普鲁士蓝类化合物负热膨胀及机理

doi:10.7503/cjcu20190631

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 388.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. 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 Jun^3,^*

^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/Abstract

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

中图分类号:

O614

TrendMD:

高其龙, 梁二军, 邢献然, 陈骏. 普鲁士蓝类化合物负热膨胀及机理. 高等学校化学学报, 2020, 41(3): 388.

GAO Qilong, LIANG Erjun, XING Xianran, CHEN Jun. Negative Thermal Expansion in Prussian Blue Analogues ^†. Chem. J. Chinese Universities, 2020, 41(3): 388.

图/表 14

Fig.1 Structures of AuCN(A), Hg(CN)2(B), Zn(CN)2(C) and Ga(CN)3(D)

Table 1 Structures and thermal expansion properties of metal cyanides

Compound	10⁶α_a/K^-1	10⁶α_c/K^-1	10⁶α_l/K^-1	ΔT/K	Crystal	Ref.
Au(CN)	61.6	-8.9		95—490	Hexagonal	[37]
Ag(CN)	70.8	-24.8		95—490	Trigonal	[37]
HT-Cu(CN)	84.1	-30.7		95—490	Trigonal	[37]
Ni(CN)₂	-6.5	61.8		28—300	Trigonal	[17]
Hg(CN)₂	22.8	71.3		100—395	Tetragonal	[38]
HgCN(NO₃)	26.1	-23.0		100—395	Hexagonal	[38]
Zn[Au(CN)₂]₂	36.9	-57.5		100—775	Hexagonal	[39]
Zn[Au(CN)₂]₂-xAgCN	4.07	-21.7		100—375	Hexagonal	[39]
Cd(CN)₂			-20.4	150—375	Cubic	[35]
Zn(CN)₂			-16.9	25—375	Cubic	[35]
Single-network Cd(CN)₂			-33.5	170—375	Cubic	[40]
Cd(CN)₂-0.64CCl₄			-16.9	240—375	Cubic	[40]
Cd(CN)₂-0.75CCl₄			-5.7	200—375	Cubic	[40]
Cd(CN)₂-CCl₄			10.0	100—240	Cubic	[40]
Me₄NCuZn(CN)₄			0.67	218—368	Cubic	[41]

Fig.3 Structure of Ga(CN)6(A) and the change of lattice constant dependence of temperature for GaFe(CN)6·2H2O(B)

Table 2 Negative thermal expansion properties in hexacyano-Prussian blue analogues

Compound	10⁶α_V/K^-1	ΔT/K	Ref.	Compound	10⁶α_V/K^-1	ΔT/K	Ref.
FeCo(CN)₆	-4.41	4.2—300	[18]	YFe(CN)₆	-33.7	300—525	[28]
GaFe(CN)₆	-12	100—475	[48]	Mn₃[Co(CN)₆]₂	-87.6	123—300	[52]
FeFe(CN)₆	-12.8	100—475	[49]	Fe₃[Co(CN)₆]₂	-58.8	123—300	[52]
CdPt(CN)₆	-30.06	100—240	[50]	Co₃[Co(CN)₆]₂	-119.1	123—300	[52]
MnPt(CN)₆	-19.74	100—300	[50]	Ni₃[Co(CN)₆]₂	-90.0	123—300	[52]
FePt(CN)₆	-12	100—315	[50]	Cu₃[Co(CN)₆]₂	-60.0	123—300	[52]
ZnPt(CN)₆	-10.59	100—400	[50]	Zn₃[Co(CN)₆]₂	-89.1	123—300	[52]
CoPt(CN)₆	-4.8	100—350	[50]	Fe₃[Fe(CN)₆]₂	-29.7	123—300	[52]
NiPt(CN)₆	-3.06	100—330	[50]	Cu₃[Fe(CN)₆]₂	-59.7	123—300	[52]
CuPt(CN)₆	-4.71	100—400	[50]	Zn₃[Fe(CN)₆]₂	-118.8	123—300	[52]
ErCo(CN)₆	-27	100—500	[51]	Cs_0.7Ni[Fe(CN)₆]_0.9·2.9H₂O	-1.2	100—300	[53]
LaCo(CN)₆	-43.86	100—500	[19]	Cs_0.97Cu[Fe(CN)₆]_0.99·1.1H₂O	-6.3	100—300	[53]
SmCo(CN)₆	-37.38	100—500	[19]	Cs_0.91Zn[Fe(CN)₆]_0.97·0.4H₂O	-12.3	100—300	[53]
HoCo(CN)₆	-30.15	100—500	[19]	CsCd[Fe(CN)₆]·0.5H₂O	-26.4	100—300	[53]
LuCo(CN)₆	-27.15	100—500	[19]	Rb_0.78Fe[Fe(CN)₆]_0.83·2.8H₂O	-6.3	100—300	[53]
YCo(CN)₆	-31.59	100—500	[19]	Rb_0.64Zn[Fe(CN)₆]_0.88·2.3H₂O	-17.7	100—300	[53]

