A study on the catalytic behaviors of concentrated heteropolyacid solution - I. A novel catalyst for isobutane alkylation with butene

The catalytic behaviors of a novel liquid acid catalyst (composed of heteropolyacid and acetic acid) for alkylation of isobutane with butene was investigated. As a solvent acetic acid had a synergistic effect. It enhanced the acid strength of HPA and its stability. The conditions for the formation of the catalytically active phase were studied systematically. The content of crystal water of HPA and the quantity of solvent affect the formation of active phase and the catalytic activity. Catalytically active phase consists of HPA, acetic acid and hydrocarbon produced from the reaction, as well as traces of water from the crystal water of HPA. This catalyst system is comparable to the sulfuric acid in catalytic activity.

Lewis酸对杂多酸催化异丁烷/丁烯烷基化反应的作用Ⅰ.SbCl_5的修饰作用

考察了SbCl5对杂多酸 (HPA)催化i C4 H10 /C4 H8烷基化反应的修饰作用 ,用Hammett指示剂测定了SbCl5/HPA催化剂的酸强度 .结果表明 ,经SbCl5修饰的HPA的酸强度有所提高 ,SbCl5的加入量、反应温度及反应时间对烷基化油收率及产物分布均有不同的影响.

The development in oxidation of olefins to ketones catalyzed by palladium compounds

The development in the oxidation of olefins to ketones catalyzed by palladium compounds was reviewed. Some improved methods for the oxidation of olefins catalyzed by Wacker-type catalyst systems are also summarized. For this reaction, some new catalyst systems and the reaction mechanism are described. Emphasis has been given to the applications of Pd(I)/HPA(heteropoly acid), Pd(I)/FePc (iron phthalocyanine), Pd (I)/HQ (hydroquinone)/FePc, Pd (I)/HQ/HPA, Pd (I)/CuSO4/HPA catalyst systems in the oxidation of olefins to ketones; the application of Pd(I)/LCoNO2, PdCl2 (MeCN)(2)/CuCl, Pd(OAc)(2)/ pyridine, fluorous biphasic catalyst systems in the oxidation of olefins to ketones is also surveyed.

钯配合物催化环己烯氧化合成环己酮的研究进展

综述了钯配合物催化环己烯氧化合成环己酮的研究进展。总结了环己烯氧化合成环己酮的催化体系及其催化活性。着重介绍了PdSO4 /HPA (杂多酸 ) ,Pd (OAc) 2 /BQ (苯醌 ) ,Pd (OAc) 2 /FePc (酞菁铁 ) ,Pd(OAc) 2 /HQ (氢醌 ) /FePc ,Pd (OAc) 2 /HQ /HPA ,Pd (NO3 ) 2 /CuSO4 /HPA等催化体系催化环己烯氧化的活性及其作用机理。讨论了影响环己烯氧化活性的因素

钯配合物催化烯烃氧化合成酮类物质的研究进展

本文系统地评述了钯配合物催化烯烃氧化合成酮类物质的研究进展。综述了改进 Wacker类催化剂催化活性的几种方法。总结了烯烃氧化合成酮类物质反应的几种典型催化体系及其作用机理。着重介绍了 Pd( ) /HPA(杂多酸 )、Pd( ) /Fe Pc(酞菁铁 )、 Pd( ) /HQ(氢醌 ) /Fe Pc、Pd( ) /HQ /HPA、Pd( ) /Cu SO4 /HPA等 Wacker类催化体系在烯烃氧化合成酮类物质中的应用 ;对 Pd( ) /LCo NO2 、Pd Cl2 ( Me CN) 2 /Cu Cl、Pd( OAc) 2 /吡啶、氟两相等非 Wacker类催化体系在烯烃氧化合成酮类物质中的应用也作了讨论

Electrochemical growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.

Isobutane/butene alkylation over supported heteropoly acid catalysts: I. Influence of the structure of silica

Catalysts consisting of heteropoly acids (HPAs) supported on different silica and mesoporous molecular sieves have been prepared by impregnation and the sol-gel method, respectively, and their catalytic behavior in fixed-bed alkylation of isobutane with butene has been investigated. The activity, selectivity and stability of the supported-HPA catalysts could be correlated with the surface acidity of the catalysts, the structure of supports as well as the time on stream (TOS). In the fixed-bed reactor, the acidity of the heteropoly acid is favorable to the formation of dimerization products (C-8(=)); especially, the pore size of supports was seen to have an important effect on activity and product distribution of the catalysts. Contrary to the traditional solid-acid catalysts, the supported-HPA catalysts own an excellent stability for alkylation, which makes it possible for these supported catalysts to replace the liquid-acid catalysts used in industry.

