Double-hole codoped huge-gap semiconductor ZrO2 for visible-light photocatalysis.
Double-hole doping is an effective approach to engineer the band structures of semiconductors for enhancing the photoelectrochemical performance. Here, we explore the anionic monodoping (i.e. N, C, and P) and codoping (i.e. N + N, C + S, and N + P pairs) effects on the electronic structures and photocatalytic activities of ZrO2 by performing extensive density functional theory calculations. Upon anionic monodoping, several unoccupied impurity states appear within the band gap, which may trap the photogenerated carriers and then reduce the photocatalytic efficiency. Remarkably, double-hole doping via introducing three anionic (N + N), (C + S), and (N + P) codoping pairs in ZrO2 can not only effectively narrow the band gap, but can also create several fully filled delocalized intermediate bands for preventing the recombination of the photogenerated electron-hole pairs. Moreover, the band edge positions matching well with the redox potentials of water and the improved visible light absorption ability indicate that the three examined codoped ZrO2 systems are promising photocatalysts for visible light water splitting. In short, double-hole doping via anionic pairs provides an effective path to tune the huge-gap semiconductor band structures and to develop high efficient catalysts for solar-driven water splitting.
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Materials Chemistry, Ministry of Education, College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
Jiajun
J
Wang
School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei, Anhui 230601, China. jhuang@ustc.edu.cn and Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. liqun@ustc.edu.cn.
Jing
J
Huang
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. liqun@ustc.edu.cn.
Jie
J
Meng
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. liqun@ustc.edu.cn.
Qunxiang
Q
Li
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. liqun@ustc.edu.cn.
Jinlong
J
Yang