高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 388-400.doi: 10.7503/cjcu20190631

• 庆祝《高等学校化学学报》复刊40周年专栏 • 上一篇    下一篇

普鲁士蓝类化合物负热膨胀及机理

高其龙1,梁二军1,邢献然2,陈骏3,*   

  1. 1. 郑州大学物理学院, 河南省量子功能化合物国际联合实验室, 郑州 450001
    2. 北京科技大学固体化学研究所, 北京 100083
    3. 北京科技大学数理学院, 北京 100083
  • 收稿日期:2019-12-06 出版日期:2020-03-10 发布日期:2020-01-07
  • 通讯作者: 陈骏
  • 作者简介:陈 骏, 男, 博士, 研究员, 主要从事固体化学研究. E-mail: junchen@ustb.edu.cn
  • 基金资助:
    国家自然科学基金资助(Nos.21825102);国家自然科学基金资助(Nos.21905252);国家自然科学基金资助(Nos.21731001)

Negative Thermal Expansion in Prussian Blue Analogues

GAO Qilong1,LIANG Erjun1,XING Xianran2,CHEN Jun3,*   

  1. 1. International Laboratory for Quantum Functional Materials of Henan, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, China
    2. Institute of Solid State Chemistry, University of Science and Technology Beijing, Beijing 100083, China
    3. School of Mathematics and Physics, University of Science and Technology Beijing, Beijing 100083, China
  • Received:2019-12-06 Online:2020-03-10 Published:2020-01-07
  • Contact: Jun CHEN
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21825102);† Supported by the National Natural Science Foundation of China(Nos.21905252);† Supported by the National Natural Science Foundation of China(Nos.21731001)

摘要:

负热膨胀化合物可调控材料的热膨胀系数, 在复合材料、 精密仪器等方面具有重要的应用前景, 成为近年来化学、 物理和材料工程领域的研究热点之一. 因其晶体结构主要由—M—CN—M—含有双原子氰根(CN)链组成, 许多普鲁士蓝类化合物呈现反常的热膨胀性质. 本文综述了普鲁士蓝类负热膨胀化合物结构、 热膨胀机制与系数调控等方面的研究进展. 以氰根配体数量为分类主线, 将具有反常热膨胀性的氰根配体化合物分为氰化物、 六氰基和八氰基普鲁士蓝类化合物等进行介绍, 从局域结构和平均结构角度分析了N和C原子的横向振动对负热膨胀贡献的角度解释了机理, 从客体离子或分子嵌入的方法分析了热膨胀调控原理, 并对新型普鲁士蓝类负热膨胀化合物的设计及应用进行了展望.

关键词: 负热膨胀, 普鲁士蓝类似物, 横向振动, 局域结构, 低频声子

Abstract:

Negative thermal expansion(NTE) is a promising topic for solid state chemistry, physics, and materials science. Due to the unique lattice structure characteristics, many Prussian blue analogues(PBAs) compounds have been found to exhibit NTE in the last two decades. This review is introduced for the NTE compounds progress in the PBAs. From the studies on local structure and lattice structure, the NTE mechanism is reviewed to reveal the important transverse vibrational contribution of N and C atoms. Based on this NTE mechanism, thermal expansion can be designed by inserting guest ions or molecules to reduce the contribution of transverse vibration. Finally, the perspective of PBAs is discussed for the design of new NTE PBAs compounds and the potential applications in future.

Key words: Negative thermal expansion, Prussian blue analogues, Transverse vibration, Local structure, Low frequency phonon

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