开放骨架结构磷酸铝合成中N原子环境变化对甲胺结构导向效应的影响

doi:10.7503/cjcu20170590

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (1): 12.doi: 10.7503/cjcu20170590

• 研究论文: 无机化学 • 上一篇下一篇

开放骨架结构磷酸铝合成中N原子环境变化对甲胺结构导向效应的影响

常晓文¹, 闫文付¹(), 师唯², 徐如人¹

1. 吉林大学无机合成与制备化学国家重点实验室, 化学学院, 长春 130012
2. 南开大学化学学院先进能源材料化学教育部重点实验室, 天津 300071

收稿日期:2017-08-31 出版日期:2018-01-10 发布日期:2017-12-19
作者简介:联系人简介: 闫文付, 男, 博士, 教授, 博士生导师, 主要从事无机微孔材料的晶化机理及手性分子筛的合成与应用研究. E-mail:yanw@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21571075, 21320102001, 21621001)、国家“八六三”计划项目(批准号: 2016YFB0701100)、高等学校学科创新引智计划(批准号: B17020)和吉林大学高层次科技创新团队项目资助

Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^†

CHANG Xiaowen¹, YAN Wenfu^1,^*(), SHI Wei², XU Ruren¹

1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
2. Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education), Nankai University, Tianjing 300071, China

Received:2017-08-31 Online:2018-01-10 Published:2017-12-19
Contact: YAN Wenfu E-mail:yanw@jlu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21571075, 21320102001, 21621001), the National Key Research and Development Program of China(No.2016YFB0701100), the Program of Introducing Talents of Discipline to Universities, China(No.B17020) and the Program of Science and Technology Innovative Research Team of Jilin University, China

摘要/Abstract

摘要：

以甲胺(MA)和二甲胺(DMA)为结构导向剂, 在200 ℃加热摩尔组成为n(Al₂O₃):n(P₂O₅):n(R):n(H₂O)=1:1:1:277(R=MA, DMA)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AlPO₄-53和AlPO₄-21. 质子化的甲胺和二甲胺分别位于AlPO₄-53和AlPO₄-21的骨架中以平衡骨架的负电荷. 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2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. 理论计算结果表明, 质子化甲胺和二甲胺的N原子上的电荷分别为-0.263和-0.558 e(Mulliken), 形式电荷密度分别为22.3和16.0 e/nm³, AlPO₄-53和AlPO₄-21的骨架电荷密度分别为-3.3和-3.1 e/nm³. 结果表明, 改变N原子的环境会影响其上的电荷量, 从而改变有机胺的结构导向效应, 有机胺的形式电荷密度和无机骨架电荷密度之间存在着匹配关系.

关键词: 沸石, 磷酸铝, 结构导向效应, 模板效应, 形式电荷密度, 骨架电荷密度

Abstract:

By heating the initial mixture with the molar composition of n(Al₂O₃):n(P₂O₅):n(R):n(H₂O)=1:1:1:277(R=methylamine or dimethylamine) at 200 ℃, highly crystalline three-dimensional anionic open-framework aluminophosphate of AlPO₄-53 or AlPO₄-21 was obtained. Protonated methylamine and dimethylamine were located in the framework of AlPO₄-53 and AlPO₄-21 to balance the negative charge of the framework, respectively. The crystallization processes of both initial mixtures were investigated by X-ray diffraction analysis(XRD), elemental analysis and pH measurement. Theoretical calculation shows that the charge on the N atom of protonated methylamine and dimethylamine is -0.263 and -0.558 e(Mulliken), respectively. The corresponding formal charge density is 22.3 and 16.0 e/nm³, respectively. The framework charge density of AlPO₄-53 and AlPO₄-21 is -3.3 and -3.1 e/nm³, respectively. These results indicate that the environment change around N atom can affect the amount of charge on it, which accordingly affects its structure-directing ability. A charge matching between the formal charge density of organic amines and the framework charge density was observed.

Key words: Zeolite, Aluminophosphate, Structure-directing effect, Template effect, Formal charge density, Framework charge density

中图分类号:

O611.4

TrendMD:

常晓文, 闫文付, 师唯, 徐如人. 开放骨架结构磷酸铝合成中N原子环境变化对甲胺结构导向效应的影响. 高等学校化学学报, 2018, 39(1): 12.

CHANG Xiaowen, YAN Wenfu, SHI Wei, XU Ruren. Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^†. Chem. J. Chinese Universities, 2018, 39(1): 12.

图/表 4

Fig.1 Summary of the crystallization of the initial mixtures with the molar composition of n(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277(R=CH3NH2 and CH3NHCH3)

Fig.2 Simulated XRD patterns of AlPO4-53, AlPO4-21 and the experimental powder XRD patterns of solid samples isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277. (A) R=CH3NH2. Hydrothermal treatment period/h: a. 0; b. 3; c. 4; d. 72; e. simulated AlPO4-53. (B) R=CH3NHCH3. Hydrothermal treatment period/h: a. 0; b. 2.5; c. 4; d. 16; e. 96; f. simulated AlPO4-21.

Fig.3 Evolution of the concentrations of Al(a) and P(b) in the liquid phase of the samples isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277. (A) R=CH3NH2; (B) R=CH3NHCH3.

Fig.4 Evolution of the pH of the liquid phase in the products isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(CH3NH2):n(H2O)=1:1:1:277. (A) CH3NH2; (B) R=CH3OHCH3.

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开放骨架结构磷酸铝合成中N原子环境变化对甲胺结构导向效应的影响

Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^†

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开放骨架结构磷酸铝合成中N原子环境变化对甲胺结构导向效应的影响

Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates†

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Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^†