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Conduction Band Control of Oxyhalides with a Triple-Fluorite Layer for Visible Light Photocatalysis.

Authors
  • Nakada, Akinobu1, 2
  • Kato, Daichi1
  • Nelson, Ryky3
  • Takahira, Hikaru1
  • Yabuuchi, Masayoshi1
  • Higashi, Masanobu1
  • Suzuki, Hajime1
  • Kirsanova, Maria4
  • Kakudou, Naoji1
  • Tassel, Cédric1
  • Yamamoto, Takafumi1
  • Brown, Craig M5
  • Dronskowski, Richard3, 6
  • Saeki, Akinori7
  • Abakumov, Artem8
  • Kageyama, Hiroshi1, 9
  • Abe, Ryu1, 9
  • 1 Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan. , (Japan)
  • 2 PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan. , (Japan)
  • 3 Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52056 Aachen, Germany. , (Germany)
  • 4 Advanced Imaging Core Facility, Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russia.
  • 5 Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States. , (United States)
  • 6 Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, 7098 Liuxian Blvd, Nanshan District, Shenzhen, China. , (China)
  • 7 Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan. , (Japan)
  • 8 Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russia.
  • 9 CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan. , (Japan)
Type
Published Article
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Publication Date
Feb 17, 2021
Volume
143
Issue
6
Pages
2491–2499
Identifiers
DOI: 10.1021/jacs.0c10288
PMID: 33417448
Source
Medline
Language
English
License
Unknown

Abstract

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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