开放骨架磷酸铝合成中碳链长度对乙二胺结构导向效应的影响  

Influence of Carbon Chain Length on the Structure-Directing Effect of Ethylenediamine in the Synthesis of Open-Framework Aluminophosphates

作　　者：常晓文 鲁婷婷[1] 魏颖真 郭明玥 闫文付[1] 徐如人[1] CHANG Xiaowen;LU Tingting;WEI Yingzhen;GUO Mingyue;YAN Wenfu;XU Ruren(State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry,Jilin University,Changchun 130012,China)

机构地区：[1]吉林大学化学学院,无机合成与制备化学国家重点实验室,长春130012

出　　处：《应用化学》2018年第9期1138-1147,共10页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21571075,21320102001,21621001); 国家重大研发计划(2016YFB0701100); 高等学校学科创新引智计划(B17020); 吉林大学高层次科技创新团队项目资助

摘　　要：以乙二胺(EDA)和1,3-丙二胺(1,3-DAP)为结构导向剂,在180℃加热摩尔比n(Al_2O_3)∶n(P_2O_5)∶n(R)∶n(H_2O)=1∶1∶1∶277(R=EDA,1,3-DAP)的混合物,分别得到了高结晶度的三维阴离子开放骨架磷酸铝Al PO4-12和UiO-26。利用X射线粉末衍射分析、元素分析和液相酸碱度测量等表征手段,研究了两个合成体系的晶化过程以及晶化过程中液相的Al、P浓度和pH值随时间的演化。用Materials Studio中的"原子体积和表面"模块和Dmol3模块计算了双质子化乙二胺和1,3-丙二胺的体积以及Hirshfeld电荷。结果表明,双质子化EDA和1,3-DAP中N原子上的Hirshfeld电荷分别为0.073 e和0.064 e,按Hirshfeld电荷计算的电荷密度分别为1.8573和1.3400 e/nm^3,按形式电荷计算的电荷密度分别为25.44和20.94 e/nm3,而AlPO_4-12和UiO-26的骨架电荷密度分别为-6.1和-4.6 e/nm^3。结果表明,与氨基中N原子相连碳链长度的改变会影响其上的电荷量以及电荷密度,从而改变原有机胺的结构导向效应,导致晶化产物从Al PO4-12变成了具有较小电荷密度的UiO-26。By heating the initial mixture with the molar ratio of n（ Al2O3） ∶ n（ P2O5） ∶ n（ R） ∶ n（ H2O） =1∶ 1∶ 1∶ 277（ R = ethylenediamine（ EDA） or 1,3-propanediamine（ 1,3-DAP）） at 180 ℃,a highly crystalline three-dimensional anionic open-framework aluminophosphate of Al PO4-12 or UiO-26 was obtained. The crystallization processes of both initial mixtures were investigated by X-ray diffraction analysis（ XRD）,elemental analysis,and p H measurement. The volume and the Hirshfeld charge on the N atom of the diprotonated EDA and 1,3-DAP were calculated by the ＂atom volume and surface＂module and the Dmol3 module in Materials Studio,respectively. Theoretical calculation shows that the charge on the N atom of diprotonated EDA or 1,3-DAP is 0. 073 e and 0. 064 e（ Hirshfeld）,respectively. The corresponding charge density is 1. 8573 and 1. 3400 e/nm～3（ Hirshfeld）. The corresponding formal charge density is 25. 44 and 20. 94 e/nm^3,respectively. The framework charge density of Al PO4-12 and UiO-26 is-6. 1 e/nm^3 and-4. 6 e/nm^3,respectively. These results indicate that the change in the length of carbon-chain connected to the N atom in the amino group can affect the amount of charge and the charge density on it,which accordingly affects its initial structure-directing ability,resulting the crystallization product changed from AlPO4-12 to UiO-26 with a smaller charge density.

关 键 词：沸石 磷酸铝 结构导向效应 电荷量 电荷密度 

分 类 号：O611.4[理学—无机化学]