锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的低温燃烧合成

以LiNO3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、CO(NH2)2为原料,通过低温燃烧法在空气中合成了锂离子正极材料LiNi1/3Mn1/3Co1/3O2.采用XRD研究了合成产物的物相与结构,用SEM研究了合成产物的形貌,考察了点火温度、回火温度,回火时间以及锂过量对合成产物电化学性能的影响.研究结果表明,合成产物与层状LiNiO2的结构相同,属α-NaFeO2型层状结构,合成产物的粒度较小且比较均匀,并具有良好的电化学性能.采用低温燃烧法在空气中合成LiNi1/3Mn1/3Co1/3O2的最佳条件为:500℃点火,850℃回火20h,锂过量为15mol%.在此条件下得到的合成产物首次放电比容量达到158.9mAh/g.     

三聚氰胺杂多酸盐的制备和性能研究

本文以三聚氰胺,磷钼钒酸和磷钼酸为原料在1.0mol/LHNO_3溶液中反应,合成了三聚氰胺磷钼钒酸盐(MPMV)和三聚氰胺磷钼酸盐(MPM)的结晶。经测定MPMV和MPM的分子式分别为3[C_3N_3(NH_2)_2NH_2·H]HPMo_(11)VO_(40)·nH_2O和[C_3N_3(NH_2)_2NH_2·H]H_2PMo_(12)O_(40)·nH_2O,MPMV和MPM结晶均属单斜晶系。对比了MPMV和MPM的离子交换特性和催化性能,表明MPMV和MPM对铯都有很高的离子交换选择性,K_d值分别为1198.7ml/g和4867ml/g,是从放射性废液中分离铯—137的处理材料和氧化还原型催化剂,是具有多功能性能的无机—有机材料。     

11-钨铬杂多阴离子层状材料的制备和表征及其光催化活性

采用离子交换法制备了具有Keggin结构11-钨铬三元杂多阴离子层状材料LDH-[Cu(H2O)W11Cr O39]7-,并利用红外光谱(IR)、X-射线衍射(XRD)和扫描电子显微镜配合X-射线能量色散谱仪(SEM-EDS)对其组成和结构进行了表征。结果表明:三元杂多阴离子[Cu(H2O)W11Cr O39]7-取代了粘土板层中的NO3-离子,并且仍然保留了Keggin结构。利用合成的层状材料LDH-[Cu(H2O)W11Cr O39]7-为催化剂,对孔雀石绿进行了光催化降解实验,确定了光降解反应的最佳反应条件.在最佳反应条件下,孔雀石绿的脱色率可达98.01%。并将层状材料与杂多酸盐和粘土的光催化活性进行了比较,其光催化活性顺序为:LDH-[Cu(H2O)W11Cr O39]7-K7[Cu(H2O)W11Cr O39]Zn2Al粘土。因此表明层状材料LDH-[Cu(H2O)W11Cr O39]7具有优异的光催化活性。     

精氨酸插层氧化锰纳米结构材料的制备和表征

应用氧化法水热合成了Na型层状氧化锰[BirMO(Na)], 通过离子交换反应在0.1 mol/L HCl溶液中Na型层状氧化锰转化成H型层状氧化锰[BirMO(H)]. BirMO(H)在四甲基氢氧化铵[(CH3)4NOH]溶液中搅拌处理7 d后, 剥离生成了MnO2纳米层胶体分散液. 剥离的MnO2纳米层胶体分散液在pH＝4.0～11.0的精氨酸溶液中搅拌2 d, 得到了层间距为1.49 nm的精氨酸插层氧化锰纳米结构材料. 通过XRD, DSC-TGA, SEM, IR及元素分析对合成试样进行了分析表征. 结果表明精氨酸在氧化锰层间的插入量及插入形式与重组溶液的pH值密切相关, 其最大插入量为1.80 mmol/g.     

低热固相反应法制备纳米LiCoO2的研究(Ⅰ)

LiCoO2是目前商品锂离子电池的正极材料.虽然其价格昂贵,但与LiNiO2或LiMn2O4等相比,LiCoO2较易合成且生产工艺较成熟,因此其性能改进仍受到普遍关注.目前LiCoO2的合成方法主要是高温固相法[1～4],一般在700～900℃范围内烧结得到HT-LiCoO2;此外还可用低热法得到LT-LiCoO2[5～7];或通过CoOOH/LiOH·H2O/H2O混合物经H+/Li+离子交换得到LiCoO2[8].     

