|(C₄NH₁₂)₄|[M₄Al₁₂P₁₆O₆₄] (M = Co, Zn): New Heteroatom-Containing Aluminophosphate Molecular Sieves with Two Intersecting 8-Ring Channels

Two novel heteroatom-containing aluminophosphate molecular sieves, |(C4NH12)4|[M4Al12P16O64] (denoted MAPO-CJ69, M = Co and Zn), have been solvothermally synthesized using diethylamine as the structure-directing agent. The framework of MAPO-CJ69 exhibits a new zeolite topology which is constructed by strict alternation of metal-centered (Al/M)­O4 tetrahedra and PO4 tetrahedra to form a three-dimensional anionic [M4Al12(PO4)16]4– framework. The structure contains two intersecting 8-ring channels along the [010] and [001] directions, and the protonated diethylamine cations reside in the 8-ring channels to achieve charge neutrality. The structure of MAPO-CJ69 is composed of the 4-4- secondary building unit (SBU), which has been found in some known zeolites, such as AFR, SFO, ZON, OWE, etc. The structural relationships between these zeolites have been discussed.以二乙胺为结构导向剂，通过溶剂热法合成了两种通式为(C4NH12)4·[M4Al12P16O64]的新型含杂原子磷酸铝分子筛，记为MAPO-CJ69（其中M为Co和Zn）。MAPO-CJ69的骨架具有新型沸石拓扑结构，由金属中心（Al/M）配位的四配位氧四面体与PO4四面体严格交替连接，构筑出三维阴离子骨架[M4Al12(PO4)16]4–。该晶体结构沿[010]与[001]方向存在两组相交的八元环孔道，质子化二乙胺阳离子填充于孔道内以维持电荷平衡。MAPO-CJ69的结构由4-4次级结构基元（secondary building unit，SBU）构成，该基元已在AFR、SFO、ZON、OWE等多种已知沸石骨架中被发现。本文还讨论了此类沸石间的结构相关性。