CATALYTIC BEHAVIOR OF METAL-IONS LOCATED AT DIFFERENT SITES OF HETEROPOLYCOMPOUNDS

It was discovered experimentally that heteropolymolybdophosphoric acids (HPA) with Keggin and Dawson structure are inactive for H2O2-decomposition, while their salts (Fe3+, Cu2+, Co2+ and Mn2+) all possess more activity. It could be concluded that the act

THE CATALYTIC ACTIVITY OF HETEROPOLY ACIDS (SALTS) AND MONO-LACUNARY HETEROPOLY TUNGSTOPHOSPHORIC COMPOUND IN THE OXIDATION OF ALCOHOLS

The catalytic activity of heteropoly compounds in the oxidation of benzyl alcohol and cyclohexa nol under phase transfer conditions has been studied. The catalytic activity of six kinds of heteropoly acids with Keggin structure will drop by the order of GeMo12 (H4GeMo12O40). PW12, PMo12, SiMo12, GeW12 and SiW12. When the three protons of H3PW12O40 Were replaced by Na+ step by step, the catalytic activity will raise gradually with the drop of acidity. The addition of base and trace amount of sulfuric acid to the reaction system resulted in an increase of catalytic activity. It was found that catalytic activity of mono-lacunary heteropoly compounds is higher than that of the primary heteropoly acids (or salts). The catalytic oxidation system of HPA-H2O2-PTC is very active in the oxidation of benzyl alcohol ana cyclohexanol, but it has little activity in the oxidation of inactive compounds such as n(or iso)-proplalcohol. n-butyl alcohol and n-hexanol. Solvent has great effect on reaction, when polar compounds such as water were used as solvent, the catalytic activity is better than that when non-polar compounds were used as solvent.

ELECTROCHEMICAL STUDY OF ISOPOLYOXOMETALLATES AND HETEROPOLYOXOMETALLATES FILM MODIFIED MICROELECTRODES .1. PRETREATMENT AND MODIFICATION OF THE MO80-26(4-) MODIFIED CARBON-FIBER MICROELECTRODE

In this paper the preparation of isopoly- and heteropolyoxometallates (IPA and HPA) thin film modified carbon fiber (CF) microelectrodes and the factor that influences the modification of IPA and HPA films are described. IPA and HPA film modified CF microelectrodes can all be prepared by cyclic potential scan and simple dip coating. The modified electrodes prepared are very stable and reversible in acidic solution with monolayer characteristics. The electrochemical pretreatment of CF microelectrodes plays an important role in the modification of IPA and HPA film. The absorption of IPA and HPA film on electrode surfaces has been discussed on the basis of surface conditions of the CF microelectrode and the structure of IPA and HPA.

Variations in the eastern Indian Ocean warm pool and its relation to the dipole in the tropical Indian Ocean

Based on the monthly average SST and 850 hPa monthly average wind data, the seasonal, interannual and long-term variations in the eastern Indian Ocean warm pool (EIWP) and its relationship to the Indian Ocean Dipole (IOD), and its response to the wind over the Indian Ocean are analyzed in this study. The results show that the distribution range, boundary and area of the EIWP exhibited obviously seasonal and interannual variations associated with the ENSO cycles. Further analysis suggests that the EIWP had obvious long-term trend in its bound edge and area, which indicated the EIWP migrated westwards by about 14 longitudes for its west edge, southwards by about 5 latitudes for its south edge and increased by 3.52x10(6) km(2) for its area, respectively, from 1950 to 2002. The correlation and composite analyses show that the anomalous westward and northward displacements of the EIWP caused by the easterly wind anomaly and the southerly wind anomaly over the eastern equatorial Indian Ocean played an important and direct role in the formation of the IOD.

Role of snow depth in spring of Tibetan Plateau in onset of South China Sea summer monsoon

The role of snow depth of Tibetan Plateau in the onset of South China Sea summer monsoon and the influence of ENSO on snow depth of Tibetan Plateau are investigated with use of data from ECMWF reanalysis and NCEP/NCAR reanalysis. The results are as follows: (1) The snow depth data from ECMWF reanalysis are tested and reliable, and can be used to study the influence of snow depth of Tibetan Plateau on the onset of South China Sea summer monsoon; (2) Anomaly of snow depth of Tibetan Plateau causes anomaly in air temperature and its contrast between the Indian Ocean and the continent resulting in easterly wind anomaly over 500 hPa and hence as well as in the atmospheric circulation in the lower layer. For the year of negative anomaly of snow depth a westerly wind anomaly with a cyclone pair takes place, while for positive anomaly of snow depth an easterly anomaly occurs with an anticyclone pair; (3) While positive anomaly of SST occurs in the eastern Pacific Ocean, positive anomaly of air pressure also takes place over the eastern Indian Ocean and the South China Sea, causing stronger meridional pressure gradient between the ocean and continent and then westerly wind anomaly. At the same time, the atmospheric pressure increases in the northern Tibetan Plateau, northerly wind gets stronger, and subtropical front strengthens. All of these are favorable for snowfall over Tibetan Plateau.

