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

Journal Article · Tue Nov 15 00:00:00 EST 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.08.030· OSTI ID:21580049

Adak, Sourav ^[1]; Daemen, Luke L; Hartl, Monika ^[2]; Williams, Darrick ^[3]; Summerhill, Jennifer ^[4]; Nakotte, Heinz ^[1]

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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)

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.

• OSTI ID: 21580049
• Journal Information: Journal of Solid State Chemistry, Vol. 184, 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.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

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