Li3PO4包覆LiMn2O4正极材料的结构表征和电化学性能

采用共沉淀法在尖晶石LiMn2O4颗粒表面包覆Li3PO4.XRD、SEM研究结果表明,包覆后的材料仍为尖晶石结构,粒径均匀.电化学性能测试表明,Li3PO4包覆层的存在,减少了正极材料与电解液的直接接触,抑制了高温下电解液对LiMn2O4材料的侵蚀,从而有效改善了高温下材料的循环性能.在40℃时,包覆样品的比容量衰减率都低于未包覆样品,其中包覆1%Li3PO4的样品的初始比容量为110.4mAh/g,50次循环后比容量为84.1mAh/g.     

氧化镍纳米晶体的制备及其过程分析

为了开发一种新型纳米氧化镍催化剂,能有效地应用于生物质气化过程中去除焦油,本文采用均匀沉淀法成功地制备了纳米氧化镍晶体,并利用TGA、FTIR、XRD、BET、YEM等分析手段对前驱体和产品的性能进行了表征.同时,对前驱体的分解过程进行了全面的分析.分析结果表明前驱体是水合碱式碳酸镍,其分子式为NiCO3·Ni(OH)2·nH2O,它能在360℃下完全分解转化为纳米NiO,同时煅烧条件对合成纳米NiO的晶体粒径影响很大.实验证实所得纳米NiO颗粒呈球形,分散性好,纯度较高,属立方晶系结构,平均粒径约为7.5nm,其BET表面积为187.98m2/g,这显示纳米NiO晶体具有作为高效催化材料的应用可行性.     

热丝和射频等离子体化学气相沉积法制备定向碳纳米管薄膜

采用热丝和射频等离子体复合化学气相沉积设备(PE-HF-CVD),以CH4、H2和N2为反应气体.在较低衬底温度下(500℃),用简单的催化剂制备方法--旋涂法在硅片上涂覆Ni(NO3)2溶液,经热处理及H2还原后的Ni颗粒为催化剂,在硅衬底上制备出了垂直于硅片且定向生长的碳纳米管薄膜.扫描电子显微镜(SEM)和透射电子显微镜(TEM)结果显示,1 mol/l的硝酸镍溶液旋涂硅片所得催化剂制得的碳纳米管管径为30～50 nm,长度超过4μm,定向性好.并用拉曼光谱(Raman)对不同摩尔浓度Ni(NO3)2溶液条件下制备的碳纳米管薄膜样品进行了表征.     

Co-Catalyzed Asymmetric Intramolecular [3+2] Cycloaddition of Yne-Alkylidenecyclopropanes and its Reaction Mechanism

Developing new transition metal-catalyzed asymmetric cycloadditions for the synthesis of five-membered carbocycles (FMCs) is a research frontier in reaction development due to the ubiquitous presence of chiral FMCs in various functional molecules. Reported here is our discovery of a highly enantioselective intramolecular [3+2] cycloaddition of yne-alkylidenecyclopropanes (yne-ACPs) to bicyclo[3.3.0]octadiene and bicyclo[4.3.0]nonadiene molecules using a cheap Co catalyst and commercially available chiral ligand (S)-Xyl-BINAP. This reaction avoids the use of precious Pd and Rh catalysts, which are usually the choices for [3+2] reactions with ACPs. The enantiomeric excess in the present reaction can be up to 92 %. Cationic cobalt(I) species was suggested by experiments as the catalytic species. DFT calculations showed that this [3+2] reaction starts with oxidative cyclometallation of alkyne and ACP, followed by ring opening of the cyclopropyl (CP) group and reductive elimination to form the cycloadduct. This mechanism is different from previous [3+2] reactions of ACPs, which usually start from CP cleavage, not from oxidative cyclization.     

Fluorinated α-Diimine Nickel Mediated Ethylene (Co)Polymerization

Fluorine substituents in transition metal catalysts are of great importance in olefin polymerization catalysis; however, the comprehensive effect of fluorine substituents is elusive in seminal late transition metal α-diimine catalytic system. In this contribution, fluorine substituents at various positions (ortho-, meta-, and para-F) and with different numbers (F_n; n=0, 1, 2, 3, 5) were installed into the well-defined N-terphenyl amine and thus were studied for the first time in the nickel α-diimine promoted ethylene polymerization and copolymerization with polar monomers. The position of the fluorine substituent was particularly crucial in these polymerization reactions in terms of catalytic activity, polymer molecular weight, branching density, and incorporation of polar monomer, and thus a picture on the fluorine effect was given. As a notable result, the ortho-F substituted α-diimine nickel catalyst produced highly linear polyethylenes with an extremely high molecular weight (M_w=8703 kDa) and a significantly low degree of branching of 1.4/1000 C; however, the meta-F and/or para-F substituted α-diimine nickel catalysts generated highly branched (up to 80.2/1000 C) polyethylenes with significantly low molecular weights (M_w=20-50 kDa).     

Hydrodechlorination of Dichloromethane by a Metal-Free Triazole-Porphyrin Electrocatalyst: Demonstration of Main-Group Element Electrocatalysis**

In this work, the electrocatalytic reduction of dichloromethane (CH₂Cl₂) into hydrocarbons involving a main group element-based molecular triazole-porphyrin electrocatalyst H2PorT8 is reported. This catalyst converted CH₂Cl₂ in acetonitrile to various hydrocarbons (methane, ethane, and ethylene) with a Faradaic efficiency of 70 % and current density of −13 mA cm⁻² at a potential of −2.2 V vs. Fc/Fc⁺ using water as a proton source. The findings of this study and its mechanistic interpretations demonstrated that H2PorT8 was an efficient and stable catalyst for the hydrodechlorination of CH₂Cl₂ and that main group catalysts could be potentially used for exploring new catalytic reaction mechanisms.     

相对论速调管放大器杂模振荡的抑制

研究了相对论速调管放大器（RKA）输入腔和中间腔之间的高阶杂模振荡问题。通过模式分析得知杂模在谐振腔内为TM11模式,而在漂移管中表现为TE11模式,针对该模式能在漂移管中传输的特性,利用漂移管内壁涂覆吸波材料吸收杂模功率的方法进行抑制。通过3维粒子模拟程序,分析了吸波材料的电导率及涂覆长度对抑制杂模增长率的影响。利用模拟分析得到的结果,对漂移管中涂覆吸波材料的RKA输入腔及中间腔结构进行了3维模拟研究,结果显示:合适的吸波材料的引入能够很好地抑制RKA输入腔和中间腔之间的杂模振荡。     

高功率TEA CO2激光器两波长激光切换输出技术

以TEA CO2激光器通常采用的平-凹光学稳定腔为基础,提出了一种新的波长选支方法——输出窗口镀膜选支方法。利用一台高平均功率TEA CO2激光器进行了选支实验研究,结合现有光学镀膜技术,得到了中心波长为9.3 μm的激光单谱线输出,其单脉冲能量及平均功率与激光器原中心波长10.6 μm单谱线输出的相应参数基本相当。研究发现,以相同单脉冲能量激光照射热敏纸时,中心波长9.3 μm激光光斑与中心波长10.6 μm的明显不同。同时,还设计出两波长窗口密闭免调切换装置,在一台激光器上实现了10.6,9.3 μm两个中心波长激光同等功率水平的免调切换输出,切换位置误差小于5″,密封性能满足使用要求。