负载型Rh/Ys催化剂的表面微结构与性能关系的研究

通过电子透射显微镜和扫描遂道显微镜对新型高效甲醇羧基化Rh/Ys催化剂载体的内部结构和Rh在催化剂表面的分布进行分析,确定了其分布状态与催化剂制备温度之问的关系.同时,通过电子能谱和远红外光谱技术确定了Rh与载体表面碳形成的Rh←C键,并对不同条件制备的催化剂表面铑的流失和催化活性进行了对应比较,进而讨论了这类新型Rh/Ys催化剂的高活性及高稳定性的内在因素.     

Intramolecular substitutions of square planar rhodium(Ⅰ) catioriic complexes of ds-dicarbonyl nitrogen coordinated tridentate

Four kinds of square planar cis-dicarbonyl-N,N-bis(2-pyridylethyl)-p-substituted-phenylamino rhodium(Ⅰ) are reported.The changes of their structures were analyzed by XPS,IR and NMR spectroscopy The results show that the weak N→Rh coordinated bond can replace very soon the strong Rh-Cπ back donation bond to form tris-nitrogen coordinated complexes due to the steric effect when the temperature is over 50℃,This reaction is reversible.The bis-nitrogen coordinated structure of the complex recovered when put under the atmosphere of CO     

Relationship between surface microstructure and properties of supported catalyst Rh/Ys

The inner structure of Rh/Ys,a novel high efficiency supported catalyst,and the spreading of Rh on the Ys surface were analyzed through electron transmission microscopy and scanning tunnel microscopy.The relationship between the distribution of Rh over the support and the preparation temperature of th catalyst was determined.The formation of Rh-C bond was confirmed by XPS and far-IR spectra.The loss of Rh from the surface of the support and the catalytic activity under different preparation conditions have been compared.The internal factors for the high activity and high stability of the novel Rh/Ys catalyst have been discussed.     

Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.     

A catalyst for the carbonylation of methanol to acetic acid in gaseous phase

A novel Rh/Ys catalyst for the carbonylation of methanol to acetic acid in gaseous phase is reported. The porous carbon beads (Ys) prepared from the carbonation of poly(vinylidene chloride) were used as the support. This catalyst has a specific surface area of 1 000 m2/g, high mechanical strength and thermal stability. The average diameter of the pore is in the range of 0.8 - 1.2nm. Experimental evidence showed that this catalyst was of high activity and selectivity, which could compare to those of the homogeneous catalyst from Monsanto. The catalytic rate could get to 900 g AcOH/g Rh·h during the carbonylation of methanol to acetic acid. The fine spreading of Ph over the Ys surface is the key factor for the activity.     

Intramolecular reaction of polymer coordinated cationic rhodium complex

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C60的化学修饰

C_(60)分子中含Pyracylene结构。具有苯环烯烃、共轭烯烃的性质。本文讨论了它的加成反应(包括卤化,胺化等),Friedel—Crafts反应,氧化反应,Diels—Aider反应,成络反应,自由基反应和还原反应的进展。参考文献52篇。     

带有方案偏好关系的模糊多属性决策方法

针对属性值为一般模糊变量、属性权重信息完全未知但已知方案偏好关系的模糊多属性决策问题，给出了决策方法。首先通过求解一个模糊期望值模型来确定属性的权重，然后基于简单加权平均法则来计算各方案的模糊综合评价值,再根据比较模糊变量大小的期望值方法来对方案进行排序,最后给出一个算例。