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

1.通过将第1族和第2族元素的金属盐分散在表面密度为10-15个阳离子nm 2/g的载体上，<-2>并在惰性气氛中在适当温度下活化它们，获得高碱性固体催化剂。有效载体为氧化铝和氧化锆; 2.该催化剂对顺式2-丁烯、3-甲基-1-丁烯、1，2-丙烯和α-蒎烯的异构化反应，环己二烯异构化/脱氢为苯、环己烯和氢气，柠檬烯异构化/脱氢为对伞花烃的反应，均表现出较高的活性。在CsNO_3/Al_2O_3催化剂上，反应速率最高可达10 molg·<-1>h ~<-1>（-1）。金属硝酸盐在氧化铝上的催化活性顺序为：第1族元素&gt;第2族元素，且元素周期表中的低位元素催化活性较高。4.由TPD和IR/拉曼光谱可知，发现当表面密度高时，固定的金属盐以附聚相和离子相存在，当表面密度较低时，分离相。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，这是由于阴离子的分解，而阴离子的分解可能不受其抗衡阳离子的影响。NO_3^-分解为NO_2+O^-，CO_3^-<2->分解为CO_2+O^-<2->。因此，开发的新型固体碱催化剂通过使用强碱性介质如KOH、NaOH等的水溶液代替不期望的均相体系，对环境友好的多相体系具有高度的适用性。

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.