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Title: Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN) 6 Prussian Blue Analogues

Abstract

Here, the understanding of the negative thermal expansion (NTE) mechanism is vital not only for the development of new NTE compounds but also for effectively controlling thermal expansion. Here, we report an interesting isotropic NTE property in cubic GaFe(CN) 6 Prussian blue analogues (α l = –3.95 × 10 –6 K –1, 100–475 K), which is a new example to understand the complex NTE mechanism. A combined study of synchrotron X-ray diffraction, X-ray total scattering, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations shows that the NTE of GaFe(CN)6 originates from the low-frequency phonons (< ~100 cm –1), which are directly related to the transverse vibrations of the atomic –Ga–N≡C–Fe– chains. Both the Ga–N and Fe–C chemical bonds are much softer to bend than to stretch. The direct evidence that transverse vibrational contribution to the NTE of GaFe(CN) 6 is dominated by N, instead of C atoms, is illustrated. It is interesting to find that the polyhedra of GaFe(CN) 6 are not rigid, which is a starting assumption in some models describing the NTE properties of other systems. The NTE mechanism can be vividly described by the “guitar-string” effect, which would be the common feature formore » the NTE property of many open-framework functional materials, such as Prussian blue analogues, oxides, cyanides, metal–organic frameworks, and zeolites.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [3];  [1];  [4];  [4];  [5]; ORCiD logo [1];  [1]
  1. Univ. of Science and Technology Beijing, Beijing (China)
  2. Zhengzhou Univ., Zhengzhou (China)
  3. Univ. of Padova, Padova (Italy)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1472117
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gao, Qilong, Shi, Naike, Sun, Qiang, Sanson, Andrea, Milazzo, Ruggero, Carnera, Alberto, Zhu, He, Lapidus, Saul H., Ren, Yang, Huang, Qingzhen, Chen, Jun, and Xing, Xianran. Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN)6 Prussian Blue Analogues. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01526.
Gao, Qilong, Shi, Naike, Sun, Qiang, Sanson, Andrea, Milazzo, Ruggero, Carnera, Alberto, Zhu, He, Lapidus, Saul H., Ren, Yang, Huang, Qingzhen, Chen, Jun, & Xing, Xianran. Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN)6 Prussian Blue Analogues. United States. https://doi.org/10.1021/acs.inorgchem.8b01526
Gao, Qilong, Shi, Naike, Sun, Qiang, Sanson, Andrea, Milazzo, Ruggero, Carnera, Alberto, Zhu, He, Lapidus, Saul H., Ren, Yang, Huang, Qingzhen, Chen, Jun, and Xing, Xianran. Tue . "Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN)6 Prussian Blue Analogues". United States. https://doi.org/10.1021/acs.inorgchem.8b01526. https://www.osti.gov/servlets/purl/1472117.
@article{osti_1472117,
title = {Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN)6 Prussian Blue Analogues},
author = {Gao, Qilong and Shi, Naike and Sun, Qiang and Sanson, Andrea and Milazzo, Ruggero and Carnera, Alberto and Zhu, He and Lapidus, Saul H. and Ren, Yang and Huang, Qingzhen and Chen, Jun and Xing, Xianran},
abstractNote = {Here, the understanding of the negative thermal expansion (NTE) mechanism is vital not only for the development of new NTE compounds but also for effectively controlling thermal expansion. Here, we report an interesting isotropic NTE property in cubic GaFe(CN)6 Prussian blue analogues (αl = –3.95 × 10–6 K–1, 100–475 K), which is a new example to understand the complex NTE mechanism. A combined study of synchrotron X-ray diffraction, X-ray total scattering, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations shows that the NTE of GaFe(CN)6 originates from the low-frequency phonons (< ~100 cm–1), which are directly related to the transverse vibrations of the atomic –Ga–N≡C–Fe– chains. Both the Ga–N and Fe–C chemical bonds are much softer to bend than to stretch. The direct evidence that transverse vibrational contribution to the NTE of GaFe(CN)6 is dominated by N, instead of C atoms, is illustrated. It is interesting to find that the polyhedra of GaFe(CN)6 are not rigid, which is a starting assumption in some models describing the NTE properties of other systems. The NTE mechanism can be vividly described by the “guitar-string” effect, which would be the common feature for the NTE property of many open-framework functional materials, such as Prussian blue analogues, oxides, cyanides, metal–organic frameworks, and zeolites.},
doi = {10.1021/acs.inorgchem.8b01526},
url = {https://www.osti.gov/biblio/1472117}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

Perovskite-related ReO3-type structures
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Negative thermal expansion in cubic FeFe(CN) 6 Prussian blue analogues
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Negative thermal expansion behavior in orthorhombic Sc 2 (MoO 4 ) 3 and Sc 2 (WO 4 ) 3
journal, September 2019