金的化学状态对Au／CoCeOx催化剂CO氧化性能的影响

以CoCeOx复合氧化物为载体,采用沉积沉淀法制备了负载型的金催化剂,并通过不同温度的预处理控制Au的化学状态. 使用粉末X射线衍射、高分辨透射电子显微镜、程序升温还原和X射线光电子能谱对催化剂进行了表征,考察了在室温条件下该系列催化剂的一氧化碳氧化性能. 结果表明, Au/CoCeOx催化剂的CO氧化性能与催化剂表面Au 的含量成正比, Au 可能是反应的主要活性物种. 添加水汽对反应有一定的促进作用,但由于Au 不能稳定存在,特别是当催化剂表面Au 的含量过高时,在水汽的作用下Au 迅速发生歧化反应,使得催化剂的性能下降.     

新颖的TiO2@C核壳结构纳米纤维阵列电极制备及其在电化学传感器中的应用

本文提出以金属钛为基底, 在丙酮蒸气和无催化剂条件下, 通过高温反应, 直接在金属钛片上一步合成出具有核壳结构的TiO2@C纳米纤维阵列. 由于TiO2@C纳米纤维阵列在金属钛片上分布均一, 与金属钛基底有良好的结合力和电接触性能, 可直接作为电化学传感器电极. 进一步的电化学检测表明, 该电极对铁氰化钾及多巴胺等物质有良好的电化学响应, 对多巴胺检测灵敏度高, 响应的线性范围为1.0×10-7~1.0×10-4 mol/L, 检测限达2.45×10-8 mol/L. 该电极有望在生物传感、环境分析及药物分析等领域发挥重要作用.     

介孔Ce1-xZrxO2负载的Cu基催化剂在富氢条件下催化CO选择性氧化

采用多元醇为模板剂合成了介孔Ce1-xZrxO2(x=0.2,0.35,0.5)固溶体材料,并以其为载体负载CuO制备了Cu基催化剂.应用透射电子显微镜、X射线衍射、程序升温还原、程序升温脱附和N2吸附-脱附等技术对载体及催化剂进行了表征,并研究了Zr的取代比例x值对载体和Cu基催化剂性能的影响.结果表明,所有Ce1-xZrxO2样品均为介孔材料,其中Ce0.5-Zr0.5O2载体样品有较大的比表面积(181m2/g),CuO/Ce0.5Zr0.5O2催化剂样品在富氢条件下有较高的催化CO选择性氧化反应的活性和选择性.与其他催化剂样品相比,CuO/Ce0.5Zr0.5O2催化剂样品中形成的活性中心更多,分散性更好,对CO的吸附量更大,CO脱附温度更低,活性组分与载体的相互作用更强。     

Toroidal molecules formed from three distinct carbon nanotubes

In order to design nanotori for nanomechanical systems, perhaps involving oscillating components, precise physical parameters for the nanotori are necessary. Toroidal shaped molecules of carbon have been investigated previously by the present authors as constructed by connecting elbow sections formed from joining armchair and zigzag nanotubes through a pentagonal–heptagonal pair defect. In this paper, we extend this design by constructing the elbow structures from three distinct carbon nanotubes. Since for a toroidal molecule, there is a constraint on the bend angles in the elbow sections to add up to 360°, particular elbow types which can accommodate this requirement are (5,0)–(4,4)–(7,0) and (3,3)–(6,0)–(4,4). We adopt a least squares approach for the bond length to minimise the variation from the ideal carbon–carbon bond length, which is taken to be σ = 1.42 Å. Moreover, formulae for the mean generating radius of the nanotori and the mean radius of the nanotubes are obtained from certain integral expressions. This purely geometrical approach can be formally directly related to certain numerical energy minimisation methods used by a number of authors.     

Mechanistic Investigations of Surface Modification of Carbon Black and Silica by Plasma Polymerisation

Carbon black is widely used as an active filler in the rubber industry to improve the physical properties of rubber. The surface energy of carbon black is high compared to that of various elastomers like styrene–butadiene rubber (SBR), butadiene rubber (BR) and ethylene–propylene–diene rubber (EPDM). The work aims at reducing the surface energy of carbon black by modifying its surface for application especially in rubber blends. The present paper looks into the possibility of using plasma polymerisation of acetylene as a surface modification technique for carbon black in comparison with silica. Thermogravimetric analysis, wetting behaviour with various liquids of known surface tension and time of flight secondary ion mass spectrometry (ToF-SIMS) were used to characterise the carbon black before and after surface modification. The study shows that surface modification of carbon black by plasma polymerisation is difficult in comparison with silica, unless treated for long duration. The mechanistic aspects of the surface modification and the importance of active sites on the carbon black surface for effective modification are discussed in the paper.     

