具有新光学性质的Zn-Zn2SiO4纳米同轴线阵列

采用气相沉积技术在Si衬底上生长了Zn-Zn₂SiO₄芯-壳结构纳米同轴线阵列。根部呈笋状的纳米同轴线,直径约100nm,长度可以超过10μm;同轴线芯直径约50nm、壳层厚约25nm。通过X射线衍射的表征以及能量色散谱的线扫描,确定纳米同轴线的芯为Zn,壳层为Zn₂SiO₄。我们提出了一种新的生长机制,同时也为生长均匀的纳米同轴线提供一种新的技术。观察阴极荧光谱发现,纳米同轴线有三个主要发光带:强度最大的中紫外300nm发光、较弱的可见光区560nm以及红外谱区865nm的发光。对纳米同轴线截面的300nm发光峰观测发现,中紫外发光来源于Zn₂SiO₄壳层。正是这种同轴线的结构,使得其具备特殊的光学性质。     

CH3S CH2SH异化反应的理论研究

利用密度泛函理论(DFT)和从头算(ab initio)研究了CH3S←→CH2SH互异化的反应机理．采用HF、B3LYP、MP2理论水平和中等基组6-31(d)，计算了CH3S、CH2SH及其过渡态的结构参数、谐振频率、零点能(ZPF)、总能量和相对能量，并利用B3LYP／6-31(d)的方法计算了反应的内禀反应坐标(IRC)，给出了分子构型和自旋污染沿反应坐标的变化曲线，以及最小能量曲线(MEP)、绝热能量曲线．此外，利用传统过渡态理论(CTST)研究了该互异化反应的速率常数和平衡常数在200～1000K的变化．     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

Modification of a three-way catalyst washcoat by aging: A study along the longitudinal axis

This work reports the research carried out by studying aliquots extracted at different axial coordinates from Three Way Catalyst (TWC) monoliths aged under real traffic conditions. Our study focused on the catalytic properties and on several chemical and physical effects caused in the Front and Rear monolith washcoat surfaces by vehicle aging after 60,000 km. Regarding the catalytic properties, all the used aliquots showed poorer activity than their corresponding fresh counterparts. The strongest deactivation was detected for NO and hydrocarbon conversion. CO conversion was less affected and the Rear monolith was as deactivated as the Front one. The characterisation techniques (TXRF, N₂ adsorption-desorption isotherms, XRD and H₂-TPR) detected - (i) the deposition of P, Zn and Pb; (ii) the formation of CePO₄ on account of the Ce from the washcoat; (iii) thermal sintering; (iv) inhibition of the reducibility of Ce oxides - as the main effects brought about by vehicle aging conditions. The deactivation observed at the beginning of the Front monolith was the result of a combination of the former effects. When moving downstream to higher axial coordinates, Pb accumulation and the loss of specific area appeared to be the only probable sources of deactivation.     

On the behavior of ECN/RED gateways under a large number of TCP flows: Limit theorems

We consider a discrete-time stochastic model of an ECN/RED gateway where competing TCP sources share the link capacity. As the number of competing flows becomes large, the asymptotic queue behavior (normalized by the number of flows) at the gateway can be described by a simple recursion and the throughput behavior of individual TCP flows becomes asymptotically independent. A Central Limit Theorem complement is also presented, yielding a more accurate characterization of the asymptotic queue size. These results suggest a scalable yet accurate model of this complex large-scale stochastic feedback system, and crisply reveal the sources of queue fluctuations. This work was prepared through collaborative participation in the Communications and Networks Consortium sponsored by the U.S. Army Research Laboratory under the Collaborative Technology Alliance Program, Cooperative Agreement DAAD19-01-2-0011. This work was also supported by the Space and Naval Warfare Systems Center—San Diego under Contract No: N66001-00-C-8063. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Army Research Laboratory or the U.S. Government.     

Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

Studies on the Structure and Properties of Cordierite Synthesized by Talc-Magnesite

Homogeneous cordierite has been synthesized at low cost by talc-magnesite and coal gangue as the main raw materials. The mechanism of synthesizing cordierite under such a com- posing system of raw materials, and the effect of temperature on the crystal cell parameters and microstructure and thermal expansion coefficient of cordierite crystal have been studied via testing methods of XRD, SEM, etc. The result shows that the homogeneous cordierite can be synthesized by the systematic composing materials of “talc-magnesite—coal gangue—talc” with heat pre- servation at 1350 ℃ for 1 h; as the keeping time is prolonged, Al3+ and Mg2+ in cordierite crystal are replaced by a few impurity ions such as Fe3+, Fe2+, etc., and the crystal cell parameters of cordierite present an increase trend; as the high-temperature heat preservation is prolonged, the content of glassy phase in the sample is increased, its density is improved, and its thermal expansion coeffi- cient presents an increase trend.     

MgO•3B2O3-18%MgSO4-H2O过饱和溶液析出固相组成和机理研究

针对青藏高原盐湖卤水析盐过程的特点, 模拟合成MgO•3B₂O_3-18%MgSO_4-H₂O过饱和溶液, 在150 ℃水热条件下对析出固相进行研究. 用化学分析方法、X射线衍射、红外光谱进行物相鉴定. 提出了可能的结晶反应机理, 分析了水热温度对析出物相的影响及MgSO₄对硼酸镁盐的盐溶效应随水热温度的变化.     

Li^＋／MgO上乙烷氧化脱氢制乙烯的研究（Ⅱ）：催化作用机理

借助ＸＲＤ、ＩＲ、ＴＧ等技术对Ｌｉ＾＋／ＭｇＯ进行了表征，结果表明，酸、碱中心的数目，强度、催化性与Ｌｉ＾＋的添加量相关 ，起酸碱作用的表面金属离子、表面低配位氧集团、Ｏ（Ｌ ｉ＾＋Ｏ＾－）是其反应的活性物种，反应机理可能由离子基、游离基协同完成。