Studies on the alkylation of isobutane with butene over WO3/ZrO2 strong solid acid (I) - Effect of preparation, load of WO3 and calcination temperature

A series of WO3/ZrO2 strong solid acid prepared under different conditions were studied. Their crystal structures, surface properties and acidities were determined by means of XRD, DTA-TG, H-2- TPR, Laser Raman and acidity measurements. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in tetragonal phase, the addition of WO3 plays an important role to stabilize tetragonal phase of ZrO2 and thus the catalyst had a considerable surface area. WO3 in WO3/ZrO2 was dispersed and crystalized in WO3 crystalite on ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, which acts as the strong solid acid site. The catalytic properties of WO3/ZrO2 strong solid acid for alkylation of iso-butane with butene under the different conditions were investigated. They had a better reaction performance than other strong solid acids, a parallel relationship could be drawn between the catalytic activity and the amount of acid sites as well as the acidic strength of the catalysts.

WO_3/ZrO_2固体强酸催化剂上异丁烷-丁烯烷基化反应研究(Ⅰ)──钨负载量和焙烧温度的影响

制备了系列 WO3/ Zr O2 固体强酸催化剂 ,用 XRD,DTA-TG,H2 -TPR,Raman光谱和酸性测定等方法测定其晶型结构、表面状态和酸性 .结果表明 ,WO3/ Zr O2 中的 Zr O2 基本以 T晶相存在 ,WO3对稳定 T晶相有重要作用 ,样品具有较大的表面积 .分散于 Zr O2 表面上的 WO3主要以单层分散和析出的 WO3晶粒形式存在 ,部分可能与 Zr O2 作用形成 Zr— O—W键并起强酸作用 .研究了各种实验条件下的异丁烷 -丁烯烷基化反应 .与其它固体酸相比 ,具有较高的起始活性和 i-C08选择性 ,且与酸强度和酸量有较好的对应关系

Chemical bond properties of REBa2Cu3O7 and its Mossbauer spectroscopy

By using the average bond-gap model, the chemical bond properties of REBa2Cu3O7 were calculated. The calculated covalencies for Cu(1)-O and Cu(2)-O bonds in REBa2Cu3O7 compounds are 0.41 and 0.28 respectively. Mossbauer isomer shifts of Fe-57 doped in EuBa2Cu3O7-x and Sn-119 doped in YBa2Cu3O7-x were calculated by using the chemical surrounding factor, h, defined by covalency and electronic polarizability. The valence states and sites of Fe-57 in EuBa2Cu3O7 and Sn-119 in YBa2Cu3O7-x were identified.

REBa_2Cu_3O_7的化学键性质和Mssbauer谱研究

利用电介质的平均能带模型计算了 ＲＥＢａ２Ｃｕ３Ｏ７（ＲＥ＝Ｅｕ，Ｙ）的化学键参数，得到 Ｃｕ（１）－Ｏ键的平均共价性为０．４１， Ｃｕ（２）－Ｏ 键的平均共价性为 ０．２８．应用由共价性和极化率定义的化学环境因子计算了５７Ｆｅ和１１９Ｓｎ在 ＲＥＢａ２Ｃｕ３Ｏ７中的 Ｍｏｓｓｂａｕｅｒ同质界能位移，确定了 ５７Ｆｅ在 ＥｕＢａ２Ｃｕ３Ｏ７和 １１９Ｓｎ在 ＹＢａ２Ｃｕ３Ｏ７中的价态和占位情况

Electrocatalytic oxidation of hydrazines at a 4-pyridyl hydroquinone self-assembled platinum electrode and its application to amperometric detection in capillary electrophoresis

4-Pyridyl hydroquinone on a platinum electrode adsorbs through the pyridine nitrogen forming stable self-assembled layers. The electrocatalytical oxidation of hydrazines was performed by the modified electrode. The overpotential of hydrazines was decreased markedly at the self-assembled monolayer (SAM) electrode. The mechanism of hydrazine oxidation was also investigated. Amperometric detection of hydrazine under zero potential (vs Ag\AgCI\sat. KCl) was exhibited by the SAM electrode used as an electrochemical detector in a flow system. (C) 1998 Elsevier Science S.A. All rights reserved.

