Tomofumi Tada, Susumu Kitagawa, Aude Demessence, Satoshi Horike
https://pubs.rsc.org/en/Content/ArticleLanding/2020/SC/C9SC05757A#!divAbstract
Design and synthesis of solid-state ion conductors have been challenging toward various electrochemistry applications. The ion conductivity of representative inorganic solids is often dominated by the lattice vibration in terahertz region. As a new family of ion conductors, metal-organic frameworks (MOFs) are promising due to their compositional diversity and structural dynamics. Many ion-conductive MOFs have been synthesized, whereas the correlation of ion conductivity and lattice vibration of MOFs is not investigated. Here we studied the relation between proton (H+) conductivity and terahertz-regime vibrations of two-dimensional MOFs. We studied three isostructural MOFs having different divalent metal ions, and the spectroscopies clarified that the collective motion in terahertz region in 2D layers plays an essential role for efficient H+ conduction. Ab-initio calculations suggest the collective motion is dominated by the valence electronic structure depending on metal ions.
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