Enantiospecific electrodeposition of a chiral catalyst

Many biomolecules are chiral--they can exist in one of two enantiomeric forms that only differ in that their structures are mirror images of each other. Because only one enantiomer tends to be physiologically active while the other is inactive or even toxic, drug compounds are increasingly produced in an enantiomerically pure form using solution-phase homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantioselective catalysts that can more readily be separated from the products and reused. In addition, such surfaces might serve as electrochemical sensors for chiral molecules. To date, chiral surfaces have been obtained by adsorbing chiral molecules or slicing single crystals so that they exhibit high-index faces, and some of these surfaces act as enantioselective heterogeneous catalysts. Here we show that chiral surfaces can also be produced through electrodeposition, a relatively simple solution-based process that resembles biomineralization in that organic molecules adsorbed on surfaces have profound effects on the morphology of the inorganic deposits. When electrodepositing a copper oxide film on an achiral gold surface in the presence of tartrate ion in the deposition solution, the chirality of the ion determines the chirality of the deposited film, which in turn determines the film's enantiospecificity during subsequent electrochemical oxidation reactions.     

氧化银在有机合成中的应用

氧化银是有机反应中的一种常见催化剂,从催化活性、选择性及产物收率等方面综述了近15年来氧化银应用于催化有机反应的研究进展,并将氧化银与其他催化剂进行了比较．     

SnCl4对酯化反应的催化作用

SnCl4是一种强的路易士酸，对氧具有很强的配位能力。为探索SnCl4对酯化反应的催化作用，现以SnCl4为催化剂来合成常见的几种酯，并与其它几种常见的催化剂的催化活性进行了比较，还从SnCl4的用量、反应温度和反应时间、催化机理等几个方面进行了探讨，实验表明，SnCl4对酯化反应有很高的催化活性，尤其对于高沸点的伯醇和叔醇，比其它几种催化剂的催化效果更好，可代替其它几种催化剂来合成某些酯。     

铜锰复合氧化物低温催化氧化甲醛的性能研究

 采用简单的氧化还原方法,通过控制Cu和Mn物质的量之比及煅烧温度等条件合成了一系列铜锰复合氧化物。通过考察合成条件对催化剂的晶相、形貌以及催化活性的影响,从而确定最佳的工艺条件,结合X射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）等多种表征手段揭示催化剂结构和活性的关系。研究结果表明,在单一锰氧化物中,铜的掺杂促进氧物种移动,使得铜锰复合氧化物具有较低的还原温度和较强氧化还原能力,且结晶度差的无定型态同样有利于氧空穴的增加,从而有利于甲醛的催化氧化。当Cu/Mn物质的量之比为1：2、煅烧温度为300℃时制得的铜锰复合催化剂催化性能最佳,能够在90℃下完全降解甲醛。     

High-valent organometallic copper and palladium in catalysis

Copper and palladium catalysts are critically important in numerous commercial chemical processes. Improvements in the activity, selectivity and scope of these catalysts could drastically reduce the environmental impact, and increase the sustainability, of chemical reactions. One rapidly developing strategy for achieving these goals is to use 'high-valent' organometallic copper and palladium intermediates in catalysis. Here we describe recent advances involving both the fundamental chemistry and the applications of these high-valent metal complexes in numerous synthetically useful catalytic transformations.     

云南小龙潭煤催化加氢反应的研究

本文用国产的高压差热分析仪评价了五种铁催化剂对云南小龙潭煤加氢反应的催化活性。发现FeS和天然硫铁矿有良好的催化效果,而Fe_2O_3和含Fe_2O_3的工业废渣——太钢转炉飞灰的催化效果不明显。说明铁催化剂只有在以硫化物状态存在时,对煤加氢反应才呈现出较好的催化活性。予硫化后催化剂活性得到提高的事实进一步证明了这一结论。根据Freeman-Carrol法计算了Fe_2O_3、FeS太钢转炉飞灰、予硫化后的太铁转炉飞灰作催化剂时小龙潭煤加氢反应的动力学参数。同时用Speil公式计算了这些反应的热效应,建立了热效应与DTA峰前温度和峰后温度下反应产物中组分变化之间的关系。     

MoVTeO/SiO2催化剂上丙烷选择氧化制丙烯醛

用浸渍法制备了一系列不同组成的MoVTeO/SiO2催化剂,并用XRD、TPR和催化剂性能评价等方法考察了催化剂的物相结构、氧化还原性质及其对丙烷选择氧化制丙烯醛反应的催化性能.结果表明,由于组份之间的相互作用,MoO3的分散度提高,还原温度降低,且其某些晶面可能部分重构或被其它组份覆盖,因而有利于催化活性的提高和丙烯醛的生成.在考察的不同催化剂组成中,(Mo V Te)/Si原子比为6%的MoV0.2Te0.1/SiO2催化剂具有最佳的反应性能.反应条件对催化剂性能的影响说明,在丙烷选择氧化制丙烯醛反应中,丙烯为反应的中间物种.     

Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions

Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient. The introduction of catalytic systems using oxygen from air is preferred for 'green' processing. Gold catalysis is now showing potential in selective redox processes, particularly for alcohol oxidation and the direct synthesis of hydrogen peroxide. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide, hydroperoxides or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products ( approximately 98%) and significant conversions. Our finding significantly extends the discovery by Haruta that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.     

The Influence of Pore Structures and Degree of Cross-Linking on Catalytic Properties of Aminomethyl Polystyrene Resin Supported Dendritic Copper Complexes

1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homogeneous systems.The polymer-supported catalysts enhance their thermal stability,selectivity,recyclability and easy separation from reaction products leading to the operationally flexible[1-2].Such behaviour prompted us to know the effect of pore structures of polymer supporters on catalytic ...     

均相和非均相Fenton型催化剂催化氧化含酚废水

研究了均相和非均相Penton型催化剂催化氧化含酚废水．对均相催化氧化反应进行正交试验和单因数试验，确定其氧化降解特定废水的最优化条件．在Fenton反应机理的基础上，探讨了Fe^3 在均相和非均相条件下的催化氧化机理；制备了Fe^3 ／人造沸石和Fe^3 ／活性炭催化剂；进行了非均相催化氧化降解高浓度含酚废水的试验；比较了均相和非均相催化氧化反应对苯酚降解率的影响．结果发现非均相反应能大大提高苯酚降解率，使用Fe^3 ／活性炭为催化剂时可使苯酚的降解率达到93．02％．     

甲烷催化燃烧催化剂的研究进展

甲烷催化燃烧的目的是通过催化作用降低其起燃温度(T_(10))和完全转化温度(T_(90)),加深其氧化程度,从而提高燃料的利用率。简述了甲烷催化燃烧反应的机理,从种类、制备方法以及催化性能等方面详细介绍了甲烷催化燃烧催化剂的最新进展。贵金属催化剂的催化性能优越,但高成本以及热稳定性差等因素极大地限制了其应用;非贵金属催化剂尤其是复合金属氧化物催化剂(例如钙钛矿型复合金属氧化物催化剂和六铝酸盐系列催化剂等)拥有较高的催化活性,因其成本低,有更好的发展前景。提高非贵金属催化剂的低温催化活性和高温热稳定性是今后甲烷催化燃烧催化剂的主要研究方向。     

Photocatalytic degradation of benzene in gas phase by nanostructured BiPO4 catalysts

A rod-shaped BiPO4 photocatalyst was prepared by a simple hydrothermal method for light-induced catalytic degradation of stable aromatic compounds such as benzene in gas phase under ambient conditions. The samples were subjected to various technical characterizations including X-ray diffraction (XRD), transmission electron microscopy (TEM), UV/vis and FTIR spectrum, to determine the crystal structure, morphology, and optical properties of the as-prepared photocatalysts. Results indicate that BiPO4 exhibits much higher photocatalytic activity and stability under UV light irradiation than that of commercial TiO2 (Degussa P25) in the degradation of benzene to CO2. The active radical species involved in the degradation reactions over BiPO4 photocatalyst have been investigated by the spin-trapping electron paramagnetic resonance (EPR) spectra and a photoluminescence technique. Theoretical calculations reveal that BiPO4 contains highly-dispersive conduction bands, enabling high mobility of the photo-generated carries and therefore leading to fast charge transfer and separation.     

己二酸二异辛酯合成用负载磷钨酸催化剂筛选及催化作用

采用自建动态酯化反应实验装置，研究了以负载型磷钨杂多酸作为催化剂合成己二酸二异辛酯的酯化反应体系。根据多种不同载体负载的催化剂的活性和寿命。筛选出一种较为理想的硅胶负载型磷钨杂多酸催化剂。该催化剂在反应条件下，反应１ｈ，转化率达９７％。借助程序升温分解，吸附吡啶后的程序升温分解及红外等手段，对催化剂进行了表征。     

RM5型储氢材料的预处理及对合成氨的催化机制

本文研究了RM_5(R—稀土,M—过渡金属)型储氢材料作为氨合成反应催化剂时的预处理方式,表明先反复吸放氢再高温氮化的两步预处理能获得较高催化活性,第一步使样品获得较大比表面;第二步形成催化活性物种RN和金属M。同时,分析探讨了处理过程中的影响因素,提出催化活性中心是两物种的晶相接界处的机制。     

