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

1.将1族和2族元素的金属盐分散在表面密度为10 ~ 15个阳离子（nm^<-2>）的载体上，在惰性气氛中适当温度活化，得到了一种高碱性固体催化剂。氧化铝和氧化锆是有效的载体；二氧化硅和二氧化钛均无效。该催化剂在顺式丁-2-烯、3-甲基丁-1-烯、丙-1,2-二烯和α-蒎烯的异构化反应和环己二烯对苯、环己烯和氢的异构/脱氢反应以及柠檬烯对花香烃的异构/脱氢反应中表现出较高的活性。对于顺式丁-2-烯异构化反应，在CsNO_3/氧化铝催化剂上的最高反应速率为10 mol g^<-1> h^<-1>。在此反应中，金属硝酸盐对氧化铝的活性依次为1族元素>族元素>族元素，元素周期表中低排元素的活性较高。通过TPD和IR/Raman光谱分析发现，表面密度高时，金属盐以凝聚相的形式存在，表面密度低时，金属盐以离子分离相的形式存在。前者在接近自身分解温度的温度下分解，而后者在远远低于分解温度的温度下分解，这是由于阴离子的分解，而阴离子的分解可能与它的反阳离子分离。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^<2->分解为CO_2+O^<2->。人们怀疑释放出来的氧阴离子构成了碱性中心。因此，所开发的新型固体碱催化剂通过使用KOH、NaOH等强碱性介质取代不需要的均相体系，对环境友好的多相体系具有很高的适用性。

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.