日本京都大学Ryu Abe研究团队揭示了用于用于可见光催化三重结构萤石氧卤的导带调控机制。 相关研究成果于2021年1月8日发表在《美国化学会志》。

结构单元的发现为发展和调控固体材料的性质提供了新的机会。萤石型Bi2O2嵌段的化合物具有各种性质，包括无铅铁电和光催化性质。

在该项研究中，研究人员发现Bi2MO4Cl中的三层Bi2MO4块（M=Bi，La，Y）与双层Bi2O2块不同，允许广泛控制导带。根据M，Bi2MO4嵌段被Bi–O键断裂截断，产生一系列n字形链结构（M=Bi，La，Y分别为n=1，2，∞）。因此，形成的链结构是导带最小值（0.36到0.94 V vs SHE）变化的原因，这与Bi处是否存在镜像对称性有关。Bi2YO4Cl比最有效的Bi2O2基光催化剂具有更高的光导率，具有良好的可见光催化分解水的活性。

该研究扩展了增稠（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。

附：英文原文

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

Author: Akinobu Nakada, Daichi Kato, Ryky Nelson, Hikaru Takahira, Masayoshi Yabuuchi, Masanobu Higashi, Hajime Suzuki, Maria Kirsanova, Naoji Kakudou, Cédric Tassel, Takafumi Yamamoto, Craig M. Brown, Richard Dronskowski, Akinori Saeki, Artem Abakumov, Hiroshi Kageyama, Ryu Abe

Issue&Volume: January 8, 2021

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.

DOI: 10.1021/jacs.0c10288

Source: https://pubs.acs.org/doi/10.1021/jacs.0c10288