金属-氧化物界面中的金属-载体强相互作用及其对贵金属-氧化铈负载型催化材料性质调控的研究进展

从金属-氧化物界面出发,分析了金属-氧化物相互作用的两个决定因素——界面电荷迁移过程和界面物质输运过程。简要介绍了金属-载体强相互作用的发现过程和研究成果,对于金属间成键、特殊形貌结构、界面电荷迁移和界面物质输运这四种常见的金属-载体强相互作用的机制进行了讨论。最后介绍了典型的金属-载体强相互作用体系——贵金属-氧化铈负载型催化剂体系,以及最近在该体系中所取得与金属-载体相互作用相关的研究进展。     

扩散模型和凝聚模型耦合作用下胶体凝聚动力学的Monte Carlo模拟研究

以扩散模型(Ds(γ)=D0×sγ)和凝聚模型(Pij(σ)=P0×(i×j)σ)为基础,对胶体体系随时间的演变、团簇大小分布及其标度关系、团簇的重均大小S(t)的变化规律以及模型对最终分形维数的影响四个角度进行了比较研究,发现扩散指数γ0和凝聚概率指数σ0对胶体的凝聚动力学过程有相似的影响.本文在较宽的γ和σ取值范围内,对胶体的凝聚动力学进行了模拟研究,对慢速凝聚向快速凝聚的转化机理作了定量分析,并进一步分析了在团簇-团簇凝聚(CCA)模型下,得到类似扩散置限凝聚(DLA)模型的凝聚体的物理意义,结果表明:(1)γ0代表了体系中团簇或单粒做"定向运动"而非无规则的布朗运动的情况.这种"定向运动"的推动力可能来自于大团簇产生的强"长程范德华力"、"电场力"等,或来自于体系边界处的外力场的作用.(2)当σ0时,体系成为先快后慢的慢速凝聚,这可能对应大团簇为一排斥中心,即胶体颗粒存在"排斥力场"的现象.(3)证实了团簇的重均大小在凝聚过程的早期按指数规律增长,而后期按幂函数规律增长的实验现象.模拟研究还表明,胶体体系的凝聚动力学过程,在σ0时是一个存在正反馈机制的非线性动力学过程,而在σ0时则体现出负反馈的特征.     

蔗渣木聚糖微观结构的分子动力学模拟

在对木聚糖来源及其结构进行分类比较的基础上,采用分子动力学模拟方法及Materials Studio 4.0软件对蔗渣木聚糖及木糖单元等进行微观模拟计算.通过原子净电荷、电子密度和Fukui函数分析等分析方法,对蔗渣木聚糖的木糖单元进行结构优化,得到了蔗渣木聚糖的木糖单元优化构型的键长、键角和电荷密度.木糖单元原子的Hirshfeld净电荷与Fukui函数分析数据表明,木糖单元的活性中心主要在C(3)上的羟基位置,且羟基氧原子易受亲电试剂的攻击,羟基氢原子易受亲核试剂的攻击.对蔗渣木聚糖单分子链及无定形结构进行模拟,得到了蔗渣木聚糖的微观结构模型,显示蔗渣木聚糖分子具有链状结构,大致呈螺旋状.获得了蔗渣木聚糖的最优化无定形结构,并通过计算得到了其最优化无定形结构的X射线衍射图谱.研究结果为系统探讨蔗渣木聚糖及其衍生物的结构与性能关系奠定了基础.     

酚类衍生物催化加氢合成酮和醇的研究进展

正酚类衍生物是生物质木质素的模型化合物,也是煤焦油中的重要馏分和废水中的有害物质,通过酚类衍生物催化加氢可以制备环己酮和环己醇,产物环己酮和环己醇(KA油)是合成纤维尼龙6及尼龙66的单体己内酰胺和己二酸的重要原料,同时也是医药、染料等精细化学品的重要中间体[1].因此,酚类衍生物催化加氢制备环己酮和环己醇具有重要的科学意义和应用前景[2-3].目前,生物圈含木质素3×1010t左右,每年再生2×1010t.木质素也     

噻唑类缓蚀剂与青铜器表面粉状锈相互作用的理论研究

利用密度泛函(DFT)、概念DFT和自然键轨道理论(NBO)分析了3种常见的噻唑类缓蚀剂5-氨基-2-巯基-1,3,4-噻二唑(AMT)、3-氨基-5-巯基-1,2,4-三氮唑(ATA)和5-乙酰氨基-2-巯基-1,3,4-噻二唑(MAcT)及其与青铜器表面粉状锈中CuCl2作用后形成配合物X(X=Ⅰ-Ⅲ)的结构和反应性能.通过计算研究发现,AMT的缓蚀活性最强,与CuCl2之间的相互作用能最大,所形成配合物Ⅰ的二级稳定化能Eij(2)为603.37kJ·mol-1,并且配合物Ⅰ的反应活性最强,相互间形成聚合物的可能性最大.     

Lithium ion conduction and ion-polymer interaction in poly（vinyl pyrrolidone） based electrolytes blended with different plasticizers

Poly（ethylene oxide）, poly（vinyl pyrrolidone）（PEO/PVP）, lithium perchlorate salt（Li Cl O4） and different plasticizer based, gel polymer electrolytes were prepared by the solvent casting technique. XRD results show that the crystallinity decreases with the addition of different plasticizers. Consequently, there is an enhancement in the amorphousity of the samples responsible for the process of ion transport. FTIR spectroscopy is used to characterize the structure of the polymer and confirms the complexation of plasticizer with host polymer matrix. The ionic conductivity has been calculated using the bulk impedance obtained through impedance spectroscopy. Among the various plasticizers, the ethylene carbonate（EC） based complex exhibits a maximum ionic conductivity value of the order of2.7279 10 4S cm 1. Thermal stability of the prepared electrolyte films shows that they can be used in batteries at elevated temperatures. PEO（72%）/PVP（8%）/Li Cl O4（8%）/EC（12%） has the maximum ionic conductivity value which is supported by the lowest optical band gap and lowest intensity in photoluminescence spectroscopy near 400–450 nm. Two and three dimensional topographic images of the sample having a maximum ionic conductivity show the presence of micropores.     

中国财产保险公司经营效率评价及影响因素:基于CCR-BCC和Malmquist的DEA-Tobit模型北大核心

作为现代金融体系的重要组成部分,保险业的发展程度直接关系到金融业能否稳定健康发展.运用基于DEA的CCR模型、BCC模型和Malmquist指数法以及DEA-Tobit模型对2008-2011年中国36家财产保险公司经营效率及影响因素进行了实证分析,研究表明:1)从综合技术效率角度分析,达到DEA有效的保险公司数目从08年的5家上升到09年的9家,且在以后年份保持稳定数目.从静态效率均值角度分析,中国财产保险公司效率不高,各保险公司之间的差异不大.2)四年间中国财产保险公司经营效率普遍较低,然而技术进步却是提高保险公司经营效率的有效方法.3)公司经营能力与静态效率水平各分解项存在显著正相关,资本规模则与其存在显著负相关,职工素质、赔付能力及公司经营管理费用对静态效率水平各分解项影响显著性不强.     

Low generational polyamidoamine dendrimers to enhance the solubility of folic acid:A‘‘dendritic effect’’investigation

Low generational(G0–G2,G for generation) polyamidoamine(PAMAM) dendrimers were investigated as enhancers to improve the aqueous solubility of folic acid at pH 11 and pH 5.In these two cases,the solubility of folic acid increases with both the dendrimer concentration and generation.However,the solubilization mechanism is different.The electrostatic interaction between the primary amines of dendrimers and the ionized carboxylic groups of folic acid dominates the dissolution process at pH 11 while the increase of the solubility of folic acid at pH 5 is attributed to the hydrophobic encapsulation inside the dendrimer molecules.In addition,for comparison ethylenediamine was used as a small molecule control to examine the ‘‘dendritic effect' in the dendrimer-related solubilization process.Interestingly,PAMAM dendrimers exhibit,at pH 5,a significant superiority over ethylenediamine in enhancing solubility,whereas this ‘‘dendritic effect' cannot be observed under the basic condition.     

Synergistic effect of W and P on ZSM-5 and its catalytic performance in the cracking of heavy oil

In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Characterization results show that the improvement of catalytic performance could be correlated to the interaction of phosphorus and tungsten species on ZSM-5. P inhibited the aggregation of tungsten species on ZSM-5 and was conductive to convert the tungsten species with octahedral coordination into tetrahedral coordination. And this ultimately led to that more acid sites were reserved after hydrothermal treatment in the tungsten and phosphorus co-modified ZSM-5 catalyst. Phosphorus species played an important role to restrain the dehydrogenation activity of tungsten. In addition, a model reflecting the interaction between tungsten species and ZSM-5 framework was proposed.     

Performance of Co/MgO catalyst for C02 reforming of toluene as a model compound of tar derived from biomass gasification

Catalytic performances of the CO2 reforming of toluene on Co/MgO catalysts with different cobalt loadings were evaluated in a fluidized-bed reactor. The results showed that the conversion of toluene and the stability of Co/MgO increased, but the apparent reaction rate decreased at the initial stage with increasing the amount of metallic Co formed from the reduction of Co/MgO catalysts at 700 ~C. The deactivation of Co/MgO catalysts was mainly resulted from that a part of the metallic Co was oxidized by CO2 and could not be re-reduced by H2 at reaction temperature. Therefore, the excess metallic Co on the higher Co loading catalysts was beneficial to the catalyst stability.