粒子在酚醛树脂中以纳米尺寸均匀分散,复合树脂热解过程中氧化钴被还原为单质钴,从而对树脂热解过程起到了催化作用,使其由无定形玻璃态碳部分转变为石墨化碳。对热解碳的显微结构分析表明,热解碳中有大量的碳纳米管生成,其含量、形貌与氧化钴溶胶掺杂量有关。     

Syntheses and Characterization of Half—Sandwich Zirconium Complexes with Dichalcogenolate o—Carborane Ligands

Metallocene complex Cp2^ttZrCl2(Cp^tt=η^5-1,3-^tBu2C5H3)(1)has been prepared from the reaction of LiCp^tt with ZrCl4 in good yield.Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands,[Li(THF)4][Cp^ttZr(E2C2B10H10)2](E=S,2a;E=Se,2b)in which only one cyclopentadienyl ring ligand existed.Complexes 1 and 2a were structurally characterized by X-ray analyses.In complex 2a,the Zr(IV)ion is η^5-bound to one 1,3-ditert-cyclopentadienyl ring and σ-bound to four μ2-sulfur atoms of two dithio-carboranes.the zirconium atom and four sulfur atoms form a distorted pyramid.The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur stoms and the fulcrum at the zirconium stom.     

Quantum confinement effect in <Emphasis Type="Italic">β</Emphasis>-SiC nanowires

The quantum confinement effect is important in nanoelectronics and optoelectronics applications; however, there is a discrepancy between the theory of quantum confinement, which indicates that band-gap widening occurs only at small sizes, and experimental observations of band-gap widening in large-diameter nanowires (NWs). This paper reports an obvious blue shift of the absorption edge in the UV-visible absorption spectra of SiC NWs with diameters of 50–300 nm. On the basis of quantum confinement theory and high-resolution transmission electron microscopy images of SiC NWs, band-gap widening in SiC NWs with diameters of up to hundreds of nanometers is fully explained; the results could help to explain similar band-gap widening in other NWs with large diameters.     

La3+,Ce3+溶液中樟子松吸收的差异性研究

选用樟子松(Pinus sylvestris var. mongolica Litv.)为研究对象,分析其在水培条件下吸收稀土可溶态镧、铈离子(六水硝酸镧、六水硝酸铈,七水氯化镧、七水氯化铈,八水硫酸镧和八水硫酸铈)的过程,揭示樟子松修复镧、铈离子污染的机制。本研究应用吸收动力学的方法探究了樟子松在不同时间内吸收镧、铈离子的含量和速率;并通过回归分析法探究了樟子松-水培体系中吸收镧和铈离子的实测值与预测值之间的相关性。水培溶液中的镧和铈离子浓度分别设置为100, 300, 500, 1000 mg·L^-1。试验结果表明,樟子松体内的镧、铈离子含量随着水培溶液浓度升高而增加,其中,La₂(SO₄)₃, La(NO₃)₃, LaCl₃的含量范围分别为0.0014～0.0142 g, 0.0009～0.0115 g, 0.0017～0.0195 g; Ce2(SO₄)₃,Ce(NO₃