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81.
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Johansson A Håkansson M Jagner S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5311-5318
Stereochemically labile copper and zinc complexes with the N,N'-dimethylethylenediamine ligand (dmeda) have been shown to be promising precursors for the total spontaneous resolution of chiral covalent networks. (N,N')-[Cu(NO3)2(dmeda)]infinity crystallises as a conglomerate and yields either enantiopure (R,R)-1 or enantiopure (S,S)-1. A mixed-valence copper(I/II) complex, [{Cu(II)Br2(dmeda)}3(Cu(I)Br)2]infinity (2), which crystallises as a pair of interpenetrating chiral (10,3)-a nets, is formed from CuBr, CuBr2 and dmeda. One net contains ligands with solely (R,R) configuration and exhibits helices with (P) configuration while the other has solely (S,S)-dmeda ligands and gives rise to a net in which the helices have (M) configuration. The whole crystalline arrangement is racemic, because the interpenetrating chiral nets are of opposite handedness. With zinc chloride (R,S)-[ZnCl(dmeda)2]2[ZnCl4] (3) is obtained, which is a network structure, although not chiral. Total spontaneous resolution of stereochemically labile metal complexes formed from achiral or racemic building blocks is suggested as a viable route for the preparation of covalent chiral networks. Once the absolute structure of the compound has been determined by X-ray crystallography, a quantitative determination of the enantiomeric excess of the bulk product can be undertaken by means of solid-state CD spectroscopy. 相似文献
83.
Changes in the stability of the cadmium(ii) ethylenediamine complexes in mixed water—DMSO solvents were studied by pH-metry and calorimetry. Complex cations [Cd(en)]2+, [Cd(en)2]2+, and [Cd(en)3]2+ are formed in aqueous solutions, and the [Cd(en)4]2+ complex with a partially dentate ligand is stable in DMSO. An increase in the DMSO content in a solvent increases the stability of the complexes. The maximum increase in logK is observed for coordinatively saturated compounds. The thermodynamics of complexation is discussed from the viewpoint of solvation approach. Principal differences in the influence of aqueous-alcohol and aqueous-aprotic solvents on the stability of the metal amino complexes were revealed. Protolytic solvents exert a destabilizing effect on the multiligand complexes, because the coordination sphere is involved in H bonding. 相似文献
84.
E.?BertoloEmail author J.?A.?Kilner M.?Sahibzada 《Journal of Solid State Electrochemistry》2004,8(9):585-591
18O/16O isotope exchange depth profiling (IEDP) combined with secondary ion mass spectrometry (SIMS) has been used to measure the oxygen tracer diffusivity of SrCe0.95Yb0.05O3– between 800 °C and 500 °C at a nominal pressure of 200 mbar. The values of D* (oxygen tracer diffusion coefficient) and k (surface exchange coefficient) increase steadily with increasing temperature, and the activation energies are 1.13 eV and 0.96 eV, respectively. Oxygen ion conductivities have been calculated using the Nernst–Einstein equation. The transport number for oxide ions at 769 °C, the highest temperature studied, is only ~0.05. Moreover, SrCe0.95Yb0.05O3– has been studied using impedance spectroscopy under dry O2, wet O2 and wet H2 (N2/10% H2) atmospheres, over the range 850–300 °C. Above ~550 °C, SrCe0.95Yb0.05O3– shows higher conductivity in dry O2 than in wet O2 or wet H2; below that temperature the results obtained for the three atmospheres are comparable. Dry O2 shows the highest activation energy (0.77 eV); the activation energies for wet O2 and wet H2 are identical (0.62 eV).Abbreviations HTPC high-temperature proton conductor - IEDP isotope exchange depth profiling - SIMS secondary ion mass spectrometryPresented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
85.
超微孔材料具有1~2 nm的孔径,在分离、催化应用中有望展现出择形催化的能力。 寻找经济、简便的合成超微孔材料的表面活性剂体系是一项有意义的工作。 本研究以短链季铵盐(十烷基三甲基溴化铵,记为C10TAB)和不同链长脂肪酸酸盐混合胶束为模板剂,硅酸钠为硅源,成功制备出高度有序超微孔SiO2。 通过小角X射线衍射、N2吸附-脱附、傅里叶变换红外光谱、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对产品的结构和性能进行了表征。 结果表明,合成体系中脂肪酸盐碳链长、加入量、晶化温度等对产物孔道有序性有很大影响。 当选择正辛酸钠(SO)为助表面活性剂,当n(C10TAB):n(Na2SiO3):n(SO):n(H2O)=1:1.5:0.3:800,晶化温度为80 ℃时,可以得到高度有序超微孔SiO2。 煅烧后样品比表面积为1300 m2/g,孔体积0.49 cm3/g,孔径分布在1.90 nm。 相似文献
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87.
The effect of B2O3 addition on the crystallization of amorphous TiO2-ZrO2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO2-ZrO2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO2-ZrO2 into a crystalline ZrTiO4 compound, while a larger amount of boria (?8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO4 units delay, while a build-up of trigonal BO3 promote, the crystallization of amorphous TiO2-ZrO2 to form ZrTiO4 crystals. 相似文献
88.
本文以多种聚醚为软段,二异氰酸酯(MDI和TDI)为硬段,合成了多嵌段聚醚聚氨酯,以此聚氨酯为基材,与NaH及1,3-丙碳酸内酯反应,进一步合成了一系列不同离子化程度的阴离子型碳化聚氨酯离聚物,用交流阻抗谱仪测定了样品的阻抗谱,由此计算出样品的离子电导率。研究结果表明其他条件相同时,以聚乙二醇(PEG)为软段的样品具有较高的离子电导率;以聚环氧丙烷(PPO)为软段的样品次之,以聚四氢呋喃(PTMO)为软段的样品最低,对于离子化程度不同的聚氨酯离聚物以金属离子和烷氧单元之比为0.05时导电性能最好。阳离子为Li+和Na+的样品具有相近的离子电导率。 相似文献
89.
以水滑石及类水滑石为前体的Mg/Al、Co/Al及Co/Mg/Al混合氧化物的合成、表征和异丙醇催化性能 总被引:11,自引:0,他引:11
以共沉淀法合成的水滑石(HT)和类水滑石(HTLc)为前体制备了镁铝、钴铝、钴镁铝混合氧化物,采用了BET、XRD、TG-DTA、TPR、FTIR和微量量热吸附及异丙醇催化反应进行了研究。结果表明:以HT和HTLc为前体制备的混合氧化物,其比表面积较大、并随着钴含量的增加而降低。在HT中引入Co2+离子后,由于Co2+离子的氧化还原属性,削弱了水滑石层对阴离子的键合能力,从而使其热分解温度及热稳定性降低,导至焙烧后生成的混合氧化物的比表面积比不含钴的2Mg/Al混合氧化物的低。在TPR过程中,镁铝混合氧化物不被还原,而含钴的混合氧化物的还原是经由Co3+ → Co2+ → Co0的过程。混合氧化物表面含有酸性位和碱性位,并随着钴含量的变化而得到调变。含钴氧化物样品的表面以L酸为主和含有很少量的B酸。异丙醇催化反应生成丙酮的选择性最高,表明样品表面的氧化还原位是主要的,随着钴的加入及含量的增大,异丙醇催化反应的转化率也是增大的。 相似文献
90.