负载型纳米非贵金属催化剂上一氧化碳的氧化 Ⅲ.纳米Cu/γ-Al_2O_3催化剂预处理对催化剂活性的影响

以电弧等离子体法制备纳米铜活性组分．将物理法制备的负载型纳米Ｃｕ／γ－Ａｌ２Ｏ３催化剂用于催化一氧化碳氧化反应，发现在催化过程中其催化活性呈规律性变化，即初始活性较低；空气中焙烧预处理易使纳米粒子长大．催化剂的氧化与一氧化碳还原实验表明，铜氧化物活性高于零价铜     

锰铈混和氧化物气凝胶催化剂的研究

采用溶胶-凝胶法和超临界干燥技术制备出CeO2和Ce1-xMnxO2(x分别为0.05, 0.10, 0.15,0.20)气凝胶。以硝酸锰浸渍制得的氧化铈气凝胶Mn/CeO2,用TEM、BET、一氧化碳催化氧化活性评价和H2-TPR对所制备的催化剂进行了研究。TEM、BET的结果表明，随着锰含量的增加，氧化铈气凝胶的粒度减小，表面积增大。一氧化碳催化氧化活性评价显示,氧化铈中添加锰制得的催化剂的一氧化碳低温催化氧化的活性比未添加锰的氧化铈提高。且锰加入量为15 mol%时，气凝胶的催化活性最高。锰的引入方式不同，气凝胶的催化活性不同。浸渍方式负载锰所制备的Mn/CeO2气凝胶的一氧化碳催化氧化活性低于Ce1-xMnxO2(x分别为0，0.05, 0.10, 0.15,0.20)气凝胶。TPR实验发现，与氧化锰相同，氧化铈上负载的锰的还原也分三步进行。     

负载型金催化剂对CO氧化的催化性能（Ⅰ）

负载型金催化剂对ＣＯ氧化的催化性能（Ⅰ）郝郑平，安立敦，李胜利，王弘立（中国科学院兰州化学物理研究所，兰州，７３００００）关键词负载型金催化剂，一氧化碳氧化，制备因素１．前言金历来被用来做为货币保值和饰品材料，由于化学惰性和难于制备高分散微粒，直到１...     

钯(Ⅱ)/2,2′-联吡啶催化一氧化碳和苯乙烯的交替共聚反应

利用乙酸钯和２，２’－联吡啶组成的催化剂体系催化一氧化碳和苯乙烯交替共聚制备聚（１－氧代－２－苯基丙撑），考察了组成催化剂的２，２‘－联吡啶和对甲苯磺酸与钯（Ⅱ）的摩尔比对催化活性的影响，同时考察了甲醇用量，溶剂，反应温度和时间等对该催化反应的影响。     

金属壁与催化层一体化内翅片管状催化剂的研究

开发了内翅片管状金属材料经阳极氧化、封孔处理、催化剂组分负载制备金属壁与催化层一体化催化剂的制备方法。讨论了氧化膜厚度与阳极氧化时间、孔径分布与封孔处理条件，负载量与浸渍时间的关系。探讨了反应温度、孔径分布、氧化膜厚度对催化剂性能的影响，对于具有平均孔半径６￣８ｎｍ，厚度为３６μｍ的催化剂。在反应温度２００℃、空速２４００ｈ＾－１，甲醇摩尔分数０．１的条件下，甲醇脱氢生成一氧化碳的选择性接近１００     

负载型纳米非贵金属催化剂上一氧化碳的氧化：Ⅲ.纳米Cu／γ—Al2O3催化剂预？

以电弧等离子体法制备纳米铜活性组分。将物理法制备的负载型纳米Ｃｕ／γ－Ａｌ２Ｏ３催化剂用于催化一氧化碳氧化反应，发现在催化过程中其催化活性呈规律性变化，即初始活性较低；空气中焙烧预处理易使纳米粒子长大。     

氢气存在下一氧化碳偶联反应的化学和性能

实验研究了在氢气存在下，一氧化碳与亚硝酸乙酯偶联合成草酸二乙酸反应体系在典型操作条件下的化学反应和反应性能，结果表明氢气只与反应体系中的亚硝酸乙酯反应生成乙醇。由于氢气与一氧化碳在催化剂表面竞争吸附，并且氢的存在打破了生成草酸二乙酯所必需的正常的氧化还原过程：Pd^0→Pd^2 →Pd^0，因此氢的引入使一氧化碳转化率及草酸二乙酯选择性下降。此外，化学吸附测试结果表明氢气和一氧化碳是在催化剂表面同一活性中心上吸附。     

一氧化碳中温变换催化剂的研究

铁氧体是用铁氧体法处理含铬电镀废水的沉渣,它含有与一氧化碳中温变换铁铬催化剂相类似的组成.一氧化碳中温变换铁铬催化剂是国内需要量极大的一种合成氨生产用催化剂.利用铁氧体为原料制备中温变换催化剂,不但消除污染,而且变废为利,确有实际意义.本文在前一工作的基础上报导由铁氧体为原料制备的一氧化碳中温变换催化剂.     