High pressure solubility data of carbon dioxide in (tri-iso-butyl(methyl)phosphonium tosylate + water) systems

Ionic liquids are attracting great attention nowadays due to their interesting properties which make them useful in a broad range of applications including reaction media or separation/capture of environmentally hazardous gases such as carbon dioxide. In many cases, for practical and/or economical reasons, the use of aqueous solutions of ILs would be preferable to their use as pure compounds.In this work, high pressure equilibrium data for the {carbon dioxide (CO₂) + tri-iso-butyl(methyl)phosphonium tosylate [iBu₃MeP][TOS] + water system were measured at temperatures ranging from (276 to 370) K and pressures up to 100 MPa. Measurements were performed using a high-pressure cell with a sapphire window that allows direct observation of the liquid–vapour transition. Mixtures with different IL concentrations were studied in order to check the influence of the amount of IL on the solubility of CO₂ in the aqueous mixture.The results show that the presence of IL enhances the solubility of CO₂ in the (IL + water) system revealing a salting-in effect of the IL on the solubility of CO₂. The appearance of a three phase region was observed for IL concentrations higher than 4 mol% of IL in water when working at pressures between 4 and 8 MPa and temperatures between (280 and 305) K. In this range, the upper limit of the VLE region observed is shown to increase with the temperature being almost independent of the IL initial concentration in the mixture.     

Comparative simulation study of nitrogen and ammonia adsorption on graphitized and nongraphitized carbon blacks

Grand canonical Monte Carlo simulation is used to study the adsorption of nitrogen at 77 K and ammonia at 240 K to represent weakly polar and polar molecules, respectively, on infinite and finite graphite surfaces. These graphite surfaces were modeled with different percentages of carbons removed (defects) from the top graphite layer. Increasing the number of defects increases the adsorption and the isosteric heat of nitrogen at low pressure. At moderate pressures the amount adsorbed is less due to the disruption in the packing of the nitrogen in the first layer. In contrast, the adsorption of ammonia at all pressures is reduced as the percentage of defects is increased. This is due to the disruption in ammonia bonding caused by the defects. The condensation-like step change in the ammonia isotherm on the perfect graphite surface is not observed for any of these surfaces with defects even for the case of only 10% defects. At high percentage of defects the adsorption isotherm is close to Henry law behavior for much of the pressure range. The adsorption on finite surfaces shows that the amount adsorbed for both molecules decreases compared with that of the infinite surfaces, resulting from interaction potentials with the surface and other fluid molecules at the edge. The decrease is much greater for the ammonia adsorption because the bonding between ammonia molecules is disrupted, meaning that the adsorption cannot follow the mechanism of condensation seen for the infinite surface.     

Electrochemical carboxylation of fluorocontaining imines with preparation of fluorinated N-phenylphenylglycines

A possibility of obtaining fluorine-containing N-phenylphenylglycine derivatives at yields of up to 85% via the electrochemical carboxylation of corresponding benzalanilines was shown. The influence of imine's electron structure, the nature of supporting electrolyte and cathodic material on such processes is examined. It was found, that increasing electron accepting ability of the substituents in benzylidene and aniline fragments of the imine molecule lead to decrease of amino acid yields. The dependence of the N-phenyl-p-fluorophenylglycine yield on the cathode material (Zn, GC, Cu, Ag, Pt) and on the nature of the supporting electrolytes (Bu₄NBr, Et₄NBr, Et₄NClO₄, PhCH₂Me₃NClO₄, LiBF₄, LiClO₄, NaBF₄ and KBF₄) was investigated. The highest amino acid yields were obtained at cathodes (GC and Zn) that do not exhibit specific adsorption of fluorine-containing imines, as well as in the presence of background salts (Alk₄NBr) whose cations do not show tendency to strong ion pairing with anion radicals formed by the electrochemical activation of the imines.     

Organometallic chemistry and catalysis on gold metal surfaces

As in transition metal complexes, CN-R ligands adsorbed on powdered gold undergo attack by amines to give putative diaminocarbene groups on the gold surface. This reaction forms the basis for the discovery of a gold metal-catalyzed reaction of CN-R, primary amines (R′NH₂) and O₂ to give carbodiimides (R′-NCN-R). An analogous reaction of CO, RNH₂, and O₂ gives isocyanates (R-NCO), which react with additional amine to give urea (RNH)₂CO products. The gold-catalyzed reaction of CN-R with secondary amines (HNR′₂) and O₂ gives mixed ureas RNH(CO)NR′₂. In another type of gold-catalyzed reaction, secondary amines HN(CH₂R)₂ react with O₂ to undergo dehydrogenation to the imine product, RCHN(CH₂R). Of special interest is the high catalytic activity of gold powder, which is otherwise well-known for its poor catalytic properties.     

CVD synthesis of nitrogen doped carbon nanotubes using ferrocene/aniline mixtures

Nitrogen doped carbon nanotubes (N-CNTs) have been synthesized by the chemical vapour deposition (CVD) floating catalyst method using either 4-ferrocenylaniline or mixtures of varying concentrations of ferrocene/aniline together with toluene as added carbon source. The N-CNTs produced are less stable (thermal gravimetric analysis measurements), less graphitic and more disordered (transmission electron microscope measurements) than their undoped counterparts. The ratio of the Raman D- and G-band intensities increase with the nitrogen concentration used during the CNT growth. Furthermore, the transmission electron microscope (TEM) studies reveal that the CNTs are multi-walled (MW), and that the diameters of the N-MWCNTs can be controlled by systematically varying the concentrations of the nitrogen source. The TEM analysis also revealed that when ferrocenylaniline and ferrocene/aniline reactions are compared at similar Fe/N ratios, higher N doping levels are achieved (ca. 2-5×) when ferrocenylaniline is the catalyst.