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

掺杂的La_2 NiO_4中价态与电学性质的关系

由于La_2NiO_4独特的结构引起了众多研究者的广泛关注。Sr的掺杂可将半导体的La_2NiO_4转变为金属性。最近报导La_2NiO_4可能据有高温超导电性。因此,研究La_2NiO_4中掺杂引起的价态不平衡导致的半导体一金属转变,对于搞清La_2NiO_4的导电机理,开发La_2NiO_4在功能材料上的应用都是非常重要的。

立规聚甲基丙烯酸热表征研究

本文对不同立构的聚甲基丙烯酸(PMAA)进行了热表征。实验结果表明,在30℃～200℃内未出现玻璃化转变。间同PMAA分别在-245℃和-280℃发生脱水反应和脱羧,而全同PMAA只在-185℃观察到脱水反应。这种热稳定性的明显差别与不同立构PMAA链上相邻羧酸距离有关。实验数据证实PMAA脱水反应为无规反应,服从一级动力学反应方程。脱水温度和间同立构含量成正比,脱水反应活化能间同PMAA比全同PMAA高～7Kcal/mol。

Electrochemical investigations of micro-droplets formed on metals during the deliquescence of salt particles in atmosphere

CORROSION; WATER; SPECTROSCOPY; CHLORIDE; ZINC; NUCLEATION; INTERFACE; ELECTRODE; SURFACES; GROWTH

Statistical distribution of nonlinear random wave height

A statistical model of random wave is developed using Stokes wave theory of water wave dynamics. A new nonlinear probability distribution function of wave height is presented. The results indicate that wave steepness not only could be a parameter of the distribution function of wave height but also could reflect the degree of wave height distribution deviation from the Rayleigh distribution. The new wave height distribution overcomes the problem of Rayleigh distribution that the prediction of big wave is overestimated and the general wave is underestimated. The prediction of small probability wave height value of new distribution is also smaller than that of Rayleigh distribution. Wave height data taken from East China Normal University are used to verify the new distribution. The results indicate that the new distribution fits the measurements much better than the Rayleigh distribution.

全新世渤海泥质区的沉积物物质组成特征及其环境意义

本文通过对渤海泥质区不同位置岩芯的粒度、矿物、化学元素等方面的分析，结合浅地层地震剖面、AMS 14C测年、微体古生物分析、稳定同位素测量、古地磁数据等，对全新世渤海泥质区中沉积物物质组成特征、物质来源、形成历史其环境响应进行了探讨。 结果显示，在早全新世期间黄河曾流经渤海南部，其携带泥沙对渤海沉积作用造成一定影响，但不同位置沉积环境及所受黄河影响的大小存在差异。 渤海泥质区的主体部分从约6000 aBP开始形成。当时沉积记录存在突变现象，不仅显示了沉积环境氧化还原条件的改变，而且温度与盐度值的变化以及沉积速率的明显偏高以及浮游有孔虫的出现说明本区开始受到黄海暖流余脉的影响。4500 aBP以来，沉积物中重矿物组合、化学成分等与黄河沉积物已较为接近，说明此时黄河物质对渤海泥质沉积的影响已经占据主导地位。渤海泥质区虽然有着离黄河口较近的特点，但并未出现明显高于陆架其它泥质沉积区的沉积速率，说明受输运机制控制，黄河物质向泥质区的输送量不大，远不如向黄海的输出量。 北部记录着全新世期间发生的两次地磁极漂移，分别发生于2800~3100 aBP（对应Starno事件）和7500~8200 aBP。漂移发生前后，气候、物质来源与海平面均有较大变化，说明地磁极漂移对气候有着重要影响。

Viewing DVM via general behaviors of zooplankton: A way bridging the success of individual and population