一氧化碳气相催化偶联合成草酸二乙酯的研究

在固定床反应器中对一氧化碳气相催化偶联合成草酸二乙酯的双金属钯系催化剂进行了活性评价。研究结果表明，所研制的催化剂具有较高的活性、选择性和稳定性，具有工业开发价值；在较高的反应温度和浓度下，亚硝酸乙酯易分解而使一氧化碳转化率和草酸二乙酯空时收率下降；在原料气中加入适量的乙醇有助于提高草酸二乙酯的空时收率。提出了一氧化碳气相催化偶联合成草酸二乙酯的适宜的工艺条件。     

一氧化碳还原芒硝的动力学研究

一氧化碳还原芒硝的动力学研究鲁晓凤，唐玉华（四川大学化学系成都６１００６４）关键词：一氧化碳，芒硝，动力学，还原我们已对氢气还原芒硝进行了动力学研究￣［１］，本文是研究一氧化碳还原芒硝的动力学，为工业上实施气体还原芒硝提供可靠的实验数据。动力学模型Ｃ...     

超细粒子铜基甲醇触媒的HREM研究

超细粒子铜基甲醇触媒的ＨＲＥＭ研究顾永达，吕剑，戴丽珍（中国科学院山西煤炭化学研究所煤转化国家重点实验室太原０３０００１）于瀛大，关若男（中国科学院金属研究所固体原子象开放实验室沈阳１１００１５）关键词超细粒子，铜基触媒，高分辨电镜近十余年来，超细粒...     

UV photoelectron spectroscopy of carbonmonoxide adsorbed on small palladium particles

The adsorption of carbonmonoxide (CO) on palladium clusters evaporated onto a carbon substrate has been studied by photoelectron spectroscopy (UPS). Variations in the electron binding energy of the CO valence levels and an attenuation of the d-electron emission of Pd as a function of particle size has been observed.     

Synthesis of polyglycolic acid copolymers from cationic copolymerization of C1 feedstocks and long chain epoxides

Polyglycolic acid (PGA), which is an important biodegradable polymer, can traditionally be synthesized through the ring opening polymerization of glycolide (with mostly using tin octanoate catalyst). Our previous studies revealed that PGA was alternatively synthesized with one-step cationic polymerization of formaldehyde from trioxane and carbonmonoxide (CO), sustainable C1 feedstocks obtainable from biomethanol or biogas. PGA and its copolymers can be mainly used for the biomedical applications due to their biocompatibility and biodegradability. In order to utilize PGA in other marketing materials such as packaging, PGA should be specifically engineered to improve its physical properties by a copolymerization strategy utilizing appropriate comonomers since PGA displays brown or beige color and is not soluble in most organic solvents due to its very high crystallinity. In this study; to improve on the physical properties of PGA, such as melting temperature and solubility, polymerizations of trioxane, CO and a minor amount of epoxides with long side chains were performed under the same reaction condition as PGA homopolymer synthesis (DCM solvent, at 800 psi, with triflic acid catalyst, reaction time of 72 h). The results have shown that optimum polymerizations were achieved at lower reaction temperatures than that of PGA homopolymer synthesis (110 °C versus 170 °C). The melting temperatures of all copolymers are lower, and the colors of the copolymers have become lighter than that of PGA homopolymer. The solubilities of obtained copolymers also increased by increasing side chain length of epoxides in the polymer backbone.     

Flash Pyrolysis of 4-Arylmethylidene-oxazolones and -isoxazolones. A Versatile Synthesis of Arylacetylenes. Preliminary communication

Flash pyrolysis of 4-benzylidene-2-phenyl-5(4H)-oxazolone ( 1 ) yields carbonmonoxide, benzene, biphenyl, diphenylacetonitrile, and 2,3-diphenylsuccinonitrile; N-benzoylphenylketenimine is implicated as the primary intermediate. The flash pyrolysis of 4-arylmethylidene-3-methyl-5(4H)-isoxazolones ( 3 ) yields carbon dioxide, acetonitrile, and phenylacetylenes substituted by alkoxy, chloro, dimethylamino, and hydroxy groups, in yields of 45–95%. Arylmethylidenecarbenes are implicated as intermediates.     

