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

doi:10.11944/j.issn.1000-0518.2018.09.180115

摘要/Abstract

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(Al₂O₃):n(P₂O₅):n(R):n(H₂O)=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AlPO₄-12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/nm³,按形式电荷计算的电荷密度分别为25.44和20.94 e/nm³,而AlPO₄-12和UiO-26的骨架电荷密度分别为-6.1和-4.6 e/nm³。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AlPO₄-12变成了具有较小电荷密度的UiO-26。

关键词: 沸石, 磷酸铝, 结构导向效应, 电荷量, 电荷密度

Abstract:

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 AlPO₄-12 or UiO-26 was obtained. The crystallization processes of both initial mixtures were investigated by X-ray diffraction analysis(XRD), elemental analysis, and pH 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/nm³(Hirshfeld). The corresponding formal charge density is 25.44 and 20.94 e/nm³, respectively. The framework charge density of AlPO₄-12 and UiO-26 is -6.1 e/nm³ and -4.6 e/nm³, 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.

Key words: zeolite, aluminophosphate, structure-directing effect, charge, charge density

常晓文, 鲁婷婷, 魏颖真, 郭明玥, 闫文付, 徐如人. 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[J]. 应用化学, 2018, 35(9): 1138-1147.

CHANG Xiaowen, LU Tingting, WEI Yingzhenx, GUO Mingyue, YAN Wenfu, XU Ruren. Influence of Carbon Chain Length on the Structure-Directing Effect of Ethylenediamine in the Synthesis of Open-Framework Aluminophosphates[J]. Chinese Journal of Applied Chemistry, 2018, 35(9): 1138-1147.

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