CAREER: Multinuclear Solid State NMR Studies in Environmental Catalysis

摘要-Klug-9733136斯坦福大学教授Christopher A.Klug将使用原位核磁共振技术研究对环境催化和能源最小化问题具有重要意义的两种催化体系。用于烯烃立体选择性聚合的负载型茂金属催化剂和用于NOx和氯代烃分解的负载型钒催化剂将被研究。PI将使用各种核磁共振技术：CPMAS、一维和二维脉冲核磁共振、同核和异核偶极耦合实验。他还将开发可多次调谐的核磁共振探针和原位催化核磁共振电池。由Stanfordos韦茅斯集团联合制备的ZR茂金属将被负载在二氧化硅或氧化铝上，并控制脱羟基程度。通过对聚丙烯短链的原位表征，研究了立体选择性聚合机理的初始步骤。在非均相催化剂上产生的聚合物的微观结构和形态将与WayMouthos小组的物理性质测定相关联。在核磁共振的另一个应用中，将制备和表征负载在氧化铝上的钒，或在钛铝上负载K的络合物促进的钒-钨。17O、51V、29Si和27Al核磁共振将用于研究MARS-Van Krevelen类型的氧插入机制和氧和钒的扩散动力学。用~(13)C、~(15)N和~(35)C核磁共振原位研究了氮氧化物与氨的SCR反应和CH_3CH_2Cl的分解。用~(39)K核磁共振研究钾的修饰及其与化学吸附剂的相互作用。在教育方面，克鲁格教授将继续努力招收少数族裔学生，并将为斯坦福大学多学科环境科学课程的工程师开发一门新的环境催化课程。

Abstract - Klug -9733136 Prof. Christopher A. Klug, of Stanford University, will use in-situ NMR techniques to study two types of catalytic systems of importance to environmental catalysis and energy minimization issues. Supported metallocene catalysts for alkene stereoselective polymerization, and supported vanadia for the decomposition of NOx and chlorohydrocarbons will be studied. The PI will use various NMR techniques: CPMAS, 1 and 2-dimensional pulse NMR, homonuclear and heteronuclear dipolar coupling experiments. He will also develop multiply tuned NMR probes and in situ catalysis-NMR cells. Zr metallocenes prepared jointly by StanfordOs Waymouth group will be supported on silica or alumina with controlled dehydroxylation level. The initial steps of the stereoselective polymerization mechanism will be studied by characterizing in situ short chains of polypropylene. The microstructure and morphology of the polymers produced on the heterogeneous catalyst will be correlated with physical property determinations by WaymouthOs group. In another application of NMR, supported vanadia over alumina or complex K-promoted vanadia-tungsta over titania-alumina will be prepared and characterized. 17O, 51V, 29Si and 27Al NMR will be used to study the Mars-Van Krevelen-type oxygen insertion mechanism and oxygen and vanadium diffusion kinetics. The SCR of NOx with ammonia and the decomposition of CH3CH2Cl will be studied in situ with 13C, 15N, and 35Cl NMR. The modifications induced by potassium and its interactions with chemisorbates will be studied with 39K NMR. On the educational side, Prof. Klug will renew efforts to recruit minority, and will develop a new course in environmental catalysis for engineers for the multidisciplinary environmental sciences curriculum at Stanford.