新型固体铁系复合盐催化剂制备及其催化酯化研究

报道新型固体复合盐催化剂（Ⅱ）的制备，应用5种催化剂分别进行催化乙酸和乙醇合成乙酸丁酯的对比试验，选出优良催化剂（Ⅱ）并进行催化酯化合成了18种酯的研究工作。通过实验证明催化剂（Ⅱ）酯化性能优良（优于固体超强酸Fe2O3/SO4^2-),操作简单，污染小。在18种酯中乙酸丁酯的产率高达97．9％。     

合成γ—甲基丙烯酰氧丙基三甲氧基硅烷的催化剂体系的研究

本文比较了氯铂酸－异丙醇（Ｉ）、氯铂酸－四氢呋喃（Ⅱ）和氯铂酸－乙酰丙酮（Ⅲ）三种铂络合物催化剂对甲基丙烯酸烯丙酯与三甲氧基硅烷的硅氢加成反应的催化性能，探讨了各种可能因素对反应凝胶的影响，考察了反应条件对催化活性和反应结果的影响。实验结果表明三种催化剂都具有较高的活性，但催化剂的络合结构状态与反应是否凝胶有关，催化剂（Ⅲ）诱导期短，反应平稳，不易引起凝胶，用催化剂（Ⅲ）合成γ－甲基丙烯酰氧丙基三     

2008第二届中国（上海）国际催化新技术、新产品、新设备展览会

首届“中国（上海）国际催化新技术、新产品、新设备展览会”于2007年3月21日～23日在上海光大会展中心举办，展览会的成功举办填补了我国催化工业领域专业展的空白，也标志着我国最大的催化展览会在国际大都市上海诞生。首届催化展共吸引来自20多个国家和地区的近百家企业参展，分别展示了催化领域的最新科技成果，展品范围包括石油工业催化剂、石油炼制催化剂、环保催化剂（汽车三元净化器、脱硫脱硝、工业水处理等）、有机化工和无机化工催化剂、贵金属材料、催化载体、各种催化仪器设备等。     

挥发性有机物燃烧催化剂的研究进展

挥发性有机物（VOCs）是主要大气污染物质，也是形成PM_2.5和臭氧的重要前体。强化挥发性有机物控制，是改善大气环境的重要途径。催化燃烧（氧化）被认为是去除VOCs最有效的方式之一，本文综述了VOCs催化燃烧常用的贵金属催化剂、非贵金属催化剂。其中，贵金属催化剂主要包括基于Pd、Pt、Ru等的催化剂，非贵金属催化剂主要包括Mn、Co、Ce、Zr等的氧化物，通常贵金属催化剂具有比非贵金属更高的氧化活性和稳定性，但对于含氮VOCs非贵金属催化剂（Mn、Cu）具有更好的氮气选择性，Cr基催化剂对于含氯VOCs燃烧具有更好的效果。此外，还重点讨论了载体、分散度、催化剂制备方法对贵金属催化剂性能的影响，并对发展VOCs氧化催化剂的研究提出了展望。     

甲烷催化燃烧催化剂催化理论与应用研究进展

概述了甲烷催化燃烧催化剂的研究现状,从组成甲烷燃烧催化剂的3个部分（基体、活性组分、氧化物载体）分别加以论述。通过掺杂一些金属和金属氧化物,不但可以提高高活性贵金属催化剂的热分解温度,还可以提高高温催化剂（如钙钛矿和六铝酸盐材料等）的催化活性。最后简要综述了甲烷催化燃烧反应机理。     

铬系聚乙烯催化剂研究开发新进展

从非均相催化体系和均相催化体系两个方面,详细介绍了铬系聚乙烯催化剂近年来的研发情况。指出了在非均相铬系聚乙烯催化体系中新型活性组分研究及新型载体应用的主要进展;分别讨论了以Cr（Ⅱ）、Cr（Ⅲ）、Cr（Ⅳ）为活性中心的新型均相铬金属配合物催化剂近年来的合成及应用情况;在此基础上,对铬系聚乙烯催化剂的研究前景进行了展望。     

