Conduction Band Control of Oxyhalides with a Triple-Fluorite Layer for Visible Light Photocatalysis
2021
Nakada, Akinobu | Katō, Daichi | Nelson, Ryky | Takahira, Hikaru | Yabuuchi, Masayoshi | Higashi, Masanobu | Suzuki, Hajime | Kirsanova, Maria | Kakudou, Naoji | Tassel, Cédric | Yamamoto, Takafumi | Brown, Craig M. | Dronskowski, Richard | Saeki, Akinori | Abakumov, Artem | Kageyama, Hiroshi | Abe, Ryu
The discovery of building blocks offers new opportunities to develop and control properties of extended solids. Compounds with fluorite-type Bi₂O₂ blocks host various properties including lead-free ferroelectrics and photocatalysts. In this study, we show that triple-layered Bi₂MO₄ blocks (M = Bi, La, Y) in Bi₂MO₄Cl allow, unlike double-layered Bi₂O₂ blocks, to extensively control the conduction band. Depending on M, the Bi₂MO₄ block is truncated by Bi–O bond breaking, resulting in a series of n-zigzag chain structures (n = 1, 2, ∞ for M = Bi, La, Y, respectively). Thus, formed chain structures are responsible for the variation in the conduction band minimum (−0.36 to −0.94 V vs SHE), which is correlated to the presence or absence of mirror symmetry at Bi. Bi₂YO₄Cl shows higher photoconductivity than the most efficient Bi₂O₂-based photocatalyst with promising visible-light photocatalytic activity for water splitting. This study expands the possibilities of thickening (2D to 3D) and cutting (2D to 1D) fluorite-based blocks toward desired photocatalysis and other functions.
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