聚合物载体－稀土金属络合物的研究 ⅩⅢ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］的结构与其稀土金属络合物催化丁二烯聚合的活性

从测得的竞聚率计算了单体链节在聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］（ＰＳＭ）中的序列分布。苯乙烯（Ｓ）或甲基丙烯酸β（甲基亚硫酰基）乙酯（Ｍ）的长序列的概率随着ＰＳＭ中相应单体含量的增加而增加。对于Ｓ和Ｍ摩尔分数大致相等的ＰＳＭ，单体链节的长序列分布函数值相接近。用与此结构相近的ＰＳＭ合成的稀土金属络合物，其催化活性不佳。在Ｍ短序列分布和Ｓ长序列分布较高的情况下，络合物的催化活性最好。所得聚丁二烯的微观结构与ＰＳＭ中单体单元的分布无关。     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

A facile and efficient method for preparation of chiral supported poly(styrene–divinylbenzene) copolymers

A new and efficient method for preparation of optically active poly(styrene–divinylbenzene) copolymers (PS-DVB) is presented here. This is carried out by Friedel–Crafts acylation reaction of chiral N-phthaloyl -leucine acid chloride with PS-DVB beads in the presence of aluminum chloride as Lewis acid catalyst and 1,2-dichloroethane as the solvent at ambient temperature. Reagents’ amounts and reaction conditions are mentioned and four samples with different amounts of functionality have been prepared. Final products were characterized by FT-IR and elemental analysis. The results obtained confirm that the above modification in preparation of chiral supported PS-DVB has been achieved well and in moderate yield.     

不饱和烃硅氢加成催化剂固载化研究进展

综述了各类负载过渡金属的催化剂体系及其在不饱和烃硅氢加成反应中的应用。负载过渡金属的催化剂具有良好的可回收性和选择性，研究主要集中在开发价廉、使用安全、环境友好和高催化性能的活性炭、氧化物或有机聚合物等负载过渡金属催化剂，并取得很好的结果。     

Selectivity Enhancement to the Exclusive Formation of Ethyltoluenes and Hydrogen During Dehydroalkylation of Toluene with Ethane

The dehydroalkylation of toluene with ethane to the isomeric ethyltoluenes was studied on 0.4Pt/H-ZSM-5 at varying contact times (1/WHSV). At a high contact time of 1.0 h, toluene disproportionation and hydrogenolysis reactions dominate, resulting in low selectivity to the desired ethyltoluenes via the alkylation reaction. However, at a low contact time of 0.12 h side reactions are eliminated, resulting in maximum selectivities to the kinetically favored ethyltoluenes and hydrogen. Results at high selectivities to ethyltoluenes provide significant insight into reaction pathways.     

Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst

Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al₂O₃ catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al₂O₃ catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h⁻¹. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 10¹⁷ s⁻¹.     

新型重整催化剂的研究——Pt／L中沸石酸碱性的作用

Ｐｔ／ＫＬ、Ｐｔ／ＢａＫＬ及Ｐｔ／ＨＬ上的铂与沸石的酸碱位发生相互作用，导致催化剂上存在不同电子状态和粒度分布的铂位，从而产生有着完全不同催化作用、不同抗硫性能的两类催化剂，即以碱性沸石为载体的“单功能”催化剂和以酸性沸石为载体的“双功能”催化剂。在Ｐｔ／ＫＬ、Ｐｔ／ＢａＫＬ催化剂上，存在着对硫敏感的具有环化脱氢功能和对硫不敏感的仅具有脱氢功能的两类铂活性位。     

Responses of practicing psychologists to a web site developed to promote empirically supported treatments.

Increased adoption of empirically supported treatments (ESTs) has been hindered in part by inadequate and inconvenient access to EST information and training. To improve diffusion of ESTs, the authors developed a Web application to provide practitioners with concise information by disorder on ESTs. The resulting site, therapyadvisor.com, was evaluated by 239 practicing psychologists to assess the usefulness of the site and explore possible interactions of EST attitudes on ratings of usefulness and impact. Two thirds of participants indicated using ESTs in practice, and limited time and resources were cited as primary barriers to EST adoption. The Web application was rated positively by most participants and was reported to increase awareness of and commitment to try ESTs among approximately 60% of participants. The results of this project support the feasibility of a Web application to increase diffusion and promote further adoption of ESTs. Technological and e-learning advances are promising directions for encouraging the adoption of ESTs specifically and evidence-based practice generally, particularly among busy practitioners who have inadequate time and resources for more traditional forms of dissemination and training. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Measurement of the Metal Surface Acidity/Electronegativity of Pt(110)

In previous work, it has been found that a hydrogen-covered Pt(110) surface is acidic, but quantification of the acidity has not yet been done. In this paper a spectroscopic method is developed to measure the acidity of a metal surface for the first time. The technique involves measuring the intensity of the N–H stretch from the C₅H₄XNH⁺ that forms when hydrogen coadsorbs with pyridine, 2-fluoropyridine and 3-fluoropyridine. The Bethe approximation is then used to estimate the metal surface acidity/electronegativity (MSAEL). The proton affinity/MSAEL of Pt(110) has been determined to be 907 ± 4 kJ/mol at high coverage. This is the first time the MSAEL has been measured on a metal surface. Implications for fuel cell catalysis are discussed.     

The concept of an endurance limit for adhesive joints

The effect of cyclic stressing on the strength of single lap adhesive joints has been studied and a considerable reduction in strength observed when the maximum stress exceeds about 40% of the ultimate tensile strength, but whether or not a true endurance limit exists is not proven. Fallacies are shown in some of the techniques which have been proposed for studying the fatigue behaviour of adhesive joints.