Research Abstract


Hydride ions in oxide hosts hidden by hydroxide ions

2014年3月24日 Nature Communications 5 : 3515 doi: 10.1038/ncomms4515


林 克郎1*, Peter V. Sushko2**, 橋本 康博3, Alexander L. Shluger2 & 細野 秀雄4

  1. 東京工業大学 応用セラミックス研究所 セキュアマテリアル研究センター
  2. ロンドン大学ユニバーシティカレッジ (英)
  3. 旭化成株式会社 新事業企画開発室
  4. 東京工業大学 フロンティア研究センター

    *現所属先:九州大学 応用化学部門

The true oxidation state of formally ‘H’ ions incorporated in an oxide host is frequently discussed in connection with chemical shifts of 1H nuclear magnetic resonance spectroscopy, as they can exhibit values typically attributed to H+. Here we systematically investigate the link between geometrical structure and chemical shift of H ions in an oxide host, mayenite, with a combination of experimental and ab initio approaches, in an attempt to resolve this issue. We demonstrate that the electron density near the hydrogen nucleus in an OH ion (formally H+ state) exceeds that in an H ion. This behaviour is the opposite to that expected from formal valences. We deduce a relationship between the chemical shift of H and the distance from the H ion to the coordinating electropositive cation. This relationship is pivotal for resolving H species that are masked by various states of H+ ions.