Why Do Carbonate Anions Have Extremely High Stability in the Interlayer Space of Layered Double Hydroxides? Case Study of Layered Double Hydroxide Consisting of Mg and Al (Mg/Al = 2)

Ryo Sasai; Hiroaki Sato; Mako Sugata; Takuya Fujimura; Shinsuke Ishihara; Kenzo Deguchi; Shinobu Ohki; Masataka Tansho; Tadashi Shimizu; Naoto Oita; Mako Numoto; Yasuhiro Fujii; Shogo Kawaguchi; Yoshiki Matsuoka; Koki Hagura; Tomohiro Abe; Chikako Moriyoshi

doi:10.1021/acs.inorgchem.9b01365

Why Do Carbonate Anions Have Extremely High Stability in the Interlayer Space of Layered Double Hydroxides? Case Study of Layered Double Hydroxide Consisting of Mg and Al (Mg/Al = 2)

Inorg Chem. 2019 Aug 19;58(16):10928-10935. doi: 10.1021/acs.inorgchem.9b01365. Epub 2019 Aug 8.

Authors

Ryo Sasai¹, Hiroaki Sato¹, Mako Sugata¹, Takuya Fujimura¹, Shinsuke Ishihara², Kenzo Deguchi³, Shinobu Ohki³, Masataka Tansho³, Tadashi Shimizu³, Naoto Oita⁴, Mako Numoto⁵, Yasuhiro Fujii^{4

5}, Shogo Kawaguchi⁶, Yoshiki Matsuoka⁷, Koki Hagura^{6

7}, Tomohiro Abe⁷, Chikako Moriyoshi⁷

Affiliations

¹ Department of Materials Chemistry, Graduate School of Natural Science and Technology , Shimane University , 1060 Nishi-Kawatsu-cho , Matsue , Shimane 690-8504 , Japan.
² World Premier International Center for Materials Nanoarchitectonics (WPI-MANA) , National Institute for Materials Science (NIMS) , 1-1 Namiki , Tsukuba , Ibaraki 305-0044 , Japan.
³ High Field NMR Group , National Institute for Materials Science (NIMS) , 3-13 Sakura , Tsukuba , Ibaraki 305-0003 , Japan.
⁴ Department of Physics and Mathematics, College of Science and Engineering , Aoyama Gakuin University , 5-10-1 Fuchinobe, Chuo-ku , Sagamihara , Kanagawa 252-5258 , Japan.
⁵ Department of Physical Sciences, College of Science and Engineering , Ritsumeikan University , 1-1-1 Noji-higashi , Kusatsu , Shiga 525-8577 , Japan.
⁶ Japan Synchrotron Radiation Research Institute (JASRI) , 1-1-1 Kouto, Sayo-Cho , Sayo-Gun , Hyogo 679-5198 , Japan.
⁷ Department of Physical Science, Graduate School of Science , Hiroshima University , 1-3-1 Kagamiyama , Higashi-Hiroshima , Hiroshima 739-8526 , Japan.

PMID: 31393726
DOI: 10.1021/acs.inorgchem.9b01365

Abstract

Layered double hydroxides (LDHs) are promising compounds in a wide range of fields. However, exchange of CO₃^2- anions with other anions is necessary, because the CO₃^2- anions are strongly affixed in the LDH interlayer space. To elucidate the reason for the extremely high stability of CO₃^2- anions intercalated in LDHs, we investigated in detail the chemical states of CO₃^2- anions and hydrated water molecules in the LDH interlayer space by synchrotron radiation X-ray diffraction, solid-state NMR spectroscopy, and Raman spectroscopy. We found the rigidity of the network structure formed between the CO₃^2- anions, hydrated water molecules, and the hydroxyl groups on the metal hydroxide layer surface to be a crucial factor underlying the stability of CO₃^2- anions in the LDH interlayer space.