Variation in joint mode of the tropical Indian-Pacific Ocean thermodynamic anomaly

Previous research has defined the index of the Indian-Pacific thermodynamic anomaly joint mode (IPTAJM) and suggested that the winter IPTAJM has an important impact on summer rainfall over China. However, the possible causes for the interannual and decadal variability of the IPTAJM are still unclear. Therefore, this work investigates zonal displacements of both the western Pacific warm pool (WPWP) and the eastern Indian Ocean warm pool (EIOWP). The relationships between the WPWP and the EIOWP and the IPTAJM are each examined, and then the impacts of the zonal wind anomalies over the equatorial Pacific and Indian Oceans on the IPTAJM are studied. The WPWP eastern edge anomaly displays significant interannual and decadal variability and experienced a regime shift in about 1976 and 1998, whereas the EIOWP western edge exhibits only distinct interannual variability. The decadal variability of the IPTAJM may be mainly caused by both the zonal migration of the WPWP and the 850 hPa zonal wind anomaly over the central equatorial Pacific. On the other hand, the zonal migrations of both the WPWP and the EIOWP and the zonal wind anomalies over the central equatorial Pacific and the eastern equatorial Indian Ocean may be all responsible for the interannual variability of the IPTAJM.

东亚低空异常季风风场时空特征分析

应用矢量经验正交函数（Vector EOF）方法和长序列网格点风距平资料对东亚季风区低空异常风场进行分析，以揭示东亚季风区矢量风场异常的主要模态及其年际、年代际振荡特征和成因。 研究方法包括： 1)EOF方法是将一个空间观测场的时间序列资料分解成若干重要的正交的空间和时间模态，从而提取大气和海洋观测资料的主要时空变率特征（即模态）。目前，EOF模态也可直接由奇异值分解（SVD）方法计算获得，勿需再对观测资料矩阵进行协方差矩阵的计算。首先将风场资料集的 分量矩阵和 分量矩阵融合成为一个新矩阵 ，然后对该新矩阵 应用SVD方法进行计算，获得 分量和 分量的主要的EOF空间模态及其统一的时间模态。最后，将 分量和 分量的各主要空间模态进行合并处理，形成矢量形式的彼此正交的EOF空间模态。由于是对矩阵 进行EOF分解（而不是对 和 分别进行EOF分解），所获得的 和 的空间特征模态对应于相同的时间系数，从而可以合并成为一个具有现实意义的特征风场（即全风矢量场）。 2)将滤波技术（例如，Butterworth滤波器）和各种谱分析技术（包括功率谱、交叉谱和奇异谱SSA）应用于时间模态，探讨其年际、年代际振荡特征及与ENSO的联系。 所使用资料为NCEP/NCAR提出的1950年1月至2004年12月850 hPa全球月平均风场网格点资料，资料分辨率为2.5°×2.5°。研究区为0～50N，100～150E。 结果表明，东亚异常季风典型流场第一模态（VEOF-1）属于ENSO相关模态，其时间模态与Nino3指数之间具有较高的负相关关系，但以季风异常滞后ENSO进程6～8个月为最显著。这表明，东亚热带和副热带季风风场变异与ENSO之间联系紧密。提出了一个VEOF-1对ENSO响应的概念模型。 前6个模态，其积累方差贡献率接近60％，基本可表达东亚季风区风场异常的典型类型。 （1）东亚异常季风模态VEOF-1以年际尺度振荡最为显著（是年际尺度振荡的代表模态），并以2～4年周期为最显著；东亚异常季风模态VEOF-2至VEOF-4则主要表现为11年～20年尺度的年代际变化。 （2）东亚异常季风VEOF-1时间模态与Nino3指数之间具有较高的负相关，并以VEOF-1落后Nino3距平变化6～8个月为最显著。 对矢量风距平流场作VEOF展开，能揭示季风变异的空间结构特征和时间振荡规律，并具有直观的天气学意义。 VEOF-1属于ENSO相关模态，其时间模态与Nino3指数之间具有较高的负相关关系，但以季风异常的响应滞后ENSO事件6～8个月为最显著。也即在它们之间的遥相关关系中，赤道东太平洋SST持续地异常升高（降低），6～8个月后东亚异常季风VEOF-1模态明显减弱（加强）。

去甲肾上腺素刺激高原鼠兔CRF的分泌

We studied the effect of neuro transmitter no repin ephrine (N E) on immuno reactive cortico trop inreleasing factor (CRF) of median eminence (M E) in the native pika (Ochotona cu rz oniae). At one hour after intra cerebrovent ricular ( icv) adm inistrat ion of N E in doses of 3.75,7.5, 15 and 30 μg/100 g BW , the CRF level ofM E increased. And the plasma cortico sterone concent rat ion also increased. Two and six days after adrenalectomy (ADX) , N E concent ration in hypothalamus declined to 76.32% and 76.27% of those in intact pika, plasma cortico rsterone concent ration also decreased to 16.57 and 2.05% of the control. These results indicated that N E have a effect on activating HPA axis through activating hypothalamic CRF in Ochotona curzoniae.