镍的二亚胺催化剂的负载化及其催化乙烯的聚合

将Ni（Ⅱ）的二亚胺催化剂[（2,6-i-PrPh）2DABAn]NiBr2通过物理吸附法负载在硅胶上,并将负载化催化剂在正己烷作溶剂的条件下用于催化乙烯的配位聚合,通过GPC、DSC、IR等对聚合物性能进行了表征,并与均相催化剂催化烯烃聚合进行对比。结果表明：通过物理吸附法所得负载化催化剂Al/Ni摩尔比约为100。在正己烷作溶剂时,负载化Ni（Ⅱ）的二亚胺催化剂能够催化乙烯的聚合。与均相催化剂聚合体系相比,负载化催化剂的催化效率降低,所得聚合物分子量降低,密度、熔点均增大。在一定温度下随Al/Ni摩尔比、乙烯压力的增大,负载化催化剂催化效率逐渐提高,聚乙烯的支化度减小,分子量、密度、熔点均增大。     

生物质热解催化剂积炭问题的研究进展

生物质催化热解获得生物油等高质产品是最有前途替代传统化石能源的方法之一,但在热解过程中存在着严重的催化剂失活问题,其中积炭是导致催化剂失活的最主要因素。本文对近年来生物质催化热解领域的催化剂积炭问题进行综述,重点介绍催化剂积炭失活原因及表征方法、积炭的影响因素分析（催化剂结构、催化剂酸性与反应温度）、抑制催化剂积炭的方法 （催化剂改性、高压反应条件等）以及积炭催化剂再生方法 （氧化灼烧再生、臭氧低温再生、非热等离子体再生等）,并介绍了近年来新兴的微波催化热解技术对催化剂积炭的抑制和消除作用,然后针对该领域目前所面临的困难和发展方向进行展望,以期为生物质催化热解过程中催化剂积炭问题研究提供理论基础。     

催化半氢化制备1,4-丁烯二醇

研究制备了聚－γ－氨丙基硅氧烷钯络合物催化剂ＰＣＡＬ，用于丁炔二醇（ＢＹ）的催化半氢化，半氢化产物丁烯二醇（ＢＥ）收率高达９５％。在相同试验条件下用Ｌｉｎｄｌａｒ催化剂作了催化半氢化丁炔二醇的对比，发现二者有相同的催化效果，就生成ＢＥ的选择性和催化剂寿命而言，ＰＣＡＬ催化剂具有更多优点。该催化剂是适用于炔醇催化半氢化的新品种催化剂。     

2006年我国催化剂技术研发新进展

（1）烯烃环氧化催化剂。中科院大连化物所在“反应控制想转移催化用于烯烃环氧化反应研究”项目研究过程中发现了活性高、选择性好、易分离回收和可循环使用的反应控制相转移催化剂。在此基础上，该所将蒽醌法制H2O2过程与反应控制相转移催化丙烯环氧化反应耦合，开发出环氧丙烷生产新技术，弥补了传统氯醇化法和共氧化法工艺存在的污染环境和联产副产品等问题。（2）丙烯酸生产催化剂。中国石油兰州石油化工公司研究院开发出一种复合多金属氧化物催化剂，该催化剂是丙烯氧化制丙烯醛、丙烯酸催化剂的核心技术，     

Cu(II), Co(II) and Ni(II) Complexes Installed on Functionalized Silica Surface for Hydrogen Peroxide Assisted Cyclohexane Oxidation

In this work, Cu(II), Co(II) and Ni(II) complexes of the Schiff base ((S,E)-2-(3,4-dimethoxybenzylideneamino)-3-(1H-imidazol-4-yl)propionic acid) were synthesized and subsequently anchored onto amine functionalized silica. They were characterized by FT-IR, UV–vis., ²⁹Si NMR, TG-DTG, ESR, FE-SEM and AFM techniques, and employed as catalysts in cyclohexane oxidation using hydrogen peroxide oxidant. Silica supported Cu(II) catalyst was shown the highest catalytic activity (70%) than rest of the catalysts used. On the other hand, all the complexes were selective as they yield only cyclohexanol and cyclohexanone. Silica supported catalysts were maintained their catalytic activity over five successive catalytic run. As these catalysts are selective, reusable and functioning well with hydrogen peroxide, they could design the environment friendly catalytic system for effective cyclohexane oxidation.     

