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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 M{sup II}{sub 3}[(M'){sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O and M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O, where M{sup II}=Mn, Fe, Co, Ni, Cu and Zn, (M'){sup 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 deg. C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3-bar m, F4-bar 3m and Pm3-bar m. 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 39.7x{sup 1}0{sup -6} K{sup -1} for Co{sub 3}[Co(CN){sub 6}]{sub 2}.12H{sub 2}O. All of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O compounds show negative thermal expansion behavior, which correlates with the Irving-Williams series for metal complex stability.more » The thermal expansion behavior for the PBAs of the M{sup II}{sub 3}[Fe{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O 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{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O compounds show positive thermal expansion behavior. - Graphical Abstract: The structure of Prussian Blue analogs (PBAs) consists of two types of metal centered octahedral units connected by cyanide ligand. Lattice and interstitial water molecules are present in these framework structures. All the PBAs of the M{sub 3}[Co(CN){sub 6}]{sub 2}.nH{sub 2}O family show negative thermal expansion (NTE) behavior. The lattice parameters and magnitude of NTE correlates inversely with the Irving-Williams series of metal complex stability. Highlights: > Thermal expansion behavior of 17 Prussian Blue Analogs has been studied via XRD. > Nine compounds display negative thermal expansion (NTE) behavior. > All compounds of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} family exhibit NTE behavior. > Magnitude of the NTE in M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} follows the order Mn>Fe>Co>Ni>Cu<Zn. > NTE materials show correlations with lattice parameters and Irving-Williams series.« less

Authors:
 [1]; ;  [2];  [3];  [4];  [1]
  1. Department of Physics, New Mexico State University, Las Cruces, NM 88003 (United States)
  2. Los Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)
  3. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)
  4. Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM 88003 (United States)
Publication Date:
OSTI Identifier:
21580049
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 184; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2011.08.030; PII: S0022-4596(11)00470-1; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CUBIC LATTICES; CYANIDES; FERROCYANIDES; INTERSTITIAL WATER; LATTICE PARAMETERS; LIGANDS; METALS; POTASSIUM COMPOUNDS; SPACE GROUPS; STABILITY; TEMPERATURE DEPENDENCE; THERMAL EXPANSION; X-RAY DIFFRACTION; ALKALI METAL COMPOUNDS; COHERENT SCATTERING; COMPLEXES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; ELEMENTS; EXPANSION; GROUND WATER; HYDROGEN COMPOUNDS; IRON COMPLEXES; OXYGEN COMPOUNDS; SCATTERING; SYMMETRY GROUPS; TRANSITION ELEMENT COMPLEXES; WATER

Citation Formats

Adak, Sourav, Los Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545, Daemen, Luke L, Hartl, Monika, Williams, Darrick, Summerhill, Jennifer, and Nakotte, Heinz. Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study. United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.08.030.
Adak, Sourav, Los Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545, Daemen, Luke L, Hartl, Monika, Williams, Darrick, Summerhill, Jennifer, & Nakotte, Heinz. Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study. United States. doi:10.1016/j.jssc.2011.08.030.
Adak, Sourav, Los Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545, Daemen, Luke L, Hartl, Monika, Williams, Darrick, Summerhill, Jennifer, and Nakotte, Heinz. Tue . "Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study". United States. doi:10.1016/j.jssc.2011.08.030.
@article{osti_21580049,
title = {Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study},
author = {Adak, Sourav and Los Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545 and Daemen, Luke L and Hartl, Monika and Williams, Darrick and Summerhill, Jennifer and Nakotte, Heinz},
abstractNote = {We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M{sup II}{sub 3}[(M'){sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O and M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O, where M{sup II}=Mn, Fe, Co, Ni, Cu and Zn, (M'){sup 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 deg. C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3-bar m, F4-bar 3m and Pm3-bar m. 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 39.7x{sup 1}0{sup -6} K{sup -1} for Co{sub 3}[Co(CN){sub 6}]{sub 2}.12H{sub 2}O. All of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O compounds show negative thermal expansion behavior, which correlates with the Irving-Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M{sup II}{sub 3}[Fe{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O 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{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O compounds show positive thermal expansion behavior. - Graphical Abstract: The structure of Prussian Blue analogs (PBAs) consists of two types of metal centered octahedral units connected by cyanide ligand. Lattice and interstitial water molecules are present in these framework structures. All the PBAs of the M{sub 3}[Co(CN){sub 6}]{sub 2}.nH{sub 2}O family show negative thermal expansion (NTE) behavior. The lattice parameters and magnitude of NTE correlates inversely with the Irving-Williams series of metal complex stability. Highlights: > Thermal expansion behavior of 17 Prussian Blue Analogs has been studied via XRD. > Nine compounds display negative thermal expansion (NTE) behavior. > All compounds of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} family exhibit NTE behavior. > Magnitude of the NTE in M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} follows the order Mn>Fe>Co>Ni>Cu<Zn. > NTE materials show correlations with lattice parameters and Irving-Williams series.},
doi = {10.1016/j.jssc.2011.08.030},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 11,
volume = 184,
place = {United States},
year = {2011},
month = {11}
}