物理化学学报 >> 2013, Vol. 29 >> Issue (05): 911-919.doi: 10.3866/PKU.WHXB201302273

热力学,动力学和结构化学 上一篇    下一篇

乙二胺导向合成的微孔晶体磷酸钴的转化现象

罗倩倩, 周世东, 任元, 李牛, 黄志鹏, 关乃佳, 项寿鹤   

  1. 南开大学化学学院 先进能源材料教育部重点实验室, 天津 300071
  • 收稿日期:2013-01-03 修回日期:2013-02-27 发布日期:2013-04-24
  • 通讯作者: 李牛 E-mail:liniu@nankai.edu.cn
  • 基金资助:

    天津市自然科学基金(12JCYBJC12700)和国家重大基础研究项目(973)(2009CB623502)资助

Phenomenon of Structural Transformation of Ethylenediamine- Oriented Synthesis of Microporous Cobalt Phosphate

LUO Qian-Qian, ZHOU Shi-Dong, REN Yuan, Li Niu, HUANG Zhi-Peng, GUAN Nai-Jia, XIANG Shou-He   

  1. Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Department of Materials Chemistry, Nankai University, Tianjin 300071, P. R. China
  • Received:2013-01-03 Revised:2013-02-27 Published:2013-04-24
  • Supported by:

    The project was supported by the Natural Science Foundation of Tianjin, China (12JCYBJC12700) and National Major Fundamental Research Program of China (973) (2009CB623502).

摘要:

以乙二胺为模板剂(SDA)合成微孔晶体磷酸钴, 可以得到多种不同的结构. 本文在合成四种不同结构类型的微孔磷酸钴(命名为CoPO-en-1, CoPO-en-2, CoPO-en-3, CoPO-en-4, en 为乙二胺的英文缩写)过程中发现, 它们之间不仅可以在水热合成条件下相互转化, 在焙烧处理条件下也能实现转化. 研究发现, 在水热合成过程中, CoPO-en-2、CoPO-en-4 分别是CoPO-en-1、CoPO-en-3 的晶化中间物, 在较低晶化温度下或者较高温度的晶化初期, 可以发现它们的身影. 一旦晶化温度升高或者晶化时间延长, 它们就分别转化为CoPO-en-1和CoPO-en-3. 在合成产物的热处理过程中发现: CoPO-en-2、CoPO-en-3、CoPO-en-4 都能够通过焙烧转化为CoPO-en-1. 这种现象表明, 几种微孔磷酸钴结构间的稳定性存在递变关系.

关键词: 磷酸钴, 乙二胺, 结构转化, 水热合成, 焙烧转化

Abstract:

Microporous cobalt phosphate structures can be synthesized using ethylenediamine as a structure directing agent. During the syntheses of CoPO-en-1, CoPO-en-2, CoPO-en-3, and CoPO-en-4, it was found that they could interconvert during hydrothermal or calcination conditions. CoPO-en-2 and CoPO-en-4 are the crystallization intermediates of CoPO-en-1 and CoPO-en-3, respectively. During hydrothermal synthesis, CoPO-en-2 and CoPO-en-4 could be obtained at lower temperature or higher temperature during the initial crystallization stage. Extended synthesis time at higher temperature the two former structures transform into the two latter. CoPO-en-2, CoPO-en-3, and CoPO-en-4 could also convert to CoPO-en-1 during calcination, and these transformations indicated the sequence of structure stability. During synthesis under hydrothermal conditions, CoPO-en-2, CoPO-en-3, and CoPO-en-4 could convert to CoPO-en-1. During muffle furnace roasting, CoPO-en-2, CoPO-en-3, and CoPO-en-4 could also convert to CoPO-en-1. Different structures in the liquid or solid phases could be transformed into the same structure using different approaches.

Key words: Cobalt phosphate, Ethylenediamine, Structural transformation, Hydrothermal synthesis, Calcination transformation

MSC2000: 

  • O643