基于不确定控制理论的最优策略研究

本文在不确定理论的框架下,研究一类带背景状态变量的最优控制模型.在乐观值准则下,利用不确定动态规划的方法,证明了不确定最优性原则,得到最优性方程.作为应用,求解一个固定缴费(DC)型养老金的最优投资策略问题,在乐观值准则下,以工资变量为背景状态变量,建立养老金模型.通过求解不确定最优性方程得到最优投资策略和最优支付率.     

减压扩散高阻密栅技术应用研究

本文对减压扩散机理及高阻密栅技术作了详细的分析,并就设备及工艺方面的关键技术进行了阐述,最后对减压扩散高方阻工艺及密栅匹配技术电池效率进行了对比分析,有以下结论:(1)减压扩散在工艺优化后,方阻均匀性得到大幅改善,达到3;以内.(2)减压扩散电池效率完全可达到常规产线的水平,且在高阻密栅方面更有优势,可有效提升太阳电池效率.     

零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Cu2O/TiO2-Bi2WO6三元复合催化剂的制备及光催化性能研究

采用水热法制备花状Bi2 WO6,并利用超声分散法制备了Cu2 O/TiO2-Bi2 WO6复合光催化剂,通过FESEM、XRD、XPS、FI-IR、UV-vis DRS和PL对光催化剂进行了分析和表征.表征结果证明:花状Bi2 WO6表面负载着碎片状的TiO2和立方体Cu2 O形成Cu2 O/TiO2-Bi2 WO6复合光催化剂;以短链脂肪酸(SCFAs)为牺牲剂,考察复合光催化剂的光催化产生氢气和烷烃的性能.实验结果表明:Cu2 O/TiO2-Bi2 WO6复合光催化剂以乙酸为牺牲剂,主要产氢气和甲烷,降解率高达91.82;;以丙酸为牺牲剂,产物主要是乙烷和丁烷,降解率高达90.70;;以丁酸为牺牲剂,除了氢气,甲烷,乙烷,丙烷,丁烷外,气体产物还含有一定量的戊烷,其降解率高达91.50;.结合反应液中间产物的成分进行检测,由此推断出光催化反应的可能机理.     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

锡苯和铅苯二聚反应的理论研究

采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯.