类球形正交LiMnO2的制备、微结构和电化学性能

以共沉淀法得到的类球形MnCO₃为前驱物，制备了类球形正交LiMnO₂(So-LiMnO₂)，采用XRD、SEM和N₂吸附技术对样品进行表征；与非球形正交LiMnO₂(No-LiMnO₂)进行了对比研究。结果表明：o-LiMnO₂的堆垛层错度、结晶状况、颗粒形貌和大小与前驱物的微结构密切相关；在80次电化学循环测试过程中，So-LiMnO₂经15次循环可达最大的放电容量152 mAh·g^-1，其容量衰减平均每次循环0.58 mAh·g^-1；而No-LiMnO₂要经过38次循环才能达到最大放电容量128 mAh·g^-1，容量衰减平均每次循环高达1.24 mAh·g^-1。TEM和EDS分析证明：由一次粒子团聚的类球形So-LiMnO₂能有效地抑制电解液对材料的腐蚀、减少Mn的溶解，从而提高了电化学循环能力。     

SrTi0.9M0.1O3-δ钙钛矿型氧化物催化剂甲烷氧化偶联反应性能的研究

The structure and catalytic properties of SrTi_0.9M_0.1O_3-δ (M=Mg，Al， Zr) perovskite-type catalysts for ox-idative coupling of methane (OCM) have been studied by using X-ray diffraction (XRD)，X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of oxygen(O₂-TPD) methods. It has been shown that doping the cations of lower valence (e.g. Mg²⁺， Al³⁺) to the B site of SrTi_0.9M_0.1O_3-δ perovskite-type catalysts results in the higher content of adsorbed oxygen species on the surface of catalysts and thus higher C₂-selectivity for OCM reaction. It is suggested that the oxygen vacancies of SrTi_0.9M_0.1O_3-δ (M=Mg， Al， Zr) perovskite-type catalysts are the sites responsible for oxygen activation， and the adsorbed oxygen species on the surface of SrTi_0.9M_0.1O_3-δ catalysts are the main active species for OCM reaction.     

Electrochemical Impedance Analysis of Thermogalvanic Cells

Thermogalvanic cells(also known as thermo-electrochemical cells) that convert waste heat energy to electricity are a new type of energy conversion device. However, the electron transfer kinetics and mass transfer of redox couples have not been thoroughly studied. Here, the ion reaction and charge transport in thermogalvanic cells are investigated by electrochemical impedance analysis. We first propose the detailed impedance model followed experimental verification on three types of electrode materials. Parameters including kinetic rate constants and ion diffusion coefficients for the electrodes are obtained by fitting the impedance data. Our study shows explicitly that impedance analysis can provide useful information on selecting suitable electrode materials for thermogalvanic cells.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

本文通过对TiCl_3-Al(C_2H_5)_3聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-l-phenyl-l-propanone with borane catalyzed by (S)-4-benzyl-5,5-diphenyl-l,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step Ⅲ exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-l-phenyl-l-propanone spontaneously, resulting in the need of 2 tool BH3 in the reaction.     

CHEMOTHERAPEUTIC POLYMERS Ⅻ. SYNTHESIS AND ANTITUMOR ACTIVITY OF POLYAMIDES CONTAINING 5-FLUOROURACILS AS PENDANT GROUP

Six polyamides with pendant 5-fluorouracil group were synthesized by the polycondensation ofdi-p-nitrophenyl N-(5-fluorouracil-1-acetyl)glutamate with a series of polymethylene diamines.All of the new polyamides obtained are soluble in water. Their chemical structures were confirmedby ~1H NMR, UV and IR spectra as well as elemental analyses. The antitumor activity of some ofthese polyamides were tested against Ehrlich Ascites Carcinoma in mice, III_a showed an inhibitionrate of 43%.     

壁电荷对ACPDP中气体击穿电压的影响

用电容平衡法测量ACPDP宏放电单元在维持放电期的壁电荷变化,并根据宏放电单元壁电荷电压和外加最小维持电压的测量结果计算实际施加在放电气体上的击穿电压,探讨壁电荷电压对放电气体实际击穿电压的影响.实验结果表明:随着ACPDP外加最小维持电压的增加,壁电荷电压升高,气体的击穿电压也随之升高;有壁电荷时的气体击穿电压明显高于无壁电荷时的气体击穿电压,随着壁电荷电压从7.62 V升高到67.89 V,有壁电荷时的气体击穿电压比无壁电荷时的气体击穿电压分别提高了6.98 V到57.09 V;壁电荷增加会显著提高了放电气体的击穿电压阈值,使ACPDP内放电气体的击穿变得困难.     

论温泉旅游的创新开发

近年来，温泉旅游发展迅速，但温泉旅游开发模式和活动项目的雷同化现象十分严重，从社会需求、温泉产品形象、温泉设计理念、温泉经营管理等方面都要求对温泉进行创新开发，温泉旅游开发的创新途径是主题创新、表现形式创新、内容创新和管理创新，只有这样温泉旅游才能可持续发展。