Thermal Expansion in 3$d$-Metal Prussian Blue Analogs -- A Survey Study

ORAL

Abstract

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions $M^{II}_{3}[(M')^{III}$\textit{(CN)}$_{6}]_{2}$\textit{.nH}$_{2}O$ and $M^{II}_{2}$\textit{[Fe}$^{II}$\textit{(CN)}$_{6}$\textit{].nH}$_{2}O$, where $M^{II}$\textit{ = Mn, Fe, Co, Ni, Cu} and \textit{Zn}, $(M')^{III}$\textit{ = Co, Fe} and $n$ = 5 to 18. Temperature-dependent X-ray diffraction studies were performed in the temperature range between -150$^{o}$C (123 K) and room temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups$Fm\overline 3 m$, $F\overline 4 3m$ and$Pm\overline 3 m$. 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 x 10$^{-6}$ K$^{-1}$ for \textit{Co}$_{3}$\textit{[Co(CN)}$_{6}]_{2.}12H_{2}O$. All of the $M^{II}_{3}$\textit{[Co}$^{III}$\textit{(CN)}$_{6}]_{2}$\textit{.nH}$_{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 $M^{II}_{3}$\textit{[Fe}$^{III}$\textit{(CN)}$_{6}]_{2}$\textit{.nH}$_{2}O$ family are found to switch between positive (for \textit{M = Mn, Co, Ni}) and negative (\textit{M = Cu, Zn}) behavior, depending on the choice of the metal cation ($M)$. On the other hand, all of the $M^{II}_{2}$\textit{[Fe}$^{II}$\textit{(CN)}$_{6}$\textit{].nH}$_{2}O$ compounds show positive thermal expansion behavior.

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Authors

  • Sourav Adak

    NMSU

  • Young-Yeal Song

    Brigham Young University, Colorado School of Mines, Colorado State University, Yale University, Department of Physics and Astronomy, Brigham Young University, Department of Mechanical Engineering, University of Utah, JILA, NIST and University of Colorado, University of Arizona, MIT, National Institute for Materials Science, Japan, Department of Mechanical Engineering, Brigham Young University, University of New Mexico, Iowa State University, Los Alamos National Lab XCP-2, Utah State University, Weber State University, New Mexico State University, College of Optical Science, University of Arizona, University of Nebraska, Lincoln, J.A. Woollam Co., U.S. Naval Research Laboratory, Arizona State University, BYU Nuclear Physics Group, Brigham Young University Physics and Astronomy, Los Alamos National Laboratory, University of Tsukuba, Japan, Colorado State University, NSF ERC for EUV science and technology, Center for Functional Nanomaterials, Brookhaven National Laboratory, University of Wisconsin, Madison, Utah Valley University, Argonne National Lab

  • Young-Yeal Song

    Brigham Young University, Colorado School of Mines, Colorado State University, Yale University, Department of Physics and Astronomy, Brigham Young University, Department of Mechanical Engineering, University of Utah, JILA, NIST and University of Colorado, University of Arizona, MIT, National Institute for Materials Science, Japan, Department of Mechanical Engineering, Brigham Young University, University of New Mexico, Iowa State University, Los Alamos National Lab XCP-2, Utah State University, Weber State University, New Mexico State University, College of Optical Science, University of Arizona, University of Nebraska, Lincoln, J.A. Woollam Co., U.S. Naval Research Laboratory, Arizona State University, BYU Nuclear Physics Group, Brigham Young University Physics and Astronomy, Los Alamos National Laboratory, University of Tsukuba, Japan, Colorado State University, NSF ERC for EUV science and technology, Center for Functional Nanomaterials, Brookhaven National Laboratory, University of Wisconsin, Madison, Utah Valley University, Argonne National Lab

  • Young-Yeal Song

    Brigham Young University, Colorado School of Mines, Colorado State University, Yale University, Department of Physics and Astronomy, Brigham Young University, Department of Mechanical Engineering, University of Utah, JILA, NIST and University of Colorado, University of Arizona, MIT, National Institute for Materials Science, Japan, Department of Mechanical Engineering, Brigham Young University, University of New Mexico, Iowa State University, Los Alamos National Lab XCP-2, Utah State University, Weber State University, New Mexico State University, College of Optical Science, University of Arizona, University of Nebraska, Lincoln, J.A. Woollam Co., U.S. Naval Research Laboratory, Arizona State University, BYU Nuclear Physics Group, Brigham Young University Physics and Astronomy, Los Alamos National Laboratory, University of Tsukuba, Japan, Colorado State University, NSF ERC for EUV science and technology, Center for Functional Nanomaterials, Brookhaven National Laboratory, University of Wisconsin, Madison, Utah Valley University, Argonne National Lab

  • Young-Yeal Song

    Brigham Young University, Colorado School of Mines, Colorado State University, Yale University, Department of Physics and Astronomy, Brigham Young University, Department of Mechanical Engineering, University of Utah, JILA, NIST and University of Colorado, University of Arizona, MIT, National Institute for Materials Science, Japan, Department of Mechanical Engineering, Brigham Young University, University of New Mexico, Iowa State University, Los Alamos National Lab XCP-2, Utah State University, Weber State University, New Mexico State University, College of Optical Science, University of Arizona, University of Nebraska, Lincoln, J.A. Woollam Co., U.S. Naval Research Laboratory, Arizona State University, BYU Nuclear Physics Group, Brigham Young University Physics and Astronomy, Los Alamos National Laboratory, University of Tsukuba, Japan, Colorado State University, NSF ERC for EUV science and technology, Center for Functional Nanomaterials, Brookhaven National Laboratory, University of Wisconsin, Madison, Utah Valley University, Argonne National Lab

  • Young-Yeal Song

    Brigham Young University, Colorado School of Mines, Colorado State University, Yale University, Department of Physics and Astronomy, Brigham Young University, Department of Mechanical Engineering, University of Utah, JILA, NIST and University of Colorado, University of Arizona, MIT, National Institute for Materials Science, Japan, Department of Mechanical Engineering, Brigham Young University, University of New Mexico, Iowa State University, Los Alamos National Lab XCP-2, Utah State University, Weber State University, New Mexico State University, College of Optical Science, University of Arizona, University of Nebraska, Lincoln, J.A. Woollam Co., U.S. Naval Research Laboratory, Arizona State University, BYU Nuclear Physics Group, Brigham Young University Physics and Astronomy, Los Alamos National Laboratory, University of Tsukuba, Japan, Colorado State University, NSF ERC for EUV science and technology, Center for Functional Nanomaterials, Brookhaven National Laboratory, University of Wisconsin, Madison, Utah Valley University, Argonne National Lab