过渡金属酯基锡修饰的夹心型铋锗酸盐的合成、结构和表征-无机化学专业论文.docxVIP

辽’j‘师范大学硕十学位论文摘 辽’j‘师范大学硕十学位论文 摘 要 本文以三缺位Keggin结构钨铋酸盐({BiW9})和钨锗酸盐({GeW9})为基本构筑 单元，采用常规水溶液合成方法，利用自组装原理，将酯基锡(SnR， R2CH2CH2COOCH3／CH2CH(CH3)COOCH3)及过渡会属离子(C02+、Mn2十)引入多金属 氧酸盐(POMs)阴离子骨架，成功地合成了5个新的有机锡及过渡金属修饰的夹心型 POMs。通过X一射线单晶衍射分析、元素分析、红外光谱分析、热重分析和电化学分析 等手段对化合物进行了表征，并研究了其在水溶液中的电化学性质及对H202还原的催 化活性。 1、以{BiW9)为基本构筑单元，将酯基锡基团引入多阴离子骨架，设计合成了1个 酯基锡修饰的夹心型化合物： Na6K4[{Sn(C3H402)}2{Sn(C3H402)(H20)}2(B-f1．BiW9033)2]·21H20 (1) 2、以{BiW9)为基本构筑单元，将酯基锡基团引入多阴离子骨架后，进一步与过渡 金属配位组装，设计合成了2个央心型的POM一过渡金属一酯基锡衍生物，实现了进 一步功能化： Na8K2[{Co(H20)3)2{Sn(C3H402)}2(B-fl-BiW9033)2]·25H20 (2) Kl o[{Mn(H20)3}2{Sn(C3H402)}2(B-fl—BiW9033)2】·30H20 (3) 3、以{GeW9)为基本构筑单元，将过渡金属Mn及酯基锡引入多阴离子骨架，设计 合成了2个“悬臂式”的POM．过渡金属．酯基锡衍生物： [C(NH2)3]10H2[Mn2{Sn(C3H402)}2(B—a—GeW9034)2]·8H20 (4) Na3K9[Mn2{Sn(CaH602)}2(B一仅一GeW9034)2]·1 7H20 (5) 关键词：三缺位Keggin结构；钨铋酸盐；钨锗酸盐；酯基锡；夹心型化合物 过渡金属／酯基锡修饰的夹心型钨铋／锗酸盐的研究Synthese，Crystal 过渡金属／酯基锡修饰的夹心型钨铋／锗酸盐的研究 Synthese，Crystal Structures，Characterizations of Sandwich—Type Polytungsto—Bismutates(一Germanates)Decorted by Transition Metals／ Estertin Abstract In this paper，five polyoxometalates with sandwich—type based on triv acant Keggin structure({BiW9}，{GeW9})have been obtained in aqueous solution by routine synthetic method．The transition metal ions of Co(II)，Mn(II)and estertin groups have been introduced into the skeletons of these polyoxoanions．All compounds have been characterized by single—crystal X—ray diffraction，elemental analysis，IR spectroscopy，TG analysis and electrochemical analysis．Their electrocatalytic properties toward the reduction of hydrogen peroxide have been investigated by cyclic voltammetry(cv)． 1．The sandwich—type polytungstobismuthate functionalized with etertin units has been designed and synthesized： ．Na6K4[{Sn(C3H402))2{Sn(C3H402)(H20)}2(Bi∥一BiW9033)2]。2 1 H20 (1) 2．Two sandwich-type polytungstobismuthates functionalized with etertin and transition metals units have been designed and synthesized： NagK2[{Co(H20)3}2{Sn(C3H402)}2(B≯-BiW9033)2]。25H20 (2) K10[{Mn(H20)3}2{Sn(C3H402)}