Development of Novel Solid Super Base and its Application to Green Chemistry

1.在惰性气氛中，以10-15阳离子的表面密度将1、2族元素的金属盐分散在载体上，并在适当的温度下活化，得到了高碱性固体催化剂。2.催化剂对顺丁烯、3-甲基-1-烯、丙二烯和α-品烯的异构化反应表现出较高的活性，环己二烯异构化/脱氢为苯、环己烯和氢气，柠檬烯异构化为对伞花烃。金属硝酸盐对Al_2O_3反应的有效性顺序为：第1族元素和第2族元素，且元素周期表中较低位置的元素活性较高。4.从TPD和IR/拉曼光谱可以看出，当表面密度较高时，金属盐既以凝聚相形式存在，在表面密度较低时以离子分离相形式存在。前者在接近其自身分解温度的温度下分解，而后者在远低于其分解温度的温度下分解，并归因于可能脱离其反阳离子的阴离子分解。5.基本性质的产生与阴离子分解密切相关。NO_3^-分解为NO_2+O^-，CO_3^-分解为CO_2+O^&t；由此开发的新型固体碱催化剂对环境友好的多相体系具有很高的适用性，通过使用强碱性介质如KOH、NaOH等来取代不受欢迎的均相体系。

1.A highly basic solid catalyst was obtained by dispersing metal salts of Group 1 and 2 elements over supports at the surface density of 10-15 cations nm^<-2> and activating them at proper temperature in an inert atmosphere. Effective supports were alumina and zirconia ; silica and titania were ineffective.2.The catalyst exhibited high activity in the isomerizations of cis-but-2-ene, 3-methyl-but-1-ene, propa-1,2-diene and α-pinene, and the isomerization/dehydrogenation of cyclohexadiene to benzene, cyclohexene and hydrogen, and of limonene to p-cymene.3.In case of the isomerization of cis but-2-ene, the highest reaction rate of 10 mol g^<-1> h^<-1> was obtained on the catalyst derived from CsNO_3/alumina. The order of effectiveness of metal nitrates on alumina for this reaction was found to be in the order of group 1 elements > group 2 elements and the elements in the lower rows in the periodic table gave higher activity.4.From TPD and IR/Raman spectroscopy, it was found that mounted metal salts existed as both an agglomerated phase when the surface density was high and an ion-separated phase when the surface density was low. The former decomposes at the temperature close to its own decomposition temperature, while the latter decomposes far below the decomposition temperature and was attributed to the anion decomposition that may be free from its counter cation.5.The generation of the basic property closely relates to the anion decomposition. NO_3^-decomposes to NO_2+O^- and CO_3^<2-> decomposes to CO_2+O^<2->. It is suspected that the liberated oxygen anion(s) constitutes basic centers.6.Thus developed novel solid base catalysts have a high applicability to environmentally benign heterogenous systems by replacing undesirable homogeneous systems using strongly basic media such as aqueous solutions of KOH,NaOH etc.