Homogeneous Catalysis. Mechanisms of Metal Catalysed Claisen Rearrangements of O-allylic-S-methyl dithiocarbonates

A number of catalysts of Pd(II), Pt (II), Rh (I) and Ir(I) induce rearrangements of O-allylic-S-methyl dithiocarbonates at 25° C. For most substrates, the Pd(II) and Pt(II) catalysts cause [3,3] sigmatropic (Claisen) rearrangements but the Rh(I) and Ir(I) catalysts give, in addition, other products depending on the catalyst and the substrate. The Claisen rearrangements observed with the Pd(II) and Pt(II) catalysts are believed to occur by a cyclization induced mechanism, whereas those rearrangements associated with the Rh(I) and Ir(I) catalysts, as well as in one case with the Pd(II) catalyst, appear to involve metal stabilized carbocation intermediates. When cyclic substrates are used retention of configuration is observed predominantly for all catalysts tried.     

Synthesis and investigation of anchored copper (II) complexes within MCM-41 as selective catalysts for epoxidation of olefins

In the present study, preparation, characterization and catalytic activity of encapsulated copper (II) complexes within MCM-41 were investigated. The mesoporous molecular sieve MCM-41 was synthesized and grafted with 3-(trimethoxysilyl)-1-propanethiol to give a thiol modified material (MCM-41-S). The prepared material successively was reacted with acrylic acid and acrylonitrile to give AA-MCM-41 and AN-MCM-41, respectively. Using hexamethyldisilazane and copper (II) chloride, copper (II) complexes in the cavities of MCM-41 (Cu-AA-MCM-41 and Cu-AN-MCM-41) were prepared. The presence of copper (II) complex on the surfaces of host matrix and the structure of prepared catalyst is investigated by FT-IR, inductively coupled plasma-optical emission spectroscopy (ICP-OES), powder X-ray diffraction (XRD) and BET nitrogen adsorption–desorption methods. The catalytic activities of the catalysts were studied in epoxidation of olefins. The results showed that activities of the prepared catalysts (Cu-AA-MCM-41 and Cu-AN-MCM-41) and their selectivity to corresponding epoxides were more than those of MCM-41. In addition, the synthesized heterogeneous catalysts were truly reusable.     

Synthesis and Characterization of Magnetic Functionalized Ni and Cu Nano Catalysts and Their Application in Oxidation,Oxidative Coupling and Various Multi-Component Reactions

Catalysis Letters - Two magnetic nano catalysts of nickel and copper, Fe3O4@SiO2@DOP-BenPyr-M(II), (M=Ni and Cu) have been synthesized. These catalysts were applied as recoverable, efficient and...     

CS2 Poisoning of Size-Selective Cubooctahedral Pd Particles in Styrene Hydrogenation

Copper, manganese and iron phthalocyanines were found to be highly efficient catalysts for cyclopropanation of olefins using ethyldiazoacetate as carbene precursor. In general copper(II)-phthalocyanine was found to be the most active catalyst followed by the Mn(II)Pc and Fe(II)Pc. Ni(II)Pc and Co(II)Pc were found to be the less active catalysts for this reactions.     

