Valence Band Engineering of Layered Bismuth Oxyhalides toward Stable Visible-Light Water Splitting: Madelung Site Potential Analysis

被引：172

作者：

Kato, Daichi ^{[1
]}

Hongo, Kenta ^{[2
,3
,4
]}

Maezono, Ryo ^{[2
]}

Higashi, Masanobu ^{[1
]}

Kunioku, Hironobu ^{[1
]}

Yabuuchi, Masayoshi ^{[1
]}

Suzuki, Hajime ^{[1
]}

Okajima, Hiroyuki ^{[1
]}

Zhong, Chengchao ^{[1
]}

Nakano, Kousuke ^{[2
]}

Abe, Ryu ^{[1
,5
]}

Kageyama, Hiroshi ^{[1
,5
]}

机构：

[1] Kyoto Univ, Grad Sch Engn, Dept Energy & Hydrocarbon Chem, Nishikyo Ku, Kyoto 6158510, Japan

[2] JAIST, Res Ctr Adv Comp Infrastruct, Asahidai 1-1, Nomi, Ishikawa 9231292, Japan

[3] Natl Inst Mat Sci, Ctr Mat Res Informat Integrat CMI2, 1-2-1 Sengen, Tsukuba, Ibaraki 3050047, Japan

[4] Japan Sci & Technol Agcy JST, PRESTO, Kawaguchi, Saitama 3320012, Japan

[5] Japan Sci & Technol Agcy JST, CREST, Kawaguchi, Saitama 3320012, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 51期

关键词：

OXYNITRIDE TAON PHOTOANODE; ELECTRONIC-STRUCTURE; PEROVSKITE; PHOTOCATALYST; OXIDES; EFFICIENT; OXYGEN; IRRADIATION; FABRICATION; BI4NBO8CL;

D O I：

10.1021/jacs.7b11497

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A layered oxychloride Bi4NbO8Cl is a visible-light responsive catalyst for water splitting, with its remarkable stability ascribed to the highly dispersive O-2p orbitals in the valence band, the origin of which, however, remains unclear. Here, we systematically investigate four series of layered bismuth oxyhalides, BiOX (X = Cl, Br, I), Bi4NbO8X (X = Cl, Br), Bi2GdO4X (X = Cl, Br), and SrBiO2X (X = Cl, Br, I), and found that Madelung site potentials of anions capture essential features of the valence band structures of these materials. The oxide anion in fluorite-like blocks (e.g., [Bi2O2] slab in Bi4NbO8Cl) is responsible for the upward shift of the valence band, and the degree of electrostatic destabilization changes depending on building layers and their stacking sequence. This study suggests that the Madelung analysis enables a prediction and design of the valence band structures of bismuth and other layered oxyhalides and is applicable even to a compound where DFT calculation is difficult to perform.

引用

页码：18725 / 18731

页数：7