Negative thermal expansion in cubic FeFe(CN)6 Prussian blue analogues

Naike Shi; Qilong Gao; Andrea Sanson; Qiang Li; Longlong Fan; Yang Ren; Luca Olivi; Jun Chen; Xianran Xing

doi:10.1039/c8dt05111a

Negative thermal expansion in cubic FeFe(CN)₆ Prussian blue analogues

Naike Shi
, Qilong Gao
, Andrea Sanson
, Qiang Li
, Longlong Fan
, Yang Ren
, Luca Olivi
, Jun Chen^*
, Xianran Xing

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

43 Citations (Scopus)

Abstract

Negative thermal expansion (NTE) behavior is an interesting physical phenomenon, but the number of NTE materials is limited. In this study, a new NTE compound has been found, FeFe(CN)₆ Prussian blue analogue, where the average linear coefficient of thermal expansion (α_l) is -4.260 × 10^-6 K^-1 between 100 and 450 K. The NTE properties and local vibration dynamics have been investigated by joint experiments of synchrotron X-ray diffraction, X-ray pair distribution function, and extended X-ray absorption fine structure spectroscopy. It has been observed that the Fe-C/Fe-N bonds expand with increasing temperature, while the unit cell shrinks in FeFe(CN)₆. The vibration directions of both Fe-C and Fe-N prefer to be perpendicular to the linkage of Fe-CN-Fe rather than being parallel. More pieces of evidence indicate that the transverse vibrations of N atoms dominate the NTE behavior of FeFe(CN)₆. The present results prove directly that the transverse thermal vibrations of C and N atoms are crucial for the occurrence of the NTE of Prussian blue analogues.

Original language	English
Pages (from-to)	3658-3663
Journal	Dalton Transactions
Volume	48
Issue number	11
DOIs	https://doi.org/10.1039/c8dt05111a
Publication status	Published - 21 Mar 2019
Externally published	Yes

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@article{e3d17b2a6b63456c80165b376161dd93,

title = "Negative thermal expansion in cubic FeFe(CN)6 Prussian blue analogues",

abstract = "Negative thermal expansion (NTE) behavior is an interesting physical phenomenon, but the number of NTE materials is limited. In this study, a new NTE compound has been found, FeFe(CN)6 Prussian blue analogue, where the average linear coefficient of thermal expansion (αl) is -4.260 × 10-6 K-1 between 100 and 450 K. The NTE properties and local vibration dynamics have been investigated by joint experiments of synchrotron X-ray diffraction, X-ray pair distribution function, and extended X-ray absorption fine structure spectroscopy. It has been observed that the Fe-C/Fe-N bonds expand with increasing temperature, while the unit cell shrinks in FeFe(CN)6. The vibration directions of both Fe-C and Fe-N prefer to be perpendicular to the linkage of Fe-CN-Fe rather than being parallel. More pieces of evidence indicate that the transverse vibrations of N atoms dominate the NTE behavior of FeFe(CN)6. The present results prove directly that the transverse thermal vibrations of C and N atoms are crucial for the occurrence of the NTE of Prussian blue analogues.",

author = "Naike Shi and Qilong Gao and Andrea Sanson and Qiang Li and Longlong Fan and Yang Ren and Luca Olivi and Jun Chen and Xianran Xing",

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T1 - Negative thermal expansion in cubic FeFe(CN)6 Prussian blue analogues

AU - Shi, Naike

AU - Gao, Qilong

AU - Sanson, Andrea

AU - Li, Qiang

AU - Fan, Longlong

AU - Ren, Yang

AU - Olivi, Luca

AU - Chen, Jun

AU - Xing, Xianran

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

PY - 2019/3/21

Y1 - 2019/3/21

N2 - Negative thermal expansion (NTE) behavior is an interesting physical phenomenon, but the number of NTE materials is limited. In this study, a new NTE compound has been found, FeFe(CN)6 Prussian blue analogue, where the average linear coefficient of thermal expansion (αl) is -4.260 × 10-6 K-1 between 100 and 450 K. The NTE properties and local vibration dynamics have been investigated by joint experiments of synchrotron X-ray diffraction, X-ray pair distribution function, and extended X-ray absorption fine structure spectroscopy. It has been observed that the Fe-C/Fe-N bonds expand with increasing temperature, while the unit cell shrinks in FeFe(CN)6. The vibration directions of both Fe-C and Fe-N prefer to be perpendicular to the linkage of Fe-CN-Fe rather than being parallel. More pieces of evidence indicate that the transverse vibrations of N atoms dominate the NTE behavior of FeFe(CN)6. The present results prove directly that the transverse thermal vibrations of C and N atoms are crucial for the occurrence of the NTE of Prussian blue analogues.

AB - Negative thermal expansion (NTE) behavior is an interesting physical phenomenon, but the number of NTE materials is limited. In this study, a new NTE compound has been found, FeFe(CN)6 Prussian blue analogue, where the average linear coefficient of thermal expansion (αl) is -4.260 × 10-6 K-1 between 100 and 450 K. The NTE properties and local vibration dynamics have been investigated by joint experiments of synchrotron X-ray diffraction, X-ray pair distribution function, and extended X-ray absorption fine structure spectroscopy. It has been observed that the Fe-C/Fe-N bonds expand with increasing temperature, while the unit cell shrinks in FeFe(CN)6. The vibration directions of both Fe-C and Fe-N prefer to be perpendicular to the linkage of Fe-CN-Fe rather than being parallel. More pieces of evidence indicate that the transverse vibrations of N atoms dominate the NTE behavior of FeFe(CN)6. The present results prove directly that the transverse thermal vibrations of C and N atoms are crucial for the occurrence of the NTE of Prussian blue analogues.

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