Hydride in BaTiO2.5H0.5: A Labile Ligand in Solid State Chemistry

Naoya Masuda, Yoji Kobayashi, Olivier Hernandez, Thierry Bataille, Serge Paofai, Hajime Suzuki, Clemens Ritter, Naoki Ichijo, Yasuto Noda, Kiyonori Takegoshi, Cédric Tassel, Takafumi Yamamoto, Hiroshi Kageyama

Research output: Contribution to journalArticlepeer-review

52 Scopus citations

Abstract

In synthesizing mixed anion oxides, direct syntheses have often been employed, usually involving high temperature and occasionally high pressure. Compared with these methods, here we show how the use of a titanium perovskite oxyhydride (BaTiO2.5H0.5) as a starting material enables new multistep low temperature topochemical routes to access mixed anion compounds. Similar to labile ligands in inorganic complexes, the lability of H- provides the necessary reactivity for syntheses, leading to reactions and products previously difficult to obtain. For example, BaTiO2.5N0.2 can be prepared with the otherwise inert N2 gas at 400-600 °C, in marked contrast with currently available oxynitride synthetic routes. F-/H- exchange can also be accomplished at 150 °C, yielding the oxyhydride-fluoride BaTi(O, H, F)3. For BaTiO2.4D0.3F0.3, we find evidence that further anionic exchange with OD- yields BaTiO2.4(D-)0.26(OD-)0.34, which implies stable coexistence of H+ and H- at ambient conditions. Such an arrangement is thermodynamically unstable and would be difficult to realize otherwise. These results show that the labile nature of hydride imparts reactivity to oxide hosts, enabling it to participate in new multistep reactions and form new materials.
Original languageEnglish (US)
Pages (from-to)15315-15321
Number of pages7
JournalJournal of the American Chemical Society
Volume137
Issue number48
DOIs
StatePublished - Dec 9 2015
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • Chemistry(all)
  • Catalysis

Fingerprint

Dive into the research topics of 'Hydride in BaTiO2.5H0.5: A Labile Ligand in Solid State Chemistry'. Together they form a unique fingerprint.

Cite this