物理化学学报 >> 2016, Vol. 32 >> Issue (7): 1681-1690.doi: 10.3866/PKU.WHXB201605093

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基于密度泛函理论研究锂-冠醚复合物的结构和热力学参数

赵岩1,敖银勇1,2,*(),陈建1,宋宏涛1,黄玮1,*(),彭静2   

  1. 1 中国工程物理研究院核物理与化学研究所,四川绵阳621900
    2 北京大学化学与分子工程学院,放射化学与辐射化学重点学科实验室,北京分子科学国家实验室,北京100871
  • 收稿日期:2016-03-11 发布日期:2016-07-08
  • 通讯作者: 敖银勇,黄玮 E-mail:aoyinyong@126.com;huangwei839@126.com
  • 基金资助:
    中国工程物理研究院NSAF联合基金重点项目资助(U1430234)

Density Functional Theory Studies of the Structures and Thermodynamic Parameters of Li+-Crown Ether Complexes

Yan ZHAO1,Yin-Yong AO1,2,*(),Jian CHEN1,Hong-Tao SONG1,Wei HUANG1,*(),Jing PENG2   

  1. 1 Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan Province, P. R. China
    2 Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
  • Received:2016-03-11 Published:2016-07-08
  • Contact: Yin-Yong AO,Wei HUANG E-mail:aoyinyong@126.com;huangwei839@126.com
  • Supported by:
    the Joint Fund of the National Natural Science Foundation of China and China Academy of Engineering Physics (NSAF)(U1430234)

摘要:

冠醚对碱金属离子具有高选择性,在锂元素的分离富集上有着广泛的应用。本文基于密度泛函理论(DFT)研究了冠醚环大小、取代基种类、配位原子种类和数量等因素对冠醚空间结构和热力学参数的影响。结果表明,苯并冠醚系列中的苯并-15-冠-5具有更好的配位能力,取代基、配位原子对冠醚的络合能力均有一定影响,因此可通过选择合适的冠醚环,引入供电子基团和含氮杂原子等方法来改善冠醚的分离富集能力。这对冠醚体系分离富集锂元素具有重要的指导意义。

关键词: 锂, 冠醚, 密度泛函理论, 分子结构, 热力学参数

Abstract:

Crown ethers have been widely used for lithium separation in practical applications due to their selectivity. In this study, model crown ethers having different cavity sizes, donor atoms and electron donating/ withdrawing substituent groups were systematically designed. These ethers were subsequently used to study the chemical structures and thermodynamic parameters of Li+-crown ether complexes, employing density functional theory at the B3LYP/6-311+G(d,p) level. Benzo-15-crown-5 was found to have the ability to strongly coordinate lithium ions. It was determined that the coordination ability of crown ethers for lithium ions can be tuned by varying both the substituent groups and the type and amount of donor atoms. These results should be of significant benefit in developing the practical applications of crown ethers for lithium separation.

Key words: Lithium, Crown ether, Density functional theory, Molecular structure, Thermodynamic parameter

MSC2000: 

  • O641