Conduction Band Control of Oxyhalides with a Triple-Fluorite Layer for Visible Light Photocatalysis,Journal of the American Chemical Society

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Conduction Band Control of Oxyhalides with a Triple-Fluorite Layer for Visible Light Photocatalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-01-08 , DOI: 10.1021/jacs.0c10288
Akinobu Nakada _{1,

2} , Daichi Kato ₁ , Ryky Nelson ₃ , Hikaru Takahira ₁ , Masayoshi Yabuuchi ₁ , Masanobu Higashi ₁ , Hajime Suzuki ₁ , Maria Kirsanova ₄ , Naoji Kakudou ₁ , Cédric Tassel ₁ , Takafumi Yamamoto ₁ , Craig M. Brown ₅ , Richard Dronskowski _{3,

6} , Akinori Saeki ₇ , Artem Abakumov ₈ , Hiroshi Kageyama _{1,

9} , Ryu Abe _{1,

9}

Affiliation

Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52056 Aachen, Germany
Advanced Imaging Core Facility, Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russia
Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, 7098 Liuxian Blvd, Nanshan District, Shenzhen, China
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russia
CREST, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan

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.

中文翻译：

用于可见光光催化的具有三重萤石层的卤氧化物的导带控制

积木的发现为开发和控制扩展固体的特性提供了新的机会。具有萤石型 Bi2O2 块的化合物具有各种特性，包括无铅铁电体和光催化剂。在这项研究中，我们表明与双层 Bi2O2 块不同，Bi2MO4Cl 中的三层 Bi2MO4 块（M = Bi、La、Y）可以广泛地控制导带。根据 M，Bi2MO4 块被 Bi-O 键断裂截断，导致一系列 n 字形链结构（对于 M = Bi、La、Y 分别为 n = 1、2、∞）。因此，形成的链结构导致导带最小值的变化（-0.36 至 -0.94 V vs SHE），这与 Bi 处是否存在镜像对称相关。Bi2YO4Cl 显示出比最有效的 Bi2O2 基光催化剂更高的光电导率，具有良好的可见光光催化分解水的活性。这项研究扩展了增厚（2D 到 3D）和切割（2D 到 1D）萤石基块的可能性，以实现所需的光催化和其他功能。

更新日期：2021-01-08

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