高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (3): 428.doi: 10.7503/cjcu20140894

• 研究论文: 无机化学 • 上一篇    下一篇

开放骨架磷酸铝合成中F-对有机胺结构导向效应的影响

田野1, 王淑荣2, 闫文付1(), 徐如人1, 王永睿3, 慕旭宏3   

  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. 吉林大学第二医院, 长春 130012
    3. 中国石化石油化工科学研究院, 石油化工催化材料与反应工程国家重点实验室, 北京 100083
  • 收稿日期:2014-10-09 出版日期:2015-03-10 发布日期:2015-02-04
  • 作者简介:联系人简介: 闫文付, 男, 博士, 教授, 博士生导师, 主要从事无机微孔晶体的晶化机理和手性分子筛的合成研究. E-mail: yanw@jlu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21171063)、 国家优秀青年科学基金(批准号: 21222103)、 国家重点基础研究发展规划项目(批准号: 2011CB808703)、 长江学者和创新团队发展计划(批准号: IRT101713018)和石油化工催化材料与反应工程国家重点实验室(中国石油化工股份有限公司石油化工科学研究院)开放基金资助

Influence of F- on the Structure-directing Effect of Organic Amines in the Synthesis of Open-framework Aluminophosphates

TIAN Ye1, WANG Shurong2, YAN Wenfu1,*(), XU Ruren1, WANG Yongrui3, MU Xuhong3   

  1. 1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,Jilin University, Changchun 130012, China
    2. The Second Hospital of Jilin University, Changchun 130012, China
    3. State Key Laboratory of Catalytic Materials and Reaction Engineering,Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
  • Received:2014-10-09 Online:2015-03-10 Published:2015-02-04
  • Contact: YAN Wenfu E-mail:yanw@jlu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21171063), the Excellent Young Scientists Fund, China(No.21222103), the State Basic Research Projects of China(No.2011CB808703), the Program for Chang Jiang Scholars and Innovative Research Team in University of China(No.IRT101713018), and the Open Fund of the State Key Laboratory of Catalytic Materials and Reaction Enginee-ring, China(No.RIPP, SINOPEC)

摘要:

研究了在开放骨架磷酸铝合成中氟离子对乙二胺(en)和二乙烯三胺(deta)的结构导向效应的影响. 在水热条件下, 以乙二胺为结构导向剂, 分别从摩尔组成为n(Al2O3):n(P2O5):n(en):n(H2O)=1.0:1.5:18.0:147 和n(Al2O3):n(P2O5):n(en):n(HF):n(H2O)=1.0:1.5:18.0:3.0:147的初始混合物中晶化出二维层状磷酸铝Al2P2O9·NH3(CH2)2NH3(UiO-13) 和AlF(HPO4)·NH2(CH2)2NH2(1); 以二乙烯三胺为结构导向剂, 分别从摩尔组成为n(Al2O3):n(P2O5):n(deta):n(H2O)=1.0:4.0:3.0:153 和n(Al2O3):n(P2O5):n(deta):n(HF):n(H2O)=1.0:4.0:3.0:3.0:153的初始混合物中晶化出了三维开放骨架磷酸铝Al4P5O20(H2O)2·C4N3H16(AlPO-CJ31) 和一维链状磷酸铝Al2P4O10(OH)3F·C4N3H15(2), 表明凝胶中的F-显著改变了乙二胺和二乙烯三胺的结构导向效应. 详细对比分析了UiO-13和化合物1以及AlPO-CJ31和化合物2的结构, 探讨了F-对乙二胺和二乙烯三胺的结构导向效应的影响及F-与有机胺的协同结构导向效应.

关键词: 开放骨架磷酸铝, 氟离子, 乙二胺, 二乙烯三胺, 结构导向效应

Abstract:

The significant influence of F- on the structure-directing effect of ethylenediamine(en) and diethylenetriamine(deta) in the synthesis of open-framework aluminophosphates was investigated. For the system with ethylenediamine, in the absence of F-, layered aluminophosphate Al2P2O9·NH3(CH2)2NH3(UiO-13) was obtained from the initial mixture with n(Al2O3):n(P2O5):n(en):n(H2O)=1.0:1.5:18.0:147 under hydrothermal condition, while layered aluminophosphate AlF(HPO4)·NH2(CH2)2NH2(1) was obtained from the initial mixture with n(Al2O3):n(P2O5):n(en):n(HF):n(H2O)=1.0:1.5:18.0:3.0:147. The results suggested that the F- significantly affected the structure-directing effect of ethylenediamine. For the system with diethylenetriamine, a three-dimensional(3D) open-framework aluminophosphate Al4P5O20(H2O)2·C4N3H16(AlPO-CJ31) was synthesized from the initial mixture with n(Al2O3):n(P2O5):n(deta):n(H2O)=1.0:4.0:3.0:153 under hydrothermal condition, while a one-dimensional(1D) aluminophosphate Al2P4O10(OH)3F·C4N3H15(2) was crystallized from the similar initial mixture in the presence of F-[n(Al2O3):n(P2O5):n(deta):n(HF):n(H2O)=1.0:4.0:3.0:3.0:153]. The results indicated that the structure-directing effect of diethylenetriamine was significantly altered by F-. The structural properties of open-framework aluminophosphates UiO-13, 1, AlPO-CJ31 and 2 were analyzed in detail and the influence of F- on the structure-directing effect of ethylenediamine and diethylenetriamine was discussed.

Key words: Open-framework aluminophosphate, Fluoride, Ethylenediamine, Diethylenetriamine, Structure-directing effect

中图分类号: 

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