对甲烷氧化偶联W－Mn／SiO＿2催化剂Na＿2WO＿4的流失及其影响的考察

用ＸＲＤ、ＦＴ－ＩＲ、ＥＳＲ、Ｈ２－ＴＰＲ和ＴＰＯ等方法，对Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂和其经水煮处理的一系列样品进行了表征．实验发现该催化剂中的结晶态Ｎａ２ＷＯ４易于流失，单层分布的Ｎａ２ＷＯ４在苛刻的处理条件下也有可能流失．依此，探讨了上述流失现象与Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂的催化活性及该催化剂在长时间反应中发生的ＳｉＯ２相变之间的关系，证明了结晶态Ｎａ２ＷＯ４的流失对该催化剂甲烷氧化偶联反应的催化活性只有轻微的影响，单层分布Ｎａ２ＷＯ４的流失可造成催化剂中Ｍｎ从Ｍｎ３＋转变为Ｍｎ２＋，并使催化剂的催化活性明显降低．但在水煮条件下，无论是结晶态的还是单层分布，Ｎａ２ＷＯ４的流失都没有对ＳｉＯ２的α－方石英结构产生影响     

Pt/HM和Pd/HM催化剂表面氧的恢复与供出活化能测定

催化氧化是最重要的工业催化反应之一。七十年代以来,关于氧化催化剂的基础研究取得了长足的进步,采用各种手段对氧化催化剂的表面及体相氧种进行了考察。本文作者根据研究实用氧化催化剂的经验,结合控制论方法,亦提出了多相催化氧化反应的集团结构适应性规律。近年来,作者用TPD和吸附平衡法研究了V_2O_5/SiO_2催化剂表面氧的种类、数目和供出活性,较好地关联了催化氧化的一些事实,使以上规律更趋于半定量化。在多相氧化反应中,催化剂表面活性氧不断处于供出和恢复的循环之中,催化剂表面氧中心的供     

提高大分子Fullerene含量的有效方法

通过用掺有异相物质的石墨电极进行电弧反应，所得的混合物中大分子Ｆｕｌｌｅｒｅｎｅ的含量在１０％以上，为进一步分离，提纯以及深入研究大分子Ｆｕｌｌｅｒｅｎｅ打下了基础。研究发现，阳极材料中完整石墨结构的存在是生成Ｆｕｌｌｅｒｅｎｅ的必要条件，异相物质的存在为Ｆｕｌｌｅｒｅｎｅ的生长提供了热的载体，从而使产物中大分子Ｆｕｌｌｅｒｅｎｅ的含量增加。     

白钨酸研究——Ⅶ.K3W2Cl9的制备及反应

用粉状白钨酸作原针,在一般条件下制备K₃W₂Cl₉,产率达53%,证明白钨酸是比黄钨酸优越的钨化学试剂。研究了K₃W₂Cl₉经离子又换转化为酸的形态后与Ndz₂(C0₃)₃的反应。得到了新的化合物NdW₂Cl₉,提出了一条新的制备溶解度大的各种金属离子与W₂Cl₉^3-的化合物的途径。 对K₃W₂Cl₉和NdW₂Cl₉进行了紫外可见尤谱和X针线粉末衍射的测定。     

Use of chelating resins and inductively coupled plasma mass spectrometry for simultaneous determination of trace and major elements in small volumes of saline water samples

For some saline environments (e.g. deeply percolating groundwater, interstitial water in marine sediments, water sample collected after several steps of fractionation) the volume of water sample available is limited. A technique is presented which enables simultaneous determination of major and trace elements after preconcentration of only 60 mL sample on chelating resins. Chelex-100 and Chelamine were used for the preconcentration of trace elements (Cd, Cu, Pb, Zn, Sc) and rare earth elements (La, Ce, Nd, Yb) from saline water before their measurement by inductively coupled plasma mass spectrometry. Retention of the major elements (Na, Ca, Mg) by the Chelamine resin was lower than by Chelex; this enabled their direct measurement in the solution after passage through the resin column. For trace metal recoveries both resins yield the same mass balance. Only Chelex resin enabled the quantitative recovery of rare earth elements. The major elements, trace metals and rare earth elements cannot be measured after passage through one resin only. The protocol proposes the initial use of Chelamine for measurement of trace and major elements and then passage the same sample through the Chelex resin for determination of the rare earth elements. The detection limit ranged from 1 to 12 pg mL(-1). At concentrations of 1 ng mL(-1) of trace metals and REE spiked in coastal water the precision for 10 replicates was in the range of 0.3-3.4% (RSD). The accuracy of the method was demonstrated by analyzing two standard reference waters, SLRS-3 and CASS-3.     

