基于金属复分解闭环反应合成新型杯[4]冠醚衍生物

杯[4]芳烃的上端和下端通过金属复分解闭环反应以较高产率合成一系列新型杯[4]冠醚衍生物(8a-c),目标产物结构经元素分析、IR、MS、1H NMR及13C NMR证实。     

高效液相色谱法研究H_2O_2氧化Na_2S_2O_3的反应动力学

建立了反相离子对高效液相色谱法对H2O2-Na2S2O3反应体系的反应物和中间产物进行了分离检测方法,并对此反应体系在酸性条件下的氧化反应动力学做了研究.结果表明:在25℃,pH 4.76时硫代硫酸盐氧化过程中出现的产物有:亚硫酸盐、连三硫酸盐、连四硫酸盐、连五硫酸盐、连六硫酸盐、连七硫酸盐和硫酸根,pH越低越易生成更高的连多硫酸盐;在氧化H2O2过量的情况下反应对硫代硫酸盐来说为一级反应,并测得了准一级反应速率常数.     

金属氯化醇盐的红外光谱分析

金属氯化醇盐作为一种溶胶．凝胶法新型前驱体,其分子结构较为复杂,但关于它们结构的红外光谱分析却很少。为此,文章分别对四氯化钛和三氯化铝与乙醇、异丙醇及正丁醇的反应产物——金属氯化醇盐进行了红外光谱测试分析。结果发现,由于四氯化钛中钛的反应活性参数Rn较小,同时三氯化铝中离子键较少,因此,它们与醇之间只发生了部分亲核取代反应,导致产物中残余一定量的Ti-Cl和Al-Cl键合,即反应产物为铝、钛氯化醇盐,这样造成铝氯化醇盐的红外图谱中存在Al-Cl键合振动吸收峰,而钛氯化醇盐中C-O-Ti键合的C-O伸缩振动吸收峰峰位也明显有别于纯的金属钛醇盐。     

含CL-20的改性双基推进剂的热行为及非等温反应动力学

用DSC和TG方法研究了含六硝基六氮杂异伍兹烷(CL-20)的改性双基推进剂在常压(0.1 MPa)和高压(4和7 MPa)下的热行为和高压下的热分解反应动力学. 结果表明, 该推进剂常压下DSC曲线有3个放热峰, 相应TG曲线有3个失重过程; 而高压下DSC曲线只有一个放热峰, 高压下放热峰的峰温随加热速率增大而升高. 高压下该推进剂放热分解反应机理和反应动力学参数受测试环境压强影响较弱, 反应机理是随机成核和随后生长, 放热分解反应的动力学方程可以表示为, 4 MPa时, dα/dt=1014.5(1-α)[-ln(1-α)]1/3e-17981.7/T; 7 MPa时, dα/dt=1014.7(1-α)·[-ln(1-α)]1/3e-18138.1/T.     

SO2在Fe2O3颗粒表面不同温度下非均相反应的实验模拟

使用漫反射Fourier变换红外光谱(DFTIRS)、离子色谱(IC)及透射电子显微镜(TEM)对不同温度条件下SO2在α-Fe2O3颗粒表面的非均相反应过程进行实验模拟和监测,并分析了反应剧烈波段(8.7μm)的产物硫酸盐以及颗粒吸收和后向散射光学系数的变化.结果表明,在15-45℃内,硫酸盐生成量、生成速率以及吸收系数、后向散射系数都随反应温度的升高而呈现先增加后减少的趋势;同一反应温度下,硫酸盐生成速率随时间呈现先增大后减小,最后逐渐趋于稳定的演变;光学系数变化与硫酸盐生成量之间存在较好的指数关系.在当前全球气候变暖背景下,研究结果将对深入了解真实大气中SO2与矿尘非均相反应造成的气溶胶光学特性演变,以及定量评估其辐射强迫影响具有一定意义.     

Study on Ni/C catalysts for vapor phase carbonylation of ethanol

Activated carbon-supported Ni catalysts for vapor phase carbonylation of ethanol to propionic acid in the presence of ethyl iodide as promoter were investigated. Under optimum reaction conditions, the conversions of carbon monoxide and ethanol were measured to be 81.4% and 98.4%, respectively, while the selectivity for propionic acid was found to be 98.65%. The catalyst was stable within 48 h on stream. XRD and XPS methods were used to characterize the structures and surface properties of the fresh and tested catalysts. The characterization results indicated that aggregation of nickel particles and formation of nickel iodide on the catalyst surface should be responsible for the deactivation of the catalysts.     

铁催化杂原子邻位C—H键氧化活化直接构筑C—C键

铁催化剂具有无毒和价廉易得等优点,因此,发展铁催化的有机合成反应具有环境友好和潜在的工业应用价值．C—H键的直接官能团化是目前化学研究领域的重点和热点之一,受到广泛的关注．在有机合成化学研究领域,通过C—H键的氧化形成C—X（杂原子）键已有很多报道,但是通过C—H键的氧化偶联形成C—C键的报道并不是很多,     

Nitrogen Adatom Diffusion on a Ga－Rich GaN （0001） Surface

The diffusion of N adatoms on a Ga-rich GaN(O001) surface has been studied using density-functional theory.The configuration of Ga adatoms on a Ga-rich GaN surface has been identified. The first adlayer Ga adatoms are on top of the terminating substrate Ga atoms, and the outmost adlayer Ga adatoms exist randomly at the T4 or H3 sites. A very different diffusivity of N adatoms on a Ga-rich GaN(0001) surface has been found. The excess Ga adatoms on a GaN(0001) surface reduce the diffusion barrier by 0.75eV and influence the migration path. It seems that bilayer Ga adatoms are helpful for N atom diffusion.     

Pair correlations in scale-free networks

Correlation between nodes is found to be a common and important property in many complex networks. Here we investigate degree correlations of the Barabasi－Albert (BA) scale-free model with both analytical results and simulations, and find two neighbouring regions, a disassortative one for low degrees and a neutral one for high degrees. The average degree of the neighbours of a randomly picked node is expected to diverge in the limit of infinite network size. As a generalization of the concept of correlation, we also study the correlations of other scalar properties, including age and clustering coefficient. Finally we propose a correlation measurement in bipartite networks.     

The dynamical feature of transition of a Hamiltonian system to a dissipative system

The mechanism of generation and annihilation of attractors during transition from a Hamiltonian system to a dissipative system is studied numerically using the dissipative standard map. The transient process related to the formation of attracting basins of periodic attractors is studied by discussing the evolution of the KAM tori of the standard map. The result shows that as damping increases, attractors are mainly generated from elliptic orbits of the Hamiltonian system and annihilated by colliding with unstable periodic orbits originating from the corresponding hyperbolic orbits of the Hamiltonian system. The transient process also exhibits the general feature of bifurcation.