四（对-羟基苯基）卟啉氧合配合物的室温固相合成，表征及氧合能力

采用固相反应合成了四羟基苯基卟啉与与Fe^2＋,Co^2＋金属离子的配合物,在室温下,将其与分子O2作用,提纯后得到两种固态氧合配合物．通过元素分析、红外光谱（IR）、核磁共振氢谱（^1HNMR）、电导、热分析（TG／DTA）、紫外光谱（UV）等测试手段确定了氧合配合物的组成为[Co·THPP·O2]（NO3）2·2H2O、[Fe·THPP·O2]Cl2·2H2O]，可知1mol配合物吸收了1molO2,采用失重法测定了氧合配合物中的配位氧,确定1mol金属配合物吸收1molO2形成超氧配合物．     

The Systematics of Muonium Hyperfine Constants

The hyperfine constants for muonium in elemental and binary inorganic solids suggest formation of three different families of defect centre, with distinct electronic structures. The overall range of values, spanning nearly five orders of magnitude, and their correlation with host properties such as band gap and electron affinity, reveal a deep-to-shallow instability which has profound implications for the electrical properties of hydrogen impurity in electronic materials, both semiconducting and dielectric.     

Derivatization of 1-phenyl substituted 4-amino-2-benzazepin-3-ones: evaluation of Pd-catalyzed coupling reactions

Several Pd-catalyzed reactions were explored to further functionalize the bromo-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepin-3-one scaffold (Aba). We report in this paper suitable reaction conditions for Suzuki, Buchwald-Hartwig, and Heck reactions. The substitution pattern of the starting aminobenzazepinone turned out to be crucial for the success of these transition metal-catalyzed reactions, which often required modifications of standard literature procedures. The Pd-catalyzed methods provide access to novel substitution patterns of the Aba scaffold.     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

La1-xNdxSrCoO4催化剂的合成及其催化性能

采用聚丙烯胺溶胶-凝胶法制备了类钙钛矿La1-xNDxSrCoO4(x=0.1～0.9)复合氧化物催化剂,考察了其对CO和C3H8的催化氧化活性,并运用XRD、IR和TPR等手段对催化剂进行了表征.结果表明,所制备的样品均具有K2NiF4型结构,适量Nd2O3的加入增加了LaSrCoO4的催化活性,使LaSrCoO4催化剂粒度变小、晶格畸变率变大及与氧的结合能力减弱,从而有利于CO和C3H8氧化活性的提高.     

Reaction Intermediates on TiO2(110) Identified by Time-Lapse Scanning Tunneling Microscopy

The present account describes first time examples of scanning tunneling microscope (STM) visualization of reaction intermediates on a metal oxide surface. The topographic response of reactant-adsorbed TiO₂(110) surfaces to a temperature increment or to a pressure increment was monitored as a sequence of STM images. Acetates thermally decomposing to ketene were resolved in a temperature-jump STM observation. The kinetics of the acetate consumption was determined on the number of acetates resolved in the microscope images and agreed with the macroscopic rate law of ketene production. A pressure-jump study revealed how a chemisorbed carboxylate (RCOO^-) is exchanged by another carboxylate (R'COO^-) supplied from the ambient vapor phase. An impinging R'COOH was immobilized on the top of a RCOO^- and then squeezed itself into the monolayer of the RCOO^-. One of the carboxylates in the squeezed state returned to the vapor phase via the immobilized state.     

19F+27Al耗散反应中双核系统的转动与形变

测量了¹⁹F+²⁷Al耗散反应产物B,C,N,O,F和Ne的激发函数,入射束流的能量从110.25MeV到118.75MeV, 能量步长为250keV. 从产物的 能量自关联函数中提取了反应中所形成的中间双核系统的转动惯量, 与相粘模型计算的刚体转动惯量相比较, 结果表明形成的双核系统有大的形变.     

Paper-like Microfibrous Nickel Catalyst for Hydrogen Production via NH3 Decomposition in Fuel Cell Applications

Recently, miniature H2 generator to power fuel cells for portable/micro electronic devices and passenger propulsion has been the focus of intense research activities1-3. One of the strategies is to find simple CO-free H2 production with novel microreactor…     

Assessing contaminated hydrogen peroxide for safe storage and transportation using the FTAI

Hydrogen peroxide is a very versatile oxidizing agent, and it is also environmentally compatible considering that the products of its exothermic decomposition are oxygen and water.When kept in a clean temperature-controlled environment, the self-reaction (decomposition) rate is extremely low. However, it is well known that even a small amount of contamination will dramatically increase the reaction rate. This paper describes the use of the fast thermal activity interpreter (FTAI) instrument to examine the chemical reactivity of commercially available 50% hydrogen peroxide at two different temperatures (30 and 40°C) both with and without contamination. The results show that at 30°C a small amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide by a factor of 50. When the temperature is increased to 40°C, the reaction rate is further increased by almost a factor of four. The implication for reactivity management is that at this contamination level most practical vessel sizes would require emergency venting capability. An evaluation was then performed to determine the emergency venting requirement for the safe transportation or storage of the contaminated hydrogen peroxide. It was determined that for quantities of the material less than 5 gallons, conventional breather vents would be sufficient to accommodate the gas evolved. However, for larger quantities, a safety relief device would be needed. For example, for a 400-gallon tote bin at 40°C the required minimum vent area is estimated to be 4.3 in², corresponding to a minimum vent diameter of 2.3 inches.     

Mechanistic Insights into the Reversible Formation of Iodosylarene–Iron Porphyrin Complexes in the Reactions of Oxoiron(IV) Porphyrin π‐Cation Radicals and Iodoarenes: Equilibrium,Epoxidizing Intermediate,and Oxygen Exchange

We have shown previously that iodosylbenzene–iron(III ) porphyrin intermediates ( 2 ) are generated in the reactions of oxoiron(IV ) porphyrin π‐cation radicals ( 1 ) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2 ) are present in a reaction solution, and the fast oxygen exchange between 1 and H₂¹⁸O in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and H₂¹⁸O facilitates the oxygen exchange between the oxo group of 1 and H₂¹⁸O and that the oxygen exchange is markedly influenced by factors such as ArI incubation time, the amounts of ArI and H₂¹⁸O used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and H₂¹⁸O.