Cation-directed syntheses of novel zeolite-like metalloaluminophosphates STA-6 and STA-7 in the presence of azamacrocycle templates
作者:Paul A. Wright、Martin J. Maple、Alexandra M. Z. Slawin、Véronique Patinec、R. Alan Aitken、Simon Welsh、Paul A. Cox
DOI:10.1039/a909249h
日期:——
Hydrothermal syntheses of divalent metal cation-containing aluminophosphates, or MAPOs (M = Mg, Mn, Fe, Co or Zn), have been performed using the azamacrocycle 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane as a structure directing agent. Whereas STA-6 (St. Andrews-6), a small pore zeotype with a one-dimensional channel system, is prepared when magnesium, manganese or iron is included in the synthesis gel, a new solid, STA-7, is prepared in the presence of cobalt or zinc. The structure of STA-7 has been solved and found to possess a tetrahedrally connected framework with a fully three-dimensional interconnected small pore channel system. The organic template molecules included during synthesis can completely be removed without loss of framework integrity from the cobalt form. Syntheses using the hexaazamacrocycle 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane have also been successful in preparing STA-7 in the presence of divalent metal cations. Both STA-6 and STA-7 structure types can be considered to be built up of cages and chemical analysis and computer simulation suggest strongly that the macrocycles act to template these cages.
利用偶氮环 1,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷作为结构引导剂,对含二价金属阳离子的铝磷酸盐或 MAPOs(M = 镁、锰、铁、钴或锌)进行了水热合成。如果在合成凝胶中加入镁、锰或铁,就能制备出具有一维通道系统的小孔沸石 STA-6(圣安德鲁斯-6),而如果加入钴或锌,就能制备出新的固体 STA-7。人们已经解决了 STA-7 的结构问题,发现它具有一个四面体连接框架,其中有一个完全三维的相互连接的小孔通道系统。合成过程中加入的有机模板分子可以完全去除,而不会失去钴形式框架的完整性。使用六氮杂环 1,4,7,10,13,16-六甲基-1,4,7,10,13,16-六氮杂环十八烷进行合成,也成功地在二价金属阳离子存在下制备出了 STA-7。STA-6 和 STA-7 两种结构类型都可以被认为是由笼状结构组成的,化学分析和计算机模拟强烈表明,大环起到了模板这些笼状结构的作用。