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Title: Insulating titanium oxynitride for visible light photocatalysis

Abstract

We propose insulating titanium oxynitrides Ti n N 2 O 2 n − 3 as promising water-splitting photocatalytic materials in the visible light range. Using first-principles many-body perturbation theory based on the GW approximation, we show that corundum-type Ti 2 N 2 O (an example Ti n N 2 O 2 n − 3 compound with n = 2 ) has a smaller band gap of about 2.5 eV, which is more suitable to absorb visible light, compared to other Ti-based oxides such as TiO 2 and SrTiO 3 with a band gap of more than 3 eV. Band-gap reduction in Ti 2 N 2 O is caused by an upward shift of the valence band (negative shift to the oxidation potential of H 2 O to O 2 ) due to the presence of nitrogen 2 p states. The conduction band is dominated by Ti 3 d states and the conduction-band minimum is nearly unchanged. As a result, the band-edge potentials of Ti 2 N 2 O are better aligned to the water reduction and oxidation levels. Our theoretical predictions provide useful insights for the discovery of efficient visible-light-driven photocatalysts for water splitting.

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [6]
  1. Tokyo Inst. of Technology (Japan). Dept. of Physics; Tokyo Inst. of Technology (Japan). International Education and Research Center of Science; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  2. Univ. of Texas, Austin, TX (United States). Center for Computational Materials, Inst. for Computational Engineering and Sciences
  3. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Riverside, CA (United States). Dept. of Mechanical Engineering, Materials Science and Engineering
  4. Univ. of Texas, Austin, TX (United States). Center for Computational Materials, Inst. for Computational Engineering and Sciences; Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering; Univ. of Texas, Austin, TX (United States). Dept. of Physics
  5. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  6. Tokyo Inst. of Technology (Japan). Dept. of Physics; Tokyo Inst. of Technology (Japan). Advanced Research Center for Quantum Physics and Nanoscience; Tokyo Inst. of Technology (Japan). Materials Research Center for Element Strategy
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1542456
DOE Contract Number:  
AC02-05CH11231; FG02-06ER46286
Resource Type:
Journal Article
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 99; Journal Issue: 7; Journal ID: ISSN 2469-9950
Country of Publication:
United States
Language:
English

Citation Formats

Aoki, Yuta, Sakurai, Masahiro, Coh, Sinisa, Chelikowsky, James R., Louie, Steven G., Cohen, Marvin L., and Saito, Susumu. Insulating titanium oxynitride for visible light photocatalysis. United States: N. p., 2019. Web. doi:10.1103/PhysRevB.99.075203.
Aoki, Yuta, Sakurai, Masahiro, Coh, Sinisa, Chelikowsky, James R., Louie, Steven G., Cohen, Marvin L., & Saito, Susumu. Insulating titanium oxynitride for visible light photocatalysis. United States. doi:10.1103/PhysRevB.99.075203.
Aoki, Yuta, Sakurai, Masahiro, Coh, Sinisa, Chelikowsky, James R., Louie, Steven G., Cohen, Marvin L., and Saito, Susumu. Fri . "Insulating titanium oxynitride for visible light photocatalysis". United States. doi:10.1103/PhysRevB.99.075203.
@article{osti_1542456,
title = {Insulating titanium oxynitride for visible light photocatalysis},
author = {Aoki, Yuta and Sakurai, Masahiro and Coh, Sinisa and Chelikowsky, James R. and Louie, Steven G. and Cohen, Marvin L. and Saito, Susumu},
abstractNote = {We propose insulating titanium oxynitrides Ti n N 2 O 2 n − 3 as promising water-splitting photocatalytic materials in the visible light range. Using first-principles many-body perturbation theory based on the GW approximation, we show that corundum-type Ti 2 N 2 O (an example Ti n N 2 O 2 n − 3 compound with n = 2 ) has a smaller band gap of about 2.5 eV, which is more suitable to absorb visible light, compared to other Ti-based oxides such as TiO 2 and SrTiO 3 with a band gap of more than 3 eV. Band-gap reduction in Ti 2 N 2 O is caused by an upward shift of the valence band (negative shift to the oxidation potential of H 2 O to O 2 ) due to the presence of nitrogen 2 p states. The conduction band is dominated by Ti 3 d states and the conduction-band minimum is nearly unchanged. As a result, the band-edge potentials of Ti 2 N 2 O are better aligned to the water reduction and oxidation levels. Our theoretical predictions provide useful insights for the discovery of efficient visible-light-driven photocatalysts for water splitting.},
doi = {10.1103/PhysRevB.99.075203},
journal = {Physical Review B},
issn = {2469-9950},
number = 7,
volume = 99,
place = {United States},
year = {2019},
month = {2}
}

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