超高比表面炭载钼煤气甲烷化催化剂

以沥青中间相为原料，氢氧化钾直接活化，获得了比表面达２３６３ｍ￣２／ｇ的超高比表面炭分子筛（ＣＭＳ）。分别以ＣＭＳ、ＳｉＯ＿２、活性炭和θ－Ａｌ＿２Ｏ＿３为担体，制备了负载钼催化剂，并研究其加压甲烷化反应性能，发现活性依下面顺序增加：θ－Ａｌ＿２Ｏ＿３＜ＳｉＯ＿２＜活性炭（ＡＣ）＜ＣＭＳ。还分别以钼酸铵和磷钼酸（ＨＰＭｏ）为前驱体，制备了ＣＭＳ负载钼催化剂，并考察了其煤气甲烷化活性，发现不同的催化剂前驱体对催化剂反应活性影响很大。根据产物中ＣＨ＿４／ＣＯ＿２的变化，推测ＣＯ在钼催化剂上的甲烷化反应包括如下两个步骤：（１）３Ｈ＿２＋ＣＯ→ＣＨ＿４＋Ｈ＿２Ｏ，（２）ＣＯ＋Ｈ＿２Ｏ→ＣＯ＿２＋Ｈ＿２。     

用射频等离子体技术制备乙炔选择加氢催化剂及其性能研究

 采用射频等离子体技术制备了α－Al2O3（MgO修饰）负载钯催化剂，以乙炔选择加氢为模型反应考察了制备方法、钯含量、助剂种类及反应温度对催化剂性能的影响．结果表明，采用等离子体技术制备的催化剂具有催化活性及乙烯选择性高、操作简便和工艺流程短等优点，在50℃下反应时乙炔转化率可达100％，乙烯选择性可达71．3％，而且在反应20h后催化剂样品仍保持有高活性．CeO2助剂的加入能改善催化剂的催化性能．     

Pd／C催化剂用于苯胺氧化羰基化

研究了催化剂制备条件、助催化剂对负载型Ｐｄ／Ｃ催化剂性能的影响及氧分压、原料苯胺中硝基苯的加入对苯胺氧化羰基化反应的影响；用Ｘ光电子能谱（ＸＰＳ）、程序升温还原（ＴＰＲ）和现场红外（ＩＲ）表征钯催化剂；根据实验结果提出在Ｐｄ／Ｃ－ＮａＩ催化剂体系、醇介质中，苯胺氧化羰基化可能的反应机理．     

钯(0)/离子交换树脂对有机锡试剂和有机卤化物偶联反应的催化性能和结构表征

制备了强碱阴离子交换树脂（Ｐ－－ＣＨ２＾＋（ＣＨ３）３ＯＨ＾－，Ｄ７１７）负载钯（０）催化剂，发现它对有机锡试剂和有机卤化物的偶联反应有很高的催化活性，分离容易，可重复使用。起催化作用的是金属态钯。ＸＰＳ等实验结果表明，在催化剂中钯作为桥将功能基－Ｎ＾＋（ＣＨ３）３与ＯＨ＾－联结起来。催化剂中的钯可以看作是两配位的和配位不饱和的，经过氧化加成、金属交换、还原消除过程完成催化反应。     

二氧化硅负载聚（丙烯腈—乙烯基三乙氧基硅烷）钯（II）配合物的合…

本文合成了二氧化硅负载聚（丙烯腈－乙烯基三乙氧基硅烷）钯（Ⅱ）络合物并对该加氢催化剂及其载体进行了结构表征，证明钯与氰基络合。     

钯（0）／离子交换树脂对有机锡试剂和有机卤化物偶联反应的催化性能和结构表征

制备了强碱性阴离子交换树脂（）负载钯（０）催化剂，发现它对有机锡试剂和有机卤化物的偶联反应有很高的催化活性，分离容易，可重复使用．起催化作用的是金属态把．ＸＰＳ等实验结果表明，在催化剂中钯作为桥将功能基－Ｎ（ＣＨ３）３与ＯＨ－联结起来．催化剂中的把可以看作是两配位的和配位不饱和的，经过氧化加成、金属交换、还原消除过程完成催化反应．     

