Gas phase contributions to topochemical hydride reduction reactions

Year: 2013 DOI: 10.1016/j.jssc.2013.09.006

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Yoji Kobayashi, Zhaofei Li, Kei Hirai, Cédric Tassel, François Loyer, Noriya Ichikawa, Naoyuki Abe, Takafumi Yamamoto, Yuichi Shimakawa, Kazuyoshi Yoshimura, Olivier J. Hernandez, Mikio Takano, Hiroshi Kageyama.   Journal of Solid State Chemistry, 2013, 207, 190-193.


Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H2 and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures.