Thermal expansion in 3d-metal Prussian Blue Analogs—A survey study |
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| Authors: | Sourav Adak Luke L Daemen Monika Hartl Darrick Williams Jennifer Summerhill Heinz Nakotte |
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| Institution: | aDepartment of Physics, New Mexico State University, Las Cruces, NM 88003, USA;bLos Alamos Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545, USA;cCenter for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM 87545, USA;dDepartment of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM 88003, USA |
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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 MII3(M′)III(CN)6]2·nH2O and MII2FeII(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 Fm3?m, F4?3m and Pm3?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 39.7×10−6 K−1 for Co3Co(CN)6]2·12H2O. All of the MII3CoIII(CN)6]2·nH2O 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 MII3FeIII(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 MII2FeII(CN)6]·nH2O compounds show positive thermal expansion behavior. |
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| Keywords: | Prussian Blue Analogs Negative thermal expansion Crystal structures |
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