在杂多酸催化剂上苯和1-十二烯烷基化合成十二烷基苯

对不同ＳｉＯ２负载磷钨酸（ＰＷ）催化剂的表面性质、热稳定性、酸性、以及对苯与丙烯和１－十二烯的烷基化反应的催化活性进行了对比研究,结果表明,ＰＷ在ＳｉＯ２上的分散状况与ＳｉＯ２的比表面积和孔径大小有关,ＰＷ与载体表面作用的强弱会直接影响负载型催化剂的热性和酸性,采用不同的ＳｉＯ２可以制得比表面积、孔结构和酸强度不同的负载型ＰＷ催化剂,以满足不同催化反应的要求。     

担体对Fe-MnO催化剂CO加氢合成烯烃性能影响的TPSR表征

考察了不同担体担载的Ｆｅ－ＭｎＯ催化剂上ＣＯ加氢合成烯烃的反应。结果表明担体直接影响低碳烯烃选择性。通过对催化剂的ＣＯ，ＣＯ／Ｈ２，Ｃ２Ｈ４等吸附的ＴＰＳＲ表征及催化剂表面ＣＯ加氢微观反应的研究，证明以碱性担体为基质的ＰＢＣ催化剂具有强吸附ＣＯ能力，且生成的烯烃不易发生二次反应，因而ＰＢＣ催化剂具有较高的烯烃选择性；以酸性担体为基质的ＰＡＣ催化剂对ＣＯ为弱吸附，对Ｈ２为较强吸附，且烯烃会发生强烈的     

SBA-15负载钯催化剂的制备及其在超临界二氧化碳介质中催化Suzuki偶联反应的研究

采用3-巯丙基三甲氧基硅烷为内表面修饰剂,三甲氧基苯基硅烷为外表面修饰剂,合成了内外表面被修饰的介孔分子筛SBA-15,并制备了负载钯催化剂.应用X射线粉末衍射仪(XRD),傅立叶红外光谱仪(FT-IR),紫外可见光谱仪,扫描(SEM)、透射(TEM)电子显微镜等仪器对材料结构进行了表征.考察了负载钯催化剂在超临界二氧化碳介质中催化Suzuki偶联反应的活性,结果表明:制得的负载钯催化剂稳定、活性高;以四丁基乙酸胺为碱,对溴硝基苯与苯硼酸在90℃下反应48 h,得到71%收率的对硝基联苯.     

SiO2负载的氮化钼催化剂的合成和表征

采用ＭｏＯ３／ＳｉＯ２和ＮＨ３程序升温反应的方法合成了一系列不同Ｍｏ含量的Ｍｏ２Ｎ／ＳｉＯ２催化剂，并采用ＸＲＤ、ＢＥＴ、ＸＰＳ、ＴＰＲ、Ｈ２－ＴＰＤ和ＩＲ等手段，结合中压下吡啶加氢脱氮反应，研究了它们的表面性质和反应性能。发现Ｍｏ２Ｎ／ＳｉＯ２催化剂在反应性能和吸氢性质等方面类似于非负载的氮化钼。氮化前后，低Ｍｏ担载量催化剂的比表面积降低不大，在高Ｍｏ担载量下，由于氮化态的Ｍｏ－ＳｉＯ２催化剂上     

负载型手性钯催化剂的制备和在苯乙酮不对称加氢反应中的应用

在硅烷化硅胶上涂敷手性高分子配位体三苯基氨基甲酸纤维素酯和三（３,５－二甲基苯基氨基甲酸）纤维素酯,然后与ＰｄＣｌ３配位,制备一种新型的负载型不对称加氢催化剂,该催化剂用于苯乙酮的加氢反应,醇收率最高达１００％,但产物的对遇选择性较低的原因。     

