Ni80P20合金的非晶化度与催化活性的关联

采用淬冷法,通过改变冷却铜辊的转速,得到了一系列具有不同非晶化度的Ｎｉ８０Ｐ２０合金材料。以乙炔加氢为探针反应的催化研究结果表明,合金的催化活性随非晶化程度的增加而增加,同时,非晶态合金具有比相应的晶态金合明显优良的催化稳定性,ＸＲＤ和ＡＥＳ深度分析显示：在氧化－还原活化处理过程中,相对晶态合金而言,非晶态合金显示明显的“惰性”,活化后的表面上含有较多的对加氢反应有促进作用的氧化镍相互作用的结构。     

微波等离子体下一氧化碳氢化制乙炔反应中产物的选择性研究(英文)

采用微波等离子体技术研究了一氧化碳氢化制乙炔反应的产物选择性。对影响乙炔选择性的几个因素,如微波输入功率、反应物的比例和体系压力进行了研究。乙炔的选择性随着微波输入功率的增加,反应物比例和体系压力的降低而增大。在最佳条件下,乙炔的选择性可达到９５．８７％,甲烷选择性的变化规律和乙炔相反,乙烯和乙烷的选择性很低。等离子体中的电子温度（或能量）和密度采用了静电悬浮双探针诊断,电子密度和能量受微波输入功率和体系压力的影响。在反应中,电子能量决定化学反应是否进行,电子密度决定产物的组成。根据自由基反应理论解释了乙炔选择性在Ｈ２＋ＣＯ等离子体化学反应中随影响因素的变化规律。     

Selective catalytic reduction of NO by C2H2 over Ce-Al2O3 catalyst with rate-determining step of NO oxidation

Ce-Al2O3 catalysts prepared by co-precipitation are investigated both in NO oxidation by O2 and in selective catalytic reduction of NO by C2H2(C 2 H 2-SCR).It is found that C2H2-SCR is initiated and controlled by NO oxidation to NO 2 over Al2O3.Ce loading on Al2O3 is almost inactive for NO oxidation below 350 C,since NO2 strongly adsorbs on cerium oxide,leading to the active sites being blocked,which was characterized by temperature-programmed desorption of NO and NO 2 and Fourier transform infrared spectroscopy after NO+O 2 coadsorption over the samples.However,in the case of C2H2-SCR,Ce loading on Al 2 O 3 significantly improves the reaction by accelerating the NO oxidation step in the temperature range of 250-450 C,since the nitrate species produced by NO 2 adsorption is an active intermediate required by C2H 2-SCR.     

Towards an understanding of the helium–acetylene van der Waals complex

The weakly bound complex He–C₂D₂ is studied in the ν ₃ fundamental band of C₂D₂ (≈2440?cm^?1) using a tuneable infrared diode laser to probe a pulsed supersonic slit jet expansion. This is the first published spectrum for helium–acetylene. Transitions observed in the region of the C₂D₂ R(0) line are assigned with the help of theoretical results based on an ab initio intermolecular potential, and fitted using a simple Coriolis model. The results indicate that the complex is rather close to the free rotor limit, helping to explain the absence of previous data. Scaled parameters from the model are used to predict a spectrum for He–C₂H₂.     

Stereoselective Cyclopolymerization of Polar 1,6‐Heptadiynes by Novel,Tailor‐Made Ruthenium‐Based Metathesis Catalysts

Summary: The cyclopolymerization of 4,4‐bis(hydroxymethyl)‐1,6‐heptadiyne ( M1 ), 4‐(carboxyethyl)‐1,6‐heptadiyne ( M2 ), 4‐(hydroxymethyl)‐1,6‐heptadiyne ( M3 ), and 4‐carboxy‐1,6‐heptadiyne ( M4 ) using five different well‐defined metathesis initiators was investigated. Control of molar mass was achieved with catalysts bearing trifluoroacetate ligands. ¹³C NMR experiments showed that poly‐ M2 , prepared by the action of any catalyst consisted solely of five‐membered ring structures, i.e., 1,2‐(cyclopent‐1‐enylene)vinylene units. Effective conjugation lengths of all polymers were calculated from the corresponding UV‐Vis absorption maxima, which varied reversibly with temperature.

     

Gelation in Multiple Link System

The critical point theory is generalized to include gelation in multilink system with f functional units and J junction points. The equations derived include, as special cases, the cyclotrimerization model of J = 3, and the R–A_f model of J = 2. The theory is applied to the recent observation of the cyclotrimerization of bisphenol‐A dicyanate. The theoretical prediction agrees exactly with the Stutz‐Simak observation, D_c = 0.504, and accords with the Georjon‐Galy‐Pascault observation, giving a confirmation of the physical soundness of the theory. Under the smoothness assumption, we derive post‐gelation relationships with loop formation, the result suggesting the formation of permanent sol molecules that resist being absorbed into gel phase throughout an entire reaction process.

Representation of binary branching.     

Hydrogen bonding in acetylene containing dichlorodiazaalkadienes

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Adsorption Site Regulation to Guide Atomic Design of Ni–Ga Catalysts for Acetylene Semi-Hydrogenation

Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory-guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi-hydrogenation processes. Such Ni sites show not only preferential acetylene π-adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration-corrected high-resolution scanning transmission electron microscopy and X-ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni₅Ga₃ intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi-atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.