新型三维开放骨架磷酸铝化合物的合成及晶化过程中的共模板效应

摘要

以1,2-丙二胺(1,2-DAP)为结构导向剂, 在180 ℃加热摩尔组成为n(Al2O3)∶n(P2O5)∶n(1,2-DAP)∶n(H2O)=1∶6∶5.5∶139的初始混合物, 合成了具有AlPO-CJ31骨架结构的新型三维开放骨架磷酸铝化合物(1);加热摩尔组成为n(Al2O3)∶n(P2O5)∶n(1,2-DAP)∶n(H2O)=1∶6∶7.5∶139的初始混合物, 合成了二维层状磷酸铝化合物APDAP12-150.利用X射线粉末衍射分析(XRD)、 元素分析、 热重/差热分析等表征手段确认了化合物1的分子式为[Al4P5O20·H3O·H2O]·[H3NCH2CHNH3CH3], 质子化的水分子与双质子化的1,2-丙二胺共同起到了导向化合物1的作用.调变初始混合物中1,2-丙二胺的比例可显著影响其模板效应.1,2-丙二胺比例较低[n(1,2-DAP)=5.5]时, 产物为三维开放骨架化合物, 而当其比例较高[n(1,2-DAP)=7.5]时, 产物为二维层状化合物.%By heating the initial mixture with the molar composition of n(Al2O3)∶n(P2O5)∶n(1,2-DAP)∶n(H2O)=1∶6∶x∶139(1,2-DAP refers to 1,2-diaminopropane) at 180 ℃, a new three-dimensional open-framework aluminophosphate(compound 1) and a two-dimensional layered aluminophosphate APDAP12-150 were obtained at x=5.5 and x=7.5, respectively.The framework topology of compound 1 is the same as that of AlPO-CJ31, a three-dimensional open-framework aluminophosphate directed by the template of diethylenetriamine.By combing the results of powder X-ray diffraction analysis(XRD), elemental analysis(C, H, N) and TG-DTA analysis, the composition of compound 1 was determined and the co-templating effect of protonated water was confirmed.