Ceria supported Ru~0-Ru~(δ+) clusters as efficient catalyst for arenes hydrogenation

Selective hydrogenation of aromatic amines,especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane,is of particular interests due to the extensive applications.To conquer the existing difficulties,in selective hydrogenation,,the Ru~0-Ru~(δ+)/CeO_2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions.The morphology,electronic and chemical properties,especially the Ru~O-Ru~(δ+) clusters and reducible ceria were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),sca nning electronic microscopy(SEM),X-ray photoelectron sp ectroscopy(XPS),CO_2 tempe rature programmed deso rption(CO_2-TPD),H_2 tempe rature programmed reduction(H_2-TPR),H_2 diffuse reflectance Fourier transform infrared spectroscopy(H_2-DRIFT),Raman,etc.The 2% Ru/CeO_2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine.The volcano curve describing the activity and Ru state was found.Owning to the "acidic site isolation" by surrounding alkaline sites,condensation between the neighboring amine molecules could be effectively suppressed.The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups.     

离子色谱-质谱联用技术测定污泥样品中的痕量高氯酸盐

建立了离子色谱-质谱联用技术测定活性污泥样品中高氯酸盐的分析方法。以高容量、强亲水性的IonPacAS20(2mm)阴离子交换柱为分析柱,EGC在线产生等浓度KOH为淋洗液,淋洗液经抑制成水后将样品带入质谱检测。ESI-MS-MS以多元反应监测模式监控100.8/84.9、98.8/66.9、100.8/68.9和98.8/82.9离子对,以98.8/82.9离子对的峰面积进行定量。该方法对高氯酸盐的检出限(S/N=3)为0.01μg/L,高氯酸盐在0.05~100μg/L浓度范围内具有良好的线性,线性相关系数r=0.9988。0.2μg/L的标准溶液重复进样9次,高氯酸盐峰面积的相对标准偏差(RSD)为2.3%。运用该方法测定采自不同地区的活性污泥样品中的高氯酸盐,并对样品加标回收,得回收率在88.5%~102.2%之间。     

有序介孔材料SBA-15吸附Ru（bpy）3^2＋修饰电极的电化学发光研究

制备了具有高比表面积且二维六方高度有序的介孔分子筛SBA-15,并采用TEM和氮气吸附实验对其结构性质进行了表征.利用静电作用将三联吡啶钌[Ru(bpy)32 ]固定到表面带负电荷的SBA-15上,并将吸附有Ru(bpy)32 的SBA-15修饰到玻碳电极表面,研究了该固定化的Ru(bpy)32 的电化学发光行为.结果表明,随着三丙胺(TPA)的加入,氧化电流增加而还原电流减小,表明TPA对三价吡啶钌有催化作用,同时TPA的加入显著增强了发光强度.随着扫描速率的增加,发光强度逐渐降低.SBA-15较大的孔径和开放交联的孔结构体系促进了电极表面膜内的物质扩散和电子运动扩散.该修饰电极在5.0×10-5~1.0×10-2mol/LTPA浓度范围内,发光强度与浓度具有良好的线性关系,线性方程为y=71.7 41.2x,检出限为9.5×10-6mol/L.该电极在连续扫描下具有较好的稳定性.     

固—液界面阴离子集团构型的密度泛函理论研究

通过键合不同数量的H2PO4^-离子构造了H4P2O8^2-和H4P4O16^8-两种阴离子集 团。利用密度泛函理论对它们的构型进行优化并计算其振动频率和喇曼散射效率。 测量了固—液界面边界层的喇曼光谱并与理论计算结果进行对比分析，进一步研究 了阴离子集团的结构、聚合及脱水等过程。实验和理论研究均表明阴离子二聚体是 KDP晶体的生长基元，他们在固液界面将进一步形成多聚体分子集团，而离子集团 的脱水过程则发生在距KDP晶体表面约50μm的固—液界面边界层中。随着生长层向 界面的推进，这些分子集团将变得越来越有序。本文的研究结果对确定晶体生长界 面动力学过程、发展和完善晶体生长理论有重要意义。     

Sm修饰的Ni-MgO催化剂制备碳纳米管的研究

Carbon nanotubes (CNTs) have been synthesized over Ni-MgO and Ni-Sm-MgO catalysts by decomposition of CH₄ at 650 ℃. The addition of Sm into Ni-MgO catalyst not only promotes the catalytic activity and lifetime of the catalyst, but also improves the graphitization and heat stability of carbon nanotubes. The yield of CNTs obtained over the Ni-10Sm-MgO catalyst reaches 33 g C·(g Ni)^-1, being more than 5 times higher than that of the Ni-MgO catalyst. XRD and TPR results of the catalysts indicate that there is a remarkable interaction of Ni with Sm species, which facilitates the reduction of nickel and restrains the Ni particles from agglomerating.     

聚氯乙烯结构缺陷和热不稳定性之间关系的研究 2.各种结构缺陷含量和热脱氯化氢速率之间的关系

 本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系,揭示了不饱和总双键值,总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/M_n的相关性基础之上,从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性,首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理.     

二碘化铕的相变结构及荧光性质

本文用ＤＴＡ、Ｘ－ｒａｙ粉末衍射和荧光光度计等方法研究了ＥｕＩ２的相变和结构及荧光性质，用退火和淬火的方法得到了ＥｕＩ２的三种不同结构，并在荧光光谱上有不同的反映，首次发现ＥｕＩ２的低温变体，ＥｕＩ２－Ⅲ，正交晶系，空间群为ｐｎｍａ，ａ＝１．２２８７ｎｍ，ｂ＝０．４８８７ｎｍ，ｃ＝０．８３８４ｎｍ，Ｚ＝４。     

Saframycins 及Ecteinascidins化合物的合成研究进展

综述了两类双四氢异喹啉生物碱Saframycins和Ecteinascidins的合成研究进展. 分析了各合成路线的关键步骤, 部分讨论了各方法的优缺点, 并对其生物合成和作用机理作了简单介绍.     

[(enH)2(enH2)Sn2Se6]的合成、结构及性能研究

采用溶剂热法,以K2Se:SnCl2·2H2O∶Se∶en=1∶1∶4∶48的摩尔比,在150 ℃下反应5d,生成黄色透明柱状晶体[(enH2)2Sn2Se6·en]。该晶体属于三斜晶系 ,空间群为Pl^-,晶胞参数,a=0.8659(2)nm,b=1.1055(2)nm,c=0.66360(10)nm, a=104.44(3)°,β=110.93(3)°,γ=79.74(3)°,V=0.57198(19)nm^3,Z=1.[ (enH2)Sn2Se6]晶体由质子化的乙二胺正离子（enH)^+,(enH2)^2+和二聚硒代锡根 负离子（Sn2Se6)^4-堆积而成。在AxSn2Se6系列化合物,正离子A的大小对晶体结 构的类型产生重要的影响。研究表明,此晶体具有1.76eV的能隙（Eg）,是个半导 体,对太阳辐射具有选择吸收特性,在温度低于180℃时是稳定的。     

THERMOTROPIC LIQUID CRYSTALLINE COPOLYESTERS-SOLID STATE POLYMORPHISM

This paper offers some new evidence on the polymorphism of solid state of liquid crystalline aromatic copolyesters which were prepared in our laboratory. The effects of different treatment conditions(quenching and annealing) on solid structure have been examined mainly by DSC and X-ray diffraction. The discussion focuses on the supercooled mesophase and low temperature solid-solid transition, the shifting of double melting peaks of annealed samples and the changing of their ΔH data depending on the treatment temperature, time and thermal scanning rate.