Ring-Opening Metathesis Polymerization of 5,6-Bis(Chloromethyl)-Norbornene by Tungsten(II) and Molybdenum(II) Complexes

The reaction of endo,endo-5,6-bis(chloromethyl)bicyclo[2.2.1]hept-2-ene in the presence of seven-coordinate tungsten(II) and molybdenum(II) complexes of the type [MCl(M'Cl₃)(CO)₃(NCMe)₂] (M'=W, Mo; M=Sn, Ge) leads to ring-opening metathesis polymerization and to the formation of high-molecular-weight soluble polymers with dispersity index in the range 1.4-2.0 and number average molecular weights in the range 300 000-790 000 g mol^-1. The geometric structure of these polymers was determined by means of ¹H- and ¹³C-NMR spectroscopy. Molybdenum catalysts gave polymers with lower cis vinylene content (20-50%), whereas tungsten catalysts gave polymers with higher cis vinylene content (84-95%).     

Recyclable Enantioselective Catalysts Based on Copper(II) Complexes of 2‐(Pyridine‐2‐yl)imidazolidine‐4‐thione: Their Application in Asymmetric Henry Reactions

This paper describes the preparation of enantioselective catalysts based on derivatives of imidazolidine‐4‐thione and their subsequent anchoring by means of a sulfur atom on a polymeric carrier. First, we verified the catalytic activity and enantioselectivity in the Henry reaction of the homogeneous variants of the catalysts, i.e., the copper(II) complexes of 2‐(pyridine‐2‐yl)imidazolidine‐4‐thiones and 4‐benzylsufanyl‐2‐(pyridine‐2‐yl)imidazolines themselves. It was found that these catalysts exhibit high enantioselectivity (up to 98% ee). Subsequently, the imidazolidine‐4‐thione catalysts were immobilized by anchoring to polymeric carriers based on a copolymer of styrene and 4‐vinylbenzyl chloride. These heterogeneous catalysts were analogously tested with regard to their catalytic activity and enantioselectivity in the Henry reaction, and moreover, the possibility of their separation and reuse was studied. It was found that all the prepared immobilized catalysts are highly enantioselective (up to 97% ee). Their recycling ability was tested in Henry reaction of 2‐methoxybenzaldehyde with nitromethane. It was found that they can be recycled more than ten times without any decrease of their enantioselectivity. Therefore, they present a better means of catalysis than the original copper(II) complexes of imidazolidine‐4‐ones from both economic as well as ecological points of view. Thus, such immobilized catalysts exhibit high application potential for the asymmetric Henry reaction.

     

Ligand-modulated palladium-catalyzed aerobic alcohol oxidations

The discovery and investigation of ligand-modulated Pd-catalyzed aerobic alcohol oxidations is documented. The project has evolved from a simple empirical discovery that (-)-sparteine, in combination with Pd(II) salts, facilitates the aerobic oxidative kinetic resolution of secondary alcohols to an in-depth physical organic investigation that has provided key insights into how new, more effective catalysts can be designed. Mechanistic investigations, the substrate scope for the catalysts developed, and implications to oxidation catalysis are discussed.     

IV. Some aspects of oxidative catalysis by supported metal complexes (phtalocyanates of 3d-metals)

Using DMFA or -bromonaphtalene, phtalocyanate complexes of Fe(II),Co(II),Ni(II), Cu(II) and Zn(II) were supported onto a surface of 3-aminopropylærosil (SAA) and poly(3-aminopropyl)- siloxane (SAP). The content of fixed complexes was shown to depend on the nature of a metal, matrix and, in a lesser extent, a solvent. On going from SAA to SAP there was observed actually an inversion of the concentration sequence. That seems to be due to a matrix effect. The samples obtained were tested as the catalysts for oxydation of unsaturated hydrocarbons and alcohols.     

Strategies for immobilizing homogeneous zinc catalysts in biodiesel production

This work describes two strategies for immobilizing Zn(II) catalysts: anchorage of a [ZnCl₂(N,N)] type complex on silica and decoration of PAMAM-G0-3 dendrimers with analogous metal pendants. Both types of catalysts were able to catalyze the trans-esterification of neutral and acid soybean oil, and could be easily recycled through filtration techniques.