LiCoO2中锂离子固相扩散系数随循环次数的变化

The solid diffusion coefficient of lithium-ion in LiCoO₂ cathode material has been investigated by the capacity intermittent titration technique (CITT) at different voltages and at different charge/discharge cycles. By SEM, XRD and FTIR techniques, the structure of LiCoO₂ was studied before and after charge-discharge cycles, and the relationship between solid diffusion coefficient and crystal structure was further discussed. CITT results show that the value of Li⁺ solid diffusion coefficient of LiCoO₂ is about 10^-12 cm²·s^-1. During the whole charge-discharge cycles, the Li⁺ solid diffusion coefficient decreased within the voltage of 4.0～4.3 V, which is attributed to the change of the structure of LiCoO₂.     

铁－铜－锰氧化物／海泡石催化剂对苯羟基化为苯酚的催化作用

铁－铜－锰氧化物／海泡石催化剂对苯羟基化为苯酚的催化作用曹声春，黄孟光，李克，杜兴军（湖南大学化工系，长沙４１００８２）关键词氧化铁，氧化钢，二氧化锰，海泡石，负载型催化剂，苯，羟基化，苯酚由苯合成苯酚的现行方法存在着反应步骤多，工艺过程复杂，总转化...     

微波场中甲烷部分氧化制合成气 Ⅱ.Co/ZrO_2催化剂在微波场中的升温行为及催化活性

近年来，甲烷部分氧化制合成气（ＰＯＭ）的研究一直十分活跃［１，２］．前文报道了用于甲烷部分氧化制合成气的镍基催化剂（Ｎｉ／Ｌａ２Ｏ３）在微波场中的升温行为和催化活性［３］，发现在达到相同的ＣＨ４转化率时，微波活化方式下的催化剂床层温度比常规加热低得多...     

WOx/TiO2光催化剂的可见光催化活性机理探讨

采用磁控溅射技术在用浸渍提拉法制得的TiO2薄膜上，溅射氧化钨层,通过气相反应中光催化降解二甲苯的实验表明，WOx/TiO2薄膜具有可见光活性.通过UV-Vis吸收光谱、X射线光电子能谱（XPS）等方法对其可见光活性的机理进行探索.UV-Vis吸收光谱表明WOx,TiO2对可见光响应的范围有一定的扩展,吸收强度增加.XPS表明WOx/TiO2薄膜表面形成了明显的W杂质能级和Ti缺陷能级,这是WOx/TiO2在可见光范围有一吸收的主要原因,也是光催化剂具有可见光活性的必要条件之一，同时杂质能级的存在使半导体费米能级上移,载流子增加,光催化效率提高.     

Photografting of vinyl polymers onto ultrafine inorganic particles: Photopolymerization of vinyl monomers initiated by AZO groups introduced onto these surfaces

The photografting of polymers onto ultrafine inorganic particles, such as silica and titanium oxide, initiated by azo groups introduced onto these surfaces was investigated. The introduction of azo groups onto the particles was achieved by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with surface isocyanate groups, which were introduced by the treatment with tolylene 2,4-diisocyanate. It was found that the photopolymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole, is initiated by ultrafine particles having azo groups. The corresponding polymers were effectively grafted onto these surfaces through the propagation of the polymer from the surface radicals formed by the photodecomposition of the azo groups: e.g., the percentage of grafting of PMMA and polystyrene onto silica was reached to 112 and 176%, respectively. The percentage of grafting onto silica in the graft polymerization initiated by photodecomposition of surface azo groups was much larger than that initiated by thermal decomposition. Polymer-grafted ultrafine particles thus obtained gave a stable colloidal dispersion in good solvents for the grafted chain. © 1994 John Wiley & Sons, Inc.     

VA族元素对阳极铅(Ⅱ)氧化物膜半导体性质的影响(Ⅱ)

用光电化学电流法研究了铅、铅砷、铅锑和铅铋合金在4．5mol·L－1H2SO4溶液（22℃）中，以0．9V（vs．Hg／Hg2SO4）极化7h而形成的阳极膜中的氧化铅的半导体性质，合金添加剂砷、锑和铋对t－PbO（四方氧化铝）和o-PbO（斜方氧化铝）的禁带宽度没有影响，从量子效率和电位的关系可求Pb，Pb－lat％As（at％表示原子百分比，全文同），Pb-lat％Sb和Sb－lat％Bi上膜中t－Pbo的施主密度（ND）分别为9．3×1015，1．0×1016，3．1×1016和1．3×1017cm-3，平带位分别为-0．20，－0．22，－0．28和-0．08V（vs．Hg／Hg2SO4）．比较VA元素砷、锑和铋对上述膜中t－Pbo的ND（从而自由电子密度）和膜中t－Pbo的生长速率的影响，可认为法添加剂砷、锑和铋对阳极膜中t-Pbo的作用符合Hauffe规则．     

Ni-SDC固体氧化物燃料电池阳极的合成和性质

采用柠檬酸-硝酸盐溶胶-凝胶低温自蔓延燃烧法制备氧化镍（NiO）粉末和Ce0.8Sm0.2O1.9（SDC）粉末，并将NiO与SDC按不同质量比和不同制备工艺制备了固体氧化物燃料电池（SOFC）的阳极前身。再用自组装的还原装置将其在820℃经2．5h还原后，采用四端子法测量其电导率值。分析了阳极片电导率与阳极片微结构、Ni的质量百分数、混合研磨时间及烧结温度之间的关系。结果显示，阳极片的电导率强烈依赖于镍含量和制备工艺。     

Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

氧化苯乙烯和氧化二苯乙烯的区域选择性和立体选择性开环

本文报道 NaBH_4-CoCl_2可使氧化苯乙烯类化合物发生区域选择性开环,主要生成β-苯乙醇衍生物。对于氧化二苯乙烯类化合物,由于受到苯环的空间阻碍,使其开环能力减弱,如反式氧化二苯乙烯比顺式异构体更难于开环。