铈杂多配离子-水滑石超分子层柱材料ZnAl-Ce(PMoV)2的插层组装、表征及催化性能

以十四酸根阴离子柱撑Zn-Al水滑石Zn0.77Al0.22(OH)2.0.22C13H27COO.0.81 H2O(记为ZnAl-14A)为预撑前体,在水溶液中用离子交换法将以2∶17缺位杂多酸根离子(P2Mo16VO61)11-记为(P Mo V)为配体的稀土杂多配阴离子Ce(P2Mo16VO61)219-(记为Ce(PMoV)2)插层组装到水滑石层板间,合成了一种具有大的层间距(3.37 nm)的超分子插层材料Zn0.77Al0.23(OH)2.0.0105[Ce(P1.9Mo15.7V1.1O61)2].0.011C13H27COO.0.83H2O(记为ZnAl-Ce(PMoV)2)。用ICP,IR,XRD和DTA对产物的组成和结构进行了表征。结果表明,该产物中Ce(PMoV)2配阴离子沿其长轴垂直于层板的方向分布于水滑石层间;产物具有规整的层状结构和热稳定性;产物对乙酸与正丁醇的酯化反应,二甘醇的脱水-环化反应和H2O2氧化环己烷的反应有良好的催化性能,且易于回收重复使用。     

环丙烷衍生物在D2O离子体系中的H/D交换反应

在D2O化学反应气条件下研究了环丙烷衍生物的H/D交换反应特性.发现了三种新的产物离子[M+1]+、[M+2]+和[M+3]+.应用碰撞诱导碎裂(CID)技术研究了这些离子的碎裂反应特性.实验结果表明三种新的产物离子是由反应物与试剂离子之间发生H/D交换反应生成的.并获得了环丙烷衍生物结构中活泼氢位置及其数量的信息.     

环丙烷衍生物在CD3OD离子体系中的H/D交换反应

研究了环丙烷衍物生物在CD3OD离子体系中的H/D交换反应产物离子[M 1]^*,[M 2]^ 和[M 3]^*的碰撞诱民碎裂(CID)反应特征,实验结果表明这些产物离子是由反应物与试剂离子之间生H/D交换反应生成的,获得了环丙烷衍生物结构中活泼氢位置及其数量的信息.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

三核锰配合物[Mn3O(O2CCHClCH3)6(py)2(H2O)]·2/3H2O的合成，晶体结构及磁性

用/N-n-Bu4MnO4,醋酸锰,2-氯丙酸在无水乙醇溶剂中合成了三核锰配合物[Mn3O(O2CCHlCH3)6(py)2(H2O)]·2/3H2O(1·2/3H2O).X-射线单晶衍射确定了其晶体结构.晶体属单斜晶系、C2/c空间群.3个Mn原子构成等腰三角形结构.变温磁化率研究表明配合物1存在反铁磁性交换作用.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

钒与糖代谢及糖尿病

微量元素钒作为生物体内必需元素，经证实有很重要的生理学功能，与机体糖代谢有十分密切的关系，且能降低糖尿病动物模型的高血糖，极有可能被开发为治疗糖尿病的药物。     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

Synthesis of Tyrosol and Hydroxytyrosol Glycofuranosides and Their Biochemical and Biological Activities in Cell-Free and Cellular Assays

Tyrosol (T) and hydroxytyrosol (HOT) and their glycosides are promising candidates for applications in functional food products or in complementary therapy. A series of phenylethanoid glycofuranosides (PEGFs) were synthesized to compare some of their biochemical and biological activities with T and HOT. The optimization of glycosylation promoted by environmentally benign basic zinc carbonate was performed to prepare HOT α-L-arabino-, β-D-apio-, and β-D-ribofuranosides. T and HOT β-D-fructofuranosides, prepared by enzymatic transfructosylation of T and HOT, were also included in the comparative study. The antioxidant capacity and DNA-protective potential of T, HOT, and PEGFs on plasmid DNA were determined using cell-free assays. The DNA-damaging potential of the studied compounds for human hepatoma HepG2 cells and their DNA-protective potential on HepG2 cells against hydrogen peroxide were evaluated using the comet assay. Experiments revealed a spectrum of different activities of the studied compounds. HOT and HOT β-D-fructofuranoside appear to be the best-performing scavengers and protectants of plasmid DNA and HepG2 cells. T and T β-D-fructofuranoside display almost zero or low scavenging/antioxidant activity and protective effects on plasmid DNA or HepG2 cells. The results imply that especially HOT β-D-fructofuranoside and β-D-apiofuranoside could be considered as prospective molecules for the subsequent design of supplements with potential in food and health protection.     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.