New heterogenized C2-symmetric bis(sulfonamide)-cyclohexane-1,2-diamine-RhCp∗ complexes and their application in the asymmetric transfer hydrogenation (ATH) of ketones in water

C₂-symmetric bis(sulfonamide) ligands derived from chiral trans-(1R,2R)-cyclohexane-1,2-diamine were immobilized on silica gel and on polystyrene resin, and complexed to Rh^IIICp∗. The resulting complexes were used as catalysts in the asymmetric transfer hydrogenation (ATH) of acetophenone. The chiral secondary alcohol was obtained in high yields (>99%) and enantioselectivities (92%) with aqueous sodium formate as the hydride source. The immobilized catalysts were recycled with no loss in activity.     

Platinum carbonyl derived catalysts on inorganic and organic supports: a comparative study

Fumed silica, silica gel, silica-alumina and cross-linked (5.5%) polystyrene have been functionalized with quaternary ammonium groups and the Chini cluster [Pt₁₂(CO)₂₄]²⁻ has been anchored onto these functionalized materials by ion pairing. A catalyst has also been prepared by the adsorption of Na₂[Pt₁₂(CO)₂₄] on unfunctionalized fumed silica. The catalytic activities of the resultant materials, and that of commercially purchased 5% platinum on alumina have been studied for the hydrogenation of a variety of unsaturated compounds. The substrates studied are: α-acetamidocinnamic acid, cyclohexanone, acetophenone, methyl pyruvate, ethyl acetoacetate, nitrobenzene and benzonitrile. Compared to the polystyrene supported catalyst, the inorganic oxide supported catalysts have higher surface areas and for most of the substrates have notably higher activities. The functionalized fumed silica-based catalyst gives higher conversions than functionalized silica gel and silica-alumina-based catalysts. In the hydrogenation of acetophenone and ethyl acetoacetate, the functionalized fumed silica-based catalyst show superior activity compared to the commercial platinum catalyst, and the catalyst made by conventional adsorption method. In benzonitrile hydrogenation with all the cluster-derived catalysts a hydrazine derivative is selectively formed, but when the commercial platinum catalyst is used benzyl amine is the main product.     

Asymmetric hydrogenation of acetophenone catalyzed by cinchonidine stabilized Ir/SiO2

A series of silica (SiO₂) supported iridium catalysts stabilized by cinchona alkaloids was prepared and applied in the heterogeneous asymmetric hydrogenation of acetophenone. Cinchona alkaloids exhibited a marked ability to stabilize and disperse the Ir particles. In the presence of (1S,2S)-diphenylethylenediamine ((1S,2S)-DPEN)) as chiral modifier, the cinchonidine (CD) stabilized catalyst 5%Ir/2CD-SiO₂ exhibited excellent catalytic performance in the asymmetric hydrogenation of acetophenone in MeOH. Under the optimum conditions, the ee value of (R)-phenylethanol achieved 79.8% and no other product was produced, a higher enantioselectivity than that reported up to now for acetophenone hydrogenation catalyzed by the supported metal catalysts modified by chiral reagents. In particular, a synergistic effect between (1S,2S)-DPEN and CD was observed, which significantly accelerated the reaction rate and enhanced the enantioselectivity. The catalyst can be reused several times without a significant loss of activity and enantioselectivity.     

(1S,2S)-1,2-二苯基乙二胺修饰Ir/SiO2催化苯乙酮及其衍生物不对称加氢（英文）

不添加任何稳定剂,在碱性条件下制备了5%Ir/SiO2催化剂,并用于催化苯乙酮的不对称加氢反应中,详细考察了碱和手性修饰剂种类、氢气压力、反应温度、(1S,2S)-1,2-二苯基乙二胺((1S,2S)-DPEN)浓度对反应的影响.在优化反应条件下,5%Ir/SiO2催化剂表现出较好的反应活性和对映选择性.其中,苯乙酮不对称加氢反应的对映选择性达70%.该催化剂不需要任何稳定剂,制备方法简单,催化性能稳定,通过简单的离心分离即可循环使用.     

