α, α'-二胺基二苄基硒醚的合成

本文以苯骈三氮唑、胺和苯甲基醛为原料,发现Mannich反应,生成胺烷基化的苯骈三氮唑衍生物。在此衍生物中,苯骈三氮唑基是亲核取代反应的良好离去基团,易被强亲核试剂的硒负离子取代,生成对称α,α'-二胺基二苄基硒醚。反应易进行,产率较高,产物均为固体,易提纯。这是合成含氮原子的对称硒醚的较好方法。     

微波辅助RGD环肽的固相合成

以2-氯代三苯甲基氯树脂为载体，采用Fmoc/t-Bu/Dmab正交保护策略，在微波辅助下合成了环肽c(fKRGD)，收率22.5%，纯度94.5%，其结构经MS(ESI), MS(MALDI-TOF)和HPLC确证。     

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.     

磺酰胺类常咯啉的分子力学参数的确定

应用量子化学ＭＮＤＯ程序及分子力学ＭＭＰ２程序，确定了一些未知磺酰胺类常咯啉的分子力学参数。应用这些参数计算了几个晶体结构已知的磺酰胺类化合物，与真实结构比较，计算结果令人满意。由此说明确定的分子力学参数用于计算磺酰胺类化合物时的正确性和可行性。     

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.     

耐晒大红BBN与表面活性剂双组分光催化降解

以表面活性剂十六烷基三甲基溴化铵(CTAB)和难溶有机颜料耐晒大红BBN(简称BBN)为双组分降解底物, 以TiO2为光催化剂, 研究双组分底物的光催化降解的快慢及规律, 双组分降解的相互影响, 初步建立双组分和催化剂之间的作用模型. 结果表明, pH值及底物的浓度对双组分体系的降解都有显著影响, 碱性条件更适合体系的降解, 在中性(pH=6.8)环境中两种底物的降解效果明显高于单组分的降解. 在碱性条件下(pH=9.2), 加入BBN使CTAB的降解速率略有下降. CTAB的浓度对BBN褪色速率影响较大, 当CTAB 的浓度为1 cmc 时, BBN和CTAB的降解速率都达到最快. BBN在TiO2表面吸附性强, 且被优先降解.     

红外反射及红外—光声光谱法对青铜生锈过程的研究

在自制Cu-Sn-Pb合金表面上进行盐酸腐蚀,用红外反射及红外-光声光谱方法监测粉状锈(Cu_2(OH)_3Cl)的生长过程。结果发现,在酸性环境中Cu_2(OH)_3Cl生长迅速;二价铜锈的生成需通过一价铜锈(CuCl)这一中间产物;粉状锈有传染性,可通过空气由锈蚀样品传至无锈样品,锈体颗粒对光线的散射作用强,结合热力学计算对青铜生锈机理进行了探索。     

Synthesis of Two Novel Rhenium（I） Bipyridyl Photosensitive Dyes

Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN.     

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.