In this paper, we viewed the diel vertical migration (DVM) of copepod in the context of the animal's immediate behaviors of everyday concerns and constructed an instantaneous behavioral criterion effective for DVM and non-DVM behaviors. This criterion employed the function of 'venturous revenue' (VR), which is the product of the food intake and probability of the survival, to evaluate the gains and losses of the behaviors that the copepod could trade-off. The optimal behaviors are to find the optimal habitats to maximize VR. Two types of VRs are formulated and tested by the theoretical analysis and simulations. The sensed VR, monitoring the real-time changes of trade-offs and thereby determining the optimum habitat, is validated to be the effective objective function for the optimization of the behavior; whereas, the realized VR, quantifying the actual profit obtained by an optimal copepod in the sensed-VR-determined habitat, defines the life history of a specific age cohort. The achievement of a robust copepod overwintering stock through integrating the dynamics of the constituent age cohorts subjected to the instantaneous behavioral criterion for DVM clearly exemplified a possible way bridging the immediate pursuit of an individual and the end success of the population. (c) 2005 Published by Elsevier Ltd.

外源H_2O_2对小麦幼苗耐盐性的调节作用

以高原448小麦品种为材料,分别测定了4个处理（Hoagland营养液、Hoagland营养液＋150 mmol/LNaCl、Hoagland营养液＋150 mmol/L NaCl＋10μmol/L H_2O_2和Hoagland营养液＋10μmol/L H_2O_2）的小麦幼苗在第2、4、6、8天叶片叶绿素、丙二醛、可溶性糖和还原性谷胱甘肽含量.结果显示：外源H2O2提高了NaCl胁迫下4个时段小麦幼苗的叶绿素含量（8.27%、32.57%、10.19%、4.86%）及还原性谷胱甘肽含量（3.09%、23.97%、5.85%、2.11%）,显著提高了可溶性糖含量（14.58%、8.43%、16.68%、5.8%,P〈0.05）,而显著降低了其丙二醛含量（17.53%、14.04%、4.75%、8.47%,P〈0.05）.外源H_2O_2（10μmol/L）使NaCl胁迫下叶绿素含量和还原性谷胱甘肽含量峰值提前,同时推迟了丙二醛峰值出现的时间.研究表明,外源H2O2通过提高叶片叶绿素、可溶性糖和还原性谷胱甘肽含量以有效地增强小麦幼苗的耐盐性.

青藏高原3种主要植被类型的表观量子效率和最大光合速率的比较

以海北高寒草甸生态系统定位站的涡度相关系统连续观测的CO_2通量数据为基础,分析了青藏高原的高寒矮嵩草(Kobresia humilis)草甸、高寒金露梅(Potentilla fruticosa)灌丛草甸和高寒藏嵩草(Kobresia tibetica)沼泽化草甸等3种主要植被类型在2005年植物生长季(6-9月)的表观量子产额(a)、最大光合速率(Pmax)和呼吸速率(Reco)的变化特征.结果表明:3种植被类型白天的净生态系统CO_2交换量(NEE)和光量子通量密度(PPFD)存在明显的直角双曲线关系(P＜0.05),其a、Pmax和Reco呈现出相似的季节变化趋势,在生长季初期(6月)最小,在7月或8月份达到最大;高寒矮嵩草草甸的a、Pmax和Reco大于灌丛草甸和沼泽化草甸,而后两者差别不大.

高寒小嵩草草甸暖季草场主要植物种群的生态位

对高寒小嵩草草甸不同放牧强度下20种植物种群的优势度、生态位宽度及生态位重叠规律进行了研究.结果表明,经过2年的放牧实验,对照、轻度和中度放牧组的主要优势种均为小嵩草和垂穗披碱草,重度放牧组的主要优势种为鹅绒委陵菜和阿拉善马先蒿;由于小嵩草、矮嵩草和线叶嵩草具有耐牧和耐践踏等生物学特点,它们的生态位宽度很大(0.938,0.824,0.815);垂穗披碱草由于其耐牧和耐旱性较差,生态位宽度相对较小(0.805),且青海野青茅、异针茅、针茅、紫羊茅和双叉细柄茅等禾本科牧草的生态位宽度在放牧强度梯度上均较小(0.226,0.448,0.445,0.608,0.605),说明放牧抑制了高大禾草层片的发育,为植株矮小的莎草科牧草的生长创造了条件;异针茅和针茅之间、甘肃马先蒿和阿拉善马先蒿之间生态位重叠较小(0.500,0.572),这是种间对资源利用上分化的结果.分布于放牧演替系列2个极端的种群间生态位重叠较小,表明物种的分布是既间断又连续的.