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Proton Conduction Study on Water Confined in Channel or Layer Networks of La<sup>III</sup>M<sup>III</sup>(ox)<sub>3</sub>·10H<sub>2</sub>O (M = Cr, Co, Ru, La)

By Hisashi O̅kawa (1536268), Masaaki Sadakiyo (1536262), Kazuya Otsubo (1455952), Ko Yoneda (1536265), Teppei Yamada (480111), Masaaki Ohba (1536271) and Hiroshi Kitagawa (190936)


Proton conduction of the La<sup>III</sup>M<sup>III</sup> compounds, LaM­(ox)<sub>3</sub>·10H<sub>2</sub>O (abbreviated to <b>LaM</b>; M = Cr, Co, Ru, La; ox<sup>2–</sup> = oxalate) is studied in view of their networks. <b>LaCr</b> and <b>LaCo</b> have a ladder structure, and the ladders are woven to form a channel network. <b>LaRu</b> and <b>LaLa</b> have a honeycomb sheet structure, and the sheets are combined to form a layer network. The occurrence of these structures is explained by the rigidness versus flexibility of [M­(ox)<sub>3</sub>]<sup>3–</sup> in the framework with large La<sup>III</sup>. The channel networks of <b>LaCr</b> and <b>LaCo</b> show a remarkably high proton conductivity, in the range from 1 × 10<sup>–6</sup> to 1 × 10<sup>–5</sup> S cm<sup>–1</sup> over 40–95% relative humidity (RH) at 298 K, whereas the layer networks of <b>LaCr</b> and <b>LaCo</b> show a lower proton conductivity, ∼3 × 10<sup>–8</sup> S cm<sup>–1</sup> (40–95% RH, 298 K). Activation energy measurements demonstrate that the channels filled with water molecules serve as efficient pathways for proton transport. <b>LaCo</b> was gradually converted to La<sup>III</sup>Co<sup>II</sup>(ox)<sub>2.5</sub>·4H<sub>2</sub>O, which had no channel structure and exhibited a low proton conductivity of less than 1 × 10<sup>–10</sup> S cm<sup>–1</sup>. The conduction–network correlation of LaCo­(ox)<sub>2.5</sub>·4H<sub>2</sub>O is reported

Topics: Biophysics, Biochemistry, Cell Biology, Genetics, Molecular Biology, Cancer, Science Policy, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, Ru, conduction, RH, honeycomb sheet structure, LaIIIMIII, cm, Proton Conduction Study, LaCo show, Cr, LaM, proton conductivity, 298 K, Activation energy measurements, ladder, LaCr
Year: 2015
DOI identifier: 10.1021/acs.inorgchem.5b01176.s003
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Provided by: FigShare
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