Solid Phase Catalytic Oxidation of Alcohols by Polymer Supported Rare Earth Catalysts

Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results.     

647W灯泵浦大功率连续Nd:YAG激光器

 报道了一台灯泵浦大功率连续Nd:YAG激光器。对影响大功率固体激光器模块输出功率和光束质量的主要因素进行了理论分析，并提出提高激光器效率的措施：对聚光腔的形状、结构和材料以及冷却方式，泵浦灯的参数和材料，激光晶体的参数和镀膜进行优化设计，采用径向固定的谐振腔镜。该灯泵浦YAG晶体棒总体电光转换效率为4%，光束质量为22mm·mrad，输出功率647W。     

激光剥蚀电感耦合等离子体质谱在涂料重金属分析中的应用

将激光剥蚀进样技术(LA)与ICP-MS检测器联用,并将这一新技术应用在涂料重金属元素的检测上,通过优化LA和ICP-MS参数,并采用双气流校正技术,以13C、103Rh为双内标,有效地改善了信号强度和稳定性,同时对Hg的记忆效应进行研究,最终建立了LA-ICP-MS法测定涂料中Cr、As、Cd、Sn、Sb、Hg、Pb元素的定量分析方法,样品测定结果与湿法消解ICP-OES法基本吻合。     

ZnGeP2晶体点缺陷影响光学性能的研究进展

ZnGeP2晶体具有非线性系数大和透光波段宽的特点,是目前重要的中红外频率转换介质材料。然而,点缺陷的存在却引起了ZnGeP2晶体的额外光学吸收,影响了其应用发展。本文对ZnGeP2晶体点缺陷影响光学性能的研究进展情况做了详细的综述。利用电子顺磁共振技术研究了ZnGeP2晶体中存在的点缺陷类型;结合光学吸收和电子顺磁共振方法分析了ZnGeP2晶体点缺陷影响光学性能的机理;介绍了降低ZnGeP2晶体额外光学吸收的方法;最后,展望了围绕ZnGeP2晶体点缺陷及光学性能将开展的研究方向。     

氯化铜的少溶剂固态连串配位化学反应

在少量水的存在下,由于 NH₄[CuCl₃]对水不稳定,CuCl₂·2H₂O 与氯化铵的配位化学反应只能得到 1:2 产物(NH₄)₂[CuCl₄(H₂O)₂];但在无水乙醇中,无水 CuCl₂与氯化铵按 1:1或 1:2的物质的量之比混合时,能相应地得到 NH₄[CuCl₃]或(NH₄)₂[CuCl₄]。CuCl₂·2H₂O与 2,2''-联吡啶(bipy)的少溶剂固态化学反应仍能像固态化学反应一样,根据反应物的配比生成相应的唯一产物,但在物质的量之比为1:1的反应中发现1:2产物曾经形成。热力学分析说明,如果连串反应的后一步的Δ_rG^⊖大于前一步的,则上述反应现象是可能的。     

钒液流电池用隔离膜研究进展

钒液流电池是近年来发展最为迅猛的储能电池之一。隔膜作为钒电池的重要组成部分直接关系到钒电池的转化储能效率和使用寿命。本文综述了近年来钒电池用隔离膜的发展现状。全氟磺酸质子交换膜(Nafion膜)作为当前使用最为广泛的隔膜,从传导机理、交换机理和表面涂覆、交联、复合等表面改性技术方面入手做了深入的研究,并对比分析了各种改性方法的优缺点。对磺化的特种工程塑料为主的非氟耐热型质子交换膜和功能化的聚烯烃隔膜在钒电池中的当前进展做了全面总结,并对钒液流电池用电池隔膜的发展方向做了展望。     

生物素衍生物自组装膜制备及其覆盖度的电化学测定

利用循环伏安法和电化学交流阻抗谱研究了MBDA/Au,MBTA/Au,TBDA/Au,TBTA/Au修饰电极以及MBDA与DT混合自组装/Au、TBTA与DT混合自组装/Au修饰电极的覆盖度。结果表明这些自组装膜在金电极表面的覆盖度均比较高,达到99%以上;对同一类修饰电极,混合自组装膜的覆盖度高于单组分自组装膜的覆盖度,混合自组装体系的覆盖度随着DT比例的增加而增加;同类物质,长链化合物在金表面的覆盖度大于短链化合物,含二硫键的化合物与金电极的键合能力比含一个巯基的化合物键合能力强。     

准经典轨线方法对Ca+CD3Ⅰ→CaⅠ+CD3同位素效应的动力学研究

在扩展Lond-Eyring-Polanyi-Sato(LEPS)势能面上,采用准经典轨线方法对反应Ca+CD3I→CaI+CD3进行了动力学计算,并讨论了该反应的同位素效应.在同位素效应作用下,产物CaI的振动态分布向低振动态转移,反应体系的散射截面在低碰撞能和高碰撞能处有较小的变化.同时,受到反应物的质量因子变化的影响,产物转动取向值减少,产物转动取向增强.仅有产物的角分布受同位素效应的影响不明显.     

Synthesis, Crystal Structure and Chemical Bonding of a New Binary Lu-Sn Phase: Lu11Sn10

A new tetragonal phase of Lu11Sn10 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group I4/mmm (No.139) with a=11.2953(18), c=16.424(4), V=2095.5(7)3 , Z=4, Mr=3111.57, Dc=9.863 g/cm3 , μ=62.897 mm-1, F(000)=5124, and the final R=0.0348 and wR=0.0894 for 706 observed reflections with I>2σ(I). The structure of Lu11Sn10 may be derived from the Ho11Ge10 structural type. It is isostructural with Dy11Sn10 , featuring a three-dimensional (3D) framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional (1D) tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms. Band structure calculation based on density functional theory method indicates that Lu11Sn10 is metallic.     

火焰原子吸收法直接测定铅酸蓄电池用硫酸中铁

建立了火焰原子吸收光谱法直接测定H2SO4中Fe的方法。采用蓄电池用H2SO4样品直接配制标准加入法系列溶液,用火焰原子吸收光谱法直接测定蓄电池用H2SO4中的Fe含量。在选定的仪器测定条件下,采用标准加入法所测得的蓄电池用H2SO4中的Fe含量与国标法所测得的结果相比较无显著性差异,检出限为0.060μg/mL(n=13),1.00μg/mL Fe标准溶液平行测定13次,所得吸光度的相对标准偏差为3.3%(n=13)。本法可应用于H2SO4样品中Fe的测定。