Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

多壁碳纳米管膜湿敏特性的研究

研究了多壁碳纳米管(MWNTs)薄膜的湿敏特性，实验所用的多壁碳纳米管是用热灯丝化学气相沉积法(CVD)合成的.分别对未修饰和修饰的多壁碳纳米管膜温度和湿度特性进行研究后发现，修饰的多壁碳纳米管对温度和湿度非常敏感，且对湿度的响应时间和恢复时间短，重复性好.而未修饰的多壁碳纳米管对温度和湿度不太敏感.对修饰多壁碳纳米管的湿敏特性进行了理论分析，给出了其理论表示式. 关键词： 多壁碳纳米管 化学修饰 湿敏特性 物理吸附     

含氮类金刚石薄膜的紫外辐照研究

 用射频等离子体方法在玻璃基底上制备的类金刚石（DLC）薄膜，采用离子注入法掺氮，并对掺氮DLC薄膜紫外（UV）辐照前后的性能变化进行了研究。研究结果表明：随氮离子注入剂量及UV辐照时间的增加，位于2 930cm^-1附近的SP ³C-H吸收峰明显变小，而位于1 580cm^-1附近的SP2C-H吸收峰则明显增强，薄膜的电阻率明显呈下降趋势；随UV辐照时间的增加，位于1 078cm^-1附近的Si-O-Si键数量及位于786cm^-1附近的Si-C键数量明显增加。即氮离子注入和UV辐照明显改变了DLC薄膜的结构与特性。     

Radioactive Tracer Study of the Displacement of Iodine Adatoms from Platinized Platinum Electrode by Carbon Monoxide

Radioactive tracer studies confirm the earlier electrochemical results that carbon monoxide can virtually completely displace iodine adatoms. For the first time, it is found that iodine adatoms are not displaced by carbon monoxide when iodide anions are adsorbed in the presence of an upd silver monolayer. The possible reasons for the effect observed are discussed.     

Local adsorption sites and bondlength changes in Ni(1 0 0)/H/CO and Ni(1 0 0)/CO

The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding.     

New efficient catalysts for the aerobic oxidation of ethers

Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported.     

Total electron scattering cross sections for carbon dioxide at low electron energies

Absolute total electron scattering cross sections for carbon dioxide have been measured at low electron energies using a photoelectron source. The measurements have been carried out at 27 electron energies varying from 0.91–9.14 eV with an accuracy of ±3%. The cross sections obtained in the present experiment have been compared with other measurements and theoretical computations.