Negative Thermal Expansion in Prussian Blue Analogues †

doi:10.7503/cjcu20190631

Abstract

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

CLC Number:

O614

TrendMD:

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

Figures/Tables 14

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

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)

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.

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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