Synthesis of dendritic catalysts and application in asymmetric transfer hydrogenation

Frechet-type core-functionalized chiral diamine-based dendritic ligands and hybrid dendritic ligands condensed from polyether wedge and Newkome-type poly(ether-amide) supported multiple ligands were designed and synthesized. The solubility of hybrid dendrimers was found to be finely controlled by the polyether dendron. The catalytic efficiency and recovery use of dendritic ruthenium complexes were compared in the transfer hydrogenation of acetophenone. The core-functionalized dendritic catalysts demonstrated much better recyclability, which verified the stabilizing effects of the bulky polyether wedge on the catalytically active complex. Moreover, the dendritic catalysts were applied in the asymmetric transfer hydrogenation of ketones, enones, imine, and activated olefin, and moderate to excellent enantioselectivitiy was achieved comparable to that of monomeric catalysts.     

面包酵母用于苯乙酮的不对称还原研究

研究了面包酵母用于苯乙酮的不对称还原，分别考虑了反应温度，反应时间，底物浓度等因素对转化率和对映选择性的影响，结果表明，在合适的生物转化条件下，底物苯乙酮以中等的转化率被还原并得到较高对映体过量值的产物S－1－苯基乙醇。     

负载型金属催化剂Ru, Rh和Pd体系对CO化学吸附的理论研究(Ⅱ)

近年来, 过渡金属催化剂对CO的化学吸附已有较多的理论研究报道[1~3]. 但由于涉及到含d电子较多的过渡金属, 大多数的计算仍采用半经验方法, 即使有些计算采用了非经验方法, 但所用基组小[4,5], 考虑电子的相关作用较少. 由于对过渡金属体系用包括电子相关作用的计算方法是必要的[6], 故本文采用DFT计算方法[7]和LANL1DZ基组[8,9]进行了计算, 并在前文[10]基础上, 集中讨论SiO2的担体作用. 担体在催化剂中占有很重要的地位, 但其发挥什么作用, 一直是被探讨的重要理论课题. 本文选择以SiO2为担体研究对象, 仍以Ru, Rh, Pd为金属催化剂活性组分, 对担体如何影响CO的化学吸附和金属的催化选择性进行理论探讨, 并进一步推测最终对CO氢化反应产物的影响.     

硅胶负载聚乙烯基吡啶—钯催化剂的制备及其催化加氢性能的研究

利用硅胶表面的弱酸性和吸附性能,将某些碱性聚合物吸附在硅胶表面上,然后与PdCl_2络合,经还原,合成了硅胶负载的聚乙烯基吡啶-钯催化剂。用XPS、UV-Vis、电子显微镜等手段研究了催化剂的结构,观察了制备条件、组成等因素对其性能的影响。研究了各种反应条件与催化剂活性的关系及催化剂的稳定性和使用寿命。合成的催化剂对丙烯酸甲酯等底物具有很高的催化加氢活性。     

Solid-phase synthesis of homogeneous ruthenium catalysts on silica for the continuous asymmetric transfer hydrogenation reaction

The solid-phase synthesis of new asymmetric transfer hydrogenation catalysts as well as the use of these silica supported systems in batch and flow reactors is reported. The ruthenium complex of NH-benzyl-(1R,2S)-(-)-norephedrine covalently tethered to silica showed a high activity and enantioselectivity in the reduction of acetophenone. In three consecutive batchwise catalytic runs, we obtained ee values of 88%. In a continuous flow reactor, a very constant catalytic activity was observed; no catalyst deactivation occurred over a period of one week. This has been ascribed to successful site isolation. Using optimized conditions in this flow reactor, the ee was as high as 90% at 95% conversion. The supported catalysts generally show the same trend in catalyst performance as in solution. The viability of our approach was further shown in one example, the ruthenium(II) complex of (1S,2R)-(+)-2-amino-1,2-diphenylethanol, for which an enantiomeric excess of 58% was observed, which is nearly three times higher than its homogeneous analogue.