某些生物分子在C60—γ—环糊精／Nafion化学修饰电极上的电催化行为

研究了Ｃ６０－γ－环糊精（Ｃ６０－γ－ＣＤ）（１：１）／Ｎａｆｉｏｎ和Ｃ６０－γ－ＣＤ（１： ２）／Ｎａｆｉｏｎ化学修饰电极在水溶液中的电化学行为，发现它们都有一对一电子转移的可逆表面波，而且它们对某些生物分子有电催化作用。     

A mesoporous template route to the low-temperature preparation of efficient green light emitting Zn2SiO4:Mn phosphors

Green light emitting Zn2SiO4:Mn phosphors have been prepared via a low-temperature solid-state reaction using mesoporous silica SBA-15 template. This mesoporous silica template method features low-temperature formation of phosphors and easy doping. The structure and morphology of the phosphors were characterized by XRD, SEM, TEM, and N2 adsorption/desorption techniques, which confirmed the single crystallinity, ordered mesostructure, closed pore channels, and elongated ropelike morphology. The luminescent properties were examined by photoluminescence spectroscopy at room temperature, and the results of fluorescence decay time measurements show non-single-exponential decay behavior and a decrease of the decay time with an increase of the Mn concentration.     

二苯并噻吩亚砜的单晶结构及其π-π堆积作用理论研究

采用X射线衍射法测定二苯并噻吩亚砜单晶结构,发现晶体中二苯并噻吩亚砜分子以反平行三明治式的结构Ⅲ和反平行位移式的结构Ⅳ两种堆砌方式交替堆砌形成有序π-π堆积晶体。二苯并噻吩亚砜单晶结构属于三斜型,空间群为P1,晶体参数为:a=0.84712nm,b=0.94137nm,c=1.20380nm,α=97.866°,β=106.2630°,γ=96.437°,V=0.9014nm3,R1(全部数据)=0.0348和ωR2(全部数据)=0.0814。利用BHandH/6-31 G**方法计算了二苯并噻吩亚砜分子间的π-π堆积作用,Ⅲ和Ⅳ堆砌模式的π-π堆积效应作用能相当大,其计算值分别为-36.06kJ/mol和-39.83kJ/mol,电荷分布表明正负电荷匹配是稳定晶体π-π堆积体系的重要因素。     

PdCl2-catalyzed two-component cross-coupling cyclization of 2,3-allenoic acids with 2,3-allenols. An efficient synthesis of 4-(1',3'-dien-2'-yl)-2(5H)-furanone derivatives

Cross-coupling cyclization reaction between 2,3-allenoic acids 1 and 2,3-allenols 2, in which two allenes functioned differently, was realized to afford 4-(1',3'-dien-2'-yl)-2(5H)-furanone derivatives 3. The reaction may proceed via an oxypalladation, insertion, and beta-hydroxide elimination process. A high E-stereoselectivity of the new formed C=C double bond was observed.     

EXAMINATION OF THE SURFACE FREE ENERGY AND ACID-BASE PROPERTIES OF CELLULOSE BY THE COLUMN WICKING TECHNIQUE AND THE CRITICAL PACKING HEIGHT/DENSITY

INTRODUCTIONThe wicking technique has been used to determine the surface energy components of solids[1-7]. Generally, thereare two wicking processes in practice, i.e. thin layer wicking and column wicking. A comparison of the twowicking techniques made by van Oss et al.[2], shows that column wicking has a problem of showing differentpacking density due to some kinds of powder materials, i.e. clay can not give good repacking reproducibility[2].But thin layer wicking has a problem in sample…