摘要
Three layered aluminophosphates(UiO-15, APDAP12-150 and APDAP-150) with same topology were crystallized from an initial mixture with a molar Composition of A1203:1.SP2Os:5.5R:227HzO, where R is ethylene- diamine, 1,2-diaminopropane or 1,3-diaminopropane, respectively. The crystallization processes of UiO-15, APDAPI2-150 and APDAP-150 were investigated using solid-state NMR in combination with XRD and other cha- racterization techniques. The evolution of the coordination states of Al and P in the solid products was monitored, and the possible starting points of crystallization(core units) of UiO-15, APDAP12-150 and APDAP-150 were obtained and analyzed. The formation ofa trimer as well as a hexamer of aluminophosphate, a monomer of PO4 and a nonamer containing two three-membered rings is critical for the start of crystallization of UiO-15. The formation of a hexamer and a pentamer is critical for the start of crystallization of APDAP12-150. The formation of an A106 monomer and a pentamer containing a three-membered ring is critical for the start of crystallization ofAPDAP-150. The crystal water played a co-structure-directing role in the formation ofAPDAP-150.
Three layered aluminophosphates(UiO-15, APDAP12-150 and APDAP-150) with same topology were crystallized from an initial mixture with a molar Composition of A1203:1.SP2Os:5.5R:227HzO, where R is ethylene- diamine, 1,2-diaminopropane or 1,3-diaminopropane, respectively. The crystallization processes of UiO-15, APDAPI2-150 and APDAP-150 were investigated using solid-state NMR in combination with XRD and other cha- racterization techniques. The evolution of the coordination states of Al and P in the solid products was monitored, and the possible starting points of crystallization(core units) of UiO-15, APDAP12-150 and APDAP-150 were obtained and analyzed. The formation ofa trimer as well as a hexamer of aluminophosphate, a monomer of PO4 and a nonamer containing two three-membered rings is critical for the start of crystallization of UiO-15. The formation of a hexamer and a pentamer is critical for the start of crystallization of APDAP12-150. The formation of an A106 monomer and a pentamer containing a three-membered ring is critical for the start of crystallization ofAPDAP-150. The crystal water played a co-structure-directing role in the formation ofAPDAP-150.
基金
Supported by the National Natural Science Foundation of China(Nos.21571075, 21320102001, 21621001 ) and the National Key Research and Development Program of China(No.2016YFB0701100).