Thermal expansion in 3d-metal Prussian Blue Analogs - A survey study

Sourav Adak; Luke L. Daemen; Monika Hartl; Darrick Williams; Jennifer Summerhill; Heinz Nakotte

doi:10.1016/j.jssc.2011.08.030

Thermal expansion in 3d-metal Prussian Blue Analogs - A survey study

Sourav Adak, Luke L. Daemen, Monika Hartl, Darrick Williams, Jennifer Summerhill, Heinz Nakotte

Research output: Contribution to journal › Article › peer-review

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Abstract

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M^II ₃[(M′)^III(CN) ₆]₂·nH₂O and M^II ₂[Fe^II(CN)₆]·nH₂O, where M^II=Mn, Fe, Co, Ni, Cu and Zn, (M′)^III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3m, F43m and Pm3m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×¹0^-6 K^-1 for Co₃[Co(CN)₆]₂·12H₂O. All of the M^II ₃[Co^III(CN)₆] ₂·nH₂O compounds show negative thermal expansion behavior, which correlates with the IrvingWilliams series for metal complex stability. The thermal expansion behavior for the PBAs of the M ^II ₃[Fe^III(CN)₆]₂· nH₂O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M^II ₂[Fe ^II(CN)₆]·nH₂O compounds show positive thermal expansion behavior.

Original language	English
Pages (from-to)	2854-2861
Number of pages	8
Journal	Journal of Solid State Chemistry
Volume	184
Issue number	11
DOIs	https://doi.org/10.1016/j.jssc.2011.08.030
State	Published - Nov 2011
Externally published	Yes

Funding

This research work has been supported by Department of Energy's (DOE) Office of Basic Energy Sciences and has made use of Manuel Lujan, Jr. Neutron Scattering Center at Los Alamos National Laboratory which is funded by DOE Office of Basic Energy Sciences. Los Alamos National Laboratory is operated by Los Alamos National Security, LLC, under DOE Contract DE-AC52-06NA25396 . JS acknowledges partial support provided by Shengnian Luo at LANL ( DOE grant number: 20110585ER ).

Funders	Funder number
Department of Energy's
Basic Energy Sciences	DE-AC52-06NA25396, 20110585ER

Keywords

Crystal structures
Negative thermal expansion
Prussian Blue Analogs

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10.1016/j.jssc.2011.08.030

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@article{ee037af26acd4cb8a0de769bc373c808,

title = "Thermal expansion in 3d-metal Prussian Blue Analogs - A survey study",

abstract = "We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions MII 3[(M′)III(CN) 6]2·nH2O and MII 2[FeII(CN)6]·nH2O, where MII=Mn, Fe, Co, Ni, Cu and Zn, (M′)III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3m, F43m and Pm3m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×10-6 K-1 for Co3[Co(CN)6]2·12H2O. All of the MII 3[CoIII(CN)6] 2·nH2O compounds show negative thermal expansion behavior, which correlates with the IrvingWilliams series for metal complex stability. The thermal expansion behavior for the PBAs of the M II 3[FeIII(CN)6]2· nH2O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the MII 2[Fe II(CN)6]·nH2O compounds show positive thermal expansion behavior.",

keywords = "Crystal structures, Negative thermal expansion, Prussian Blue Analogs",

author = "Sourav Adak and Daemen, {Luke L.} and Monika Hartl and Darrick Williams and Jennifer Summerhill and Heinz Nakotte",

year = "2011",

month = nov,

doi = "10.1016/j.jssc.2011.08.030",

language = "English",

volume = "184",

pages = "2854--2861",

journal = "Journal of Solid State Chemistry",

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T1 - Thermal expansion in 3d-metal Prussian Blue Analogs - A survey study

AU - Adak, Sourav

AU - Daemen, Luke L.

AU - Hartl, Monika

AU - Williams, Darrick

AU - Summerhill, Jennifer

AU - Nakotte, Heinz

PY - 2011/11

Y1 - 2011/11

N2 - We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions MII 3[(M′)III(CN) 6]2·nH2O and MII 2[FeII(CN)6]·nH2O, where MII=Mn, Fe, Co, Ni, Cu and Zn, (M′)III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3m, F43m and Pm3m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×10-6 K-1 for Co3[Co(CN)6]2·12H2O. All of the MII 3[CoIII(CN)6] 2·nH2O compounds show negative thermal expansion behavior, which correlates with the IrvingWilliams series for metal complex stability. The thermal expansion behavior for the PBAs of the M II 3[FeIII(CN)6]2· nH2O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the MII 2[Fe II(CN)6]·nH2O compounds show positive thermal expansion behavior.

AB - We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions MII 3[(M′)III(CN) 6]2·nH2O and MII 2[FeII(CN)6]·nH2O, where MII=Mn, Fe, Co, Ni, Cu and Zn, (M′)III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3m, F43m and Pm3m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×10-6 K-1 for Co3[Co(CN)6]2·12H2O. All of the MII 3[CoIII(CN)6] 2·nH2O compounds show negative thermal expansion behavior, which correlates with the IrvingWilliams series for metal complex stability. The thermal expansion behavior for the PBAs of the M II 3[FeIII(CN)6]2· nH2O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the MII 2[Fe II(CN)6]·nH2O compounds show positive thermal expansion behavior.

KW - Crystal structures

KW - Negative thermal expansion

KW - Prussian Blue Analogs

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DO - 10.1016/j.jssc.2011.08.030

M3 - Article

AN - SCOPUS:80054941402

SN - 0022-4596

VL - 184

SP - 2854

EP - 2861

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

IS - 11

ER -

Thermal expansion in 3d-metal Prussian Blue Analogs - A survey study

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