【作者】 王宇；

【导师】 朱再明；

【作者基本信息】 辽宁师范大学 ， 无机化学， 2015， 硕士

【摘要】 以饱和Keggin型钨硅酸、钨磷酸、钼硅酸、钼磷酸4种杂多酸为母体化合物,在水溶液中,通过阳离子间的交换反应,利用直接沉淀法合成了碱金属离子、铵离子、含氮有机阳离子、过渡金属离子及过渡金属-联咪唑配阳离子等为抗衡阳离子的各种keggin结构多酸基荷移盐。并以环己酮与乙二醇反应合成环己酮乙二醇缩酮为模型反应,考察了该类荷移盐的酸催化性能,较系统地研究了抗衡阳离子、多酸类型对该类酸催化剂酸性的影响。研究结果表明,通过改变阳离子可对母体酸的酸性及溶解性进行调控,从而获得高效、可循环使用、易分离的多酸基催化剂。将铜-联咪唑配合物引入多酸体系,获得了非均相高效催化剂。本工作为深入研究开发这类催化剂奠定了坚实的实验基础,具有重要实际意义。1、当母体酸保持不变时,即杂多阴离子相同时,考察了以Na+、K+、NH4+、Bu4N+、含N有机阳离子(如质子化的咪唑、2,2’-联咪唑、2,2’-联吡啶、4,4’-联吡啶等)、Cu2+, Co2+、Mn2+、Zn2+、Ni2+、Fe3+、[Cu(H2biim)2]2+、[Co(H2biim)2]2+、[Mn(H2biim)2]2+ [Zn(H2biim)2]2+, [Ni(H2biim)2]2+、[Fe(H2biim)2]3+等为抗衡阳离子的多金属氧酸盐化合物催化合成环己酮乙二醇缩酮的酸催化性能及催化规律；2、当抗衡阳离子相同时,考察了不同杂多阴离子,如钨硅酸、钨磷酸、钼硅酸、钼磷酸等阴离子形成的多金属氧酸盐化合物催化合成环己酮乙二醇缩酮的酸催化性能及催化规律；3、通过大量实验,分别以H4SiW12O40、(H4biim)H2SiWi2O40、[Cu(H2biim)2]H2SiWi2O40为催化剂,研究了催化剂与环己酮的比例、反应物料比、反应时间及催化剂循环使用次数等因素对催化合成环己酮乙二醇缩酮效率的影响。更多还原

【Abstract】 Using four saturated Keggin-type polyoxometalates (POMs), i.e. tungstosilicic, tungstophosphoric, molybdosilicic and molybdophosphoric acids as the parent acids. In aqueous solutions, H+can be exchanged by other cations, thus the counter cations, i.e. the alkali metal ions, the ammonium ion, nitrogen-containing organic cations, transition metal ions and transition metal-biimidazole cations, charge-transfer salts based on keggin-type polyoxometalates were prepared by means of direct precipitation. And we selected the synthesis of cyclohexanone ethylene ketal as a model reaction, the catalytic activities of these charge-transfer salts were evaluated. The influences of different acid catalysts and counter cations on the catalytic performance were systemically explored. The results show that the acidic ability and solubility of the parent cmpounds can be adjusted through changing cations, thus some highly efficient, reusable, easily separated acid-catalysts based on polyoxoacids can be further obtained. Copper-2,2’-biimidazole complex was introduced into the POM system, the efficient heterogeneous catalyst was prepared. This work laid a solid experimental foundation for further research and development of these catalysts, and has an important practical significance.1. When the parent acids are the same, the catalytic activities and laws of the POMs using Na+, K+, NH4+, Bu4N+, nitrogen-containing organic cations (e.g. protonated imidazole, 2,2’-biimidazole,2,2’-bipyridine,4,4’-bipyridine, etc.), Cu2+, Co2+, Mn2+, Zn2+, Ni2+, Fe3+, [Cu(H2biim)2]2+, [Co(H2biim)2]2+, [Mn(H2biim)2]2+, [Zn(H2biim)2]2+, [Ni(H2biim)2]2+and [Fe(H2biim)2]3+as counter cations were evalued for the synthesis of cyclohexanone ethylene ketal.2. When the counter cations are the same, the catalytic activities and laws of these POMs containing different polyoxoanions, such as tungstosilicic acid, tungstophosphoric, molybdosilicic and molybdophosphoric acids were evalued for the synthesis of cyclohexanone ethylene ketal.3.Using H4SiWi2O40, (H4biim)H2SiWi2O40, [Cu(H2biim)2]H2SiWi2O40 as catalysts, respectively, the effects of the amounto of the catalyst to cyclohexanone, the molar ratio of the starting material, the reaction time, as well as the frequency of recycles on cyclohexanone ethylene ketal yield were researched.更多还原