S2O82-/ZrO2-MxOy(M=Al,Fe,Cr,Mn,Ti)固体超强酸催化剂的研制

制备了一系列金属氧化物MxOy(M=Al,Fe,Cr,Mn,Ti）促进的S2O8^2-/ZrO2-MxOy固体超强酸催化剂，用乙酸和正丁醇的酯化反应研究了制备条件对催化剂活性的影响，实验结果表明，催化剂对酯化反应有很高的催化活性，添加不同的金属氧化物对催化剂的酯化反应催化活性有不同的影响，其中Cr含量为0.5%的催化剂S2O8^2-/ZrO2-Cr2O3对乙酸和正丁醇的酯化反应具有很高的催化活性，乙酸的转化率高达86.1%，而在相同条件下，不加催化剂时乙酸的转化率仅为26.9%，制备条件对催化剂活性影响很大，通过X射线衍射分析（XRD）证实，催化剂中ZrO2主要以四方晶相（Tetragonal phase）存在，少量以单斜晶相（Monoclinic phase）存在，T相和S2O8^2-是保证催化剂活性的关键因素。     

双分子Salen金属催化剂的研究进展

双分子Salen金属配合物通过双金属活性中心的协同作用能够有效地催化多种化学反应.双金属催化剂拥有2个金属催化中心,可以同时对底物进行活化,从而加快反应速度和提高反应选择性.某些情况下,有些不能发生的新反应通过这种策略也能很好地反应.对双分子Salen金属催化剂的设计原理、最有效的合成方法作了归纳总结,并讨论了其在催化方面的应用.     

A new strategy for the generation of catalytic antibodies

The high binding affinity and specificity of antibodies for a wide range of ligands has recently been exploited in the generation of catalysts for acyl-transfer reactions, carbon-carbon bond forming and carbon-carbon bond cleaving reactions. In addition, a number of strategies are emerging for the generation of catalytic antibodies including transition state stabilization, catalysis by approximation, and the introduction of catalytic groups or cofactors into antibody combining sites. An important goal in the design of catalytic antibodies is the development of general rules relating hapten structure to the corresponding catalytic groups in the antibody combining site. We report here that electrostatic interactions between a hapten and the complementary antibody can be exploited to generate catalytic amino-acid side chains in an antibody-combining site. The antibody-catalysed reaction, a beta-elimination reaction, exhibits saturation kinetics, substrate specificity, competitive inhibition by hapten, and specific inactivation by a reagent that modifies carboxylate residues.     

含过渡金属分子筛催化环己醇与空气氧化制备环己酮

分别采用离子交换法、水热合成法和干胶转化晶化法,将非贵过渡金属引入到分子筛中合成出含过渡金属的分子筛催化剂,并将其应用于以空气为氧化剂、多相催化环己醇合成环己酮的反应中,探索高效、环保、廉价的绿色催化氧化反应体系.研究结果表明,采用水热合成法制备的含钴分子筛(CoAlPO-5)在催化空气氧化环己醇制备环己酮的反应中表现出优异的催化活性,通过考察反应温度、空气流速、反应时间、催化剂用量等探索了最佳催化反应条件是:反应温度为100℃、空气流速为40mL/min、反应时间为8h、催化剂用量为100mg时,环己醇转化率可达到38.2%,环己酮选择性达到95.8%.     

Reverse microemulsion synthesis of nanostructured complex oxides for catalytic combustion

Catalysts play an important role in many industrial processes, but their use in high-temperature applications-such as energy generation through natural gas combustion, steam reforming and the partial oxidation of hydrocarbons to produce feedstock chemicals--is problematic. The need for catalytic materials that remain stable and active over long periods at high operation temperatures, often in the presence of deactivating or even poisoning compounds, presents a challenge. For example, catalytic methane combustion, which generates power with reduced greenhouse-gas and nitrogen-oxide emissions, is limited by the availability of catalysts that are sufficiently active at low temperatures for start-up and are then able to sustain activity and mechanical integrity at flame temperatures as high as 1,300 degrees C. Here we use sol-gel processing in reverse microemulsions to produce discrete barium hexa-aluminate nanoparticles that display excellent methane combustion activity, owing to their high surface area, high thermal stability and the ultrahigh dispersion of cerium oxide on the their surfaces. Our synthesis method provides a general route to the production of a wide range of thermally stable nanostructured composite materials with large surface-to-volume ratios and an ultrahigh component dispersion that gives rise to synergistic chemical and electronic effects, thus paving the way to the development of catalysts suitable for high-temperature industrial applications.     

LaCo0.2Fe0．8O4型钙钛矿型催化剂中A位取代对耐热性能的影响

研究了LaCo0.2Fe0.8O4型钙钛矿型催化剂催化燃烧改变A位取代的程度,发现晶粒度随取代度的增加而减小,同时晶格氧的量有所增大.由于高温使晶粒度增大,晶格氧减少,而适量的晶格氧有利于催化剂活性,所以较大的取代度能够使催化剂在较高温度下保持较好活性.