Treatment of Soot by Dielectric Barrier Discharges and Ozone

The results of the presented special treatment method indicate a soot decomposition mechanism due to long-living species like ozone and a multistage process between diesel soot and ozone. Measurements inside a dielectric barrier discharge (DBD) and measurements with ozone externally generated show a strong dependence of the decomposition rate on the temperature. In addition the temperature dependence of the lifetime of ozone up to 180°C and the oxidation of carbonmonoxide to carbondioxide were investigated.     

一种新的振荡体系的研究 Ⅰ. 四极质谱对溶解气体振荡释放现象的考察

本文对溶解气体振荡释放体系使用了四极质谱进行追踪检测。确认了该体系为一种振荡的物理体系。对溶解气体振荡释放过程的实验考察表明该体系对溶解气体的放空流量等均有阈值要求。该体系对温度的变化是敏感的。在本文的实验条件下, 体系对压力、搅拌等扰动是稳定的。体系内的丙烯与合成气在一定的条件下还可以发生一种“协同”作用。实验考察表明, 溶解气体振荡释放过程的产生是由于体系在过饱和状态下成核机制所致。在非平衡条件下, 气泡生长与上升过程所造成的负反馈条件是形成周期性现象的根本原因。本机制应对溶解度大而且沸点相差也大的二元气液体系具有普适性。     

Complex Analysis of Phosphate-based Material Oxidation

The thermal stability of sample Mo(PO₃)₃ that is the initial material for novel catalysts for carbonmonoxide oxidation has been studied. It has been concluded that molybdenum(III) methaphosphate is stable up to 435°C. Processes of partial oxidation and layering of specimens are determined. Novel material based on partial oxidized Mo(PO₃)₃ gives significant rise of the carbon oxidation rate. The molybdenum(III) metaphosphate is of a definite interest in view of its application in practice as initial material for new catalysts row formation with different content of Mo(PO₃)₃ and MoOPO₄ layers. This revised version was published online in August 2006 with corrections to the Cover Date.     

POLYKETONE FROM ETHYLENE WITH CARBON MONOXIDE CATALYZED BY NOVEL CATALYST SYSTEMS BASED ON COPPER WITH BIDENTATE PHOSPHORUS CHELATING LIGANDS

Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.     

Substituted tertiary phosphine Ru(II) organometallics: catalytic utility on the hydrolysis of etofibrate in pharmaceuticals

Some new organometallics of ruthenium(II) of the type [RuCl(2)(COD)(CO)L] (1a-f) and [RuCl(2)(COD)L(2)] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl(2)(COD)(CO)(CH(3)CN)] (1) and [RuCl(2)(COD)(CH(3)CN)(2)] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to produce compounds of the type [RuCl(2)(CO)L(2)] (3a-f). These compounds were characterized by elemental analysis, IR, NMR ((1)H, (13)C and (31)P), mass and electronic spectral data. The catalytic activity of all these organometallics were studied and found that they are efficient catalysts for hydrolysis of etofibrate. The hydrolyzed product was separated by column chromatography and the percent yields are found in the range of 98.6-99.1%.     

COMPLEXES OF HEXATERTIARY PHOSPHINES AND ARSINES AND THEIR REACTION WITH SMALL MOLECULES

Abstract

The synthesis of a new sexadentate ligand, P,P,P′,P′-tetrakis(2-diphenylarsinoethyl)α, α′-diphospha-p-xylene (TDADX) and the preparation of its iridium(I), rhodium(I) and ruthenium (II) complexes are described. When M=Ir and Rh, MCl(CO)(PPh₃)₂ reacts in benzene solution with the ligand TDADX to yield the complexes, [Ir(TDADX)] Cl and Rh₂ Cl₂ (TDADX). RuCl(CO)(PPh₃)₃ Cl reacts with this ligand to yield [RuCl(TDADX)]Cl. Complexes of P,P,P′,P′-tetrakis(2-diphenylphosphinoethyl-α,α-diphospha-p-xylene(TDDX) were also studied for comparison. Molecular hydrogen reacts with the complexes Ir₂ Cl₂ (TDDX), [Ir(TDADX)] Cl and [RuCl(TDADX)] Cl to form the corresponding hydrido complexes. Reaction of molecular oxygen with Rh₂ Cl₂ (TDADX) resulted in the formation of the dioxygen complex. Ir(I), Rh(I) and Ru(II) complexes of TDDX and TDADX react with carbonmonoxide to give mixed ligand carbonyl complexes. The complexes Ir₂ Cl₂ (TDDX), [Ir(TDADX)] Cl, and [RuCl(TDADX)] Cl react with nitric oxide to yield nitrosyl complexes. Infrared spectral data are provided for adducts formed with hydrogen, oxygen, carbon monoxide and nitric oxide.