Fig.5 Comparison between the “apparent” and the “true” Ga—N and Fe—C bond lengths in GaFe(CN)6 as a function of temperature(A), Ga—N(B) and Fe—C(C) perpendicular(⊥) and parallel(‖) MSRDs of Ga—N atomic pairs of GaFe(CN)6 as a function of temperature, anisotropy of the relative thermal vibrations of the Ga—N and Fe—C atomic pairs of GaFe(CN)6 determined by EXAFS(D)[48] Copyright 2018, American Chemical Society.

Fig.6 Sketch of the cubic structure of GaFe(CN)6 consisting of alternating GaN6 and FeC6 octahedra(A), the negative thermal expansion of GaFe(CN)6 derived from the transverse vibrations of CN cyanogen ions(B) and the transverse vibrations of CN cyanogen ions hindered by guest ions or molecules(C)[57] (A) The empty space indicated by the dash circle can host guest ions or molecules. Copyright 2018, American Chemical Society.

Fig.7 Temperature dependence of the relative change in lattice constant of GaFe(CN)6-based compounds(A)[57] and the coefficient of thermal expansion for YFe(CN)6-based materials within different guests(B)[28] (A) Copyright 2018, American Chemical Society; (B) copyright 2017, Wiley.

Fig.8 ADPs depiction and its temperature dependence for N atoms in YFe(CN)6(A,C) and YFe(CN)6·4H2O(B,D), respectively, the temperature dependence of MSRDs of the Fe—C atomic and the frequency dependence of mode Grüneisen parameters in YFe(CN)6(E,G) and KYFe(CN)6(F,H), respectively[28] Copyright 2017, Wiley.

Fig.10 Structure of Ag3Co(CN)6, the strongest bonding interactions, which occur within Co—CN—Ag—NC—Co linkages, all lie parallel to the crystallographic [101] directions(A) and the lattice parameters for Ag3Co(CN)6 as a function of temperature(B)[20] (B) Inset show the sketch of large changes for Ag…Ag and [Co(CN)6]…[Co(CN)6] unit. Copyright 2008, Science.

Table 3 Thermal expansion prepoerties of Ag3Co(CN)6-typed PBAs

Compound	10⁶a/K^-1	10⁶c/K^-1	ΔT/K	Ref.
H₃Co(CN)₆	12.0(4)	-8.8(3)	4—300	[65]
D₃Co(CN)₆	17.4(6)	-5.04(24)	8—304	[65]
Cu₃Co(CN)₆	25.4(5)	-43.5(8)	100—596	[66]
Ag₃Co(CN)₆	145.9(6)	-122.1(3)	16—500	[20]
Ag₃Fe(CN)₆	124.0(10)	-113(3)	8—310	[20]
In[Au(CN)₂]₃	86.1—83.9	-62.2—-63.3	100—395	[62]
In[Ag(CN)₂]₃	104—106	-85—-83	100—395	[62]
KCd[Au(CN)₂]₃	72.9—71.4	-56.1—-57.1	100—395	[62]
KCd[Ag(CN)₂]₃	76.6—74.9	-64.3—-65.6	100—395	[62]
KNi[Au(CN)₂]₃	59.7—58.7	-42.2—-42.7	100—395	[62]
KMn[Ag(CN)₂]₃	61(2)	-60(3)	100—395	[62]

Fig.11 Structure schematic of Ni2Ⅱ[WⅣ(CN)8]·6H2O(A) and Ni2Ⅱ[WⅣ(CN)8](B), the comparison physical property of Ni2Ⅱ[WⅣ(CN)8]·6H2O and Ni2Ⅱ[WⅣ(CN)8] in magnetism(C) and thermal expansion(D) [32] Copyright 2016, American Chemical Society.

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普鲁士蓝类化合物负热膨胀及机理

Negative Thermal Expansion in Prussian Blue Analogues ^†

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普鲁士蓝类化合物负热膨胀及机理

Negative Thermal Expansion in Prussian Blue Analogues †

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Negative Thermal Expansion in Prussian Blue Analogues ^†