TY - JOUR
T1 - Improved thermodynamic stability and visible light absorption in Zr+X codoped (X = S, Se and Te) BaTiO3 photocatalysts: A first-principles study
AU - Zulfiqar, Waqas
AU - Alay-e-Abbas, Syed Muhammad
N1 - Funding Information:
The authors are grateful to the Higher Education Commission of Pakistan for financial support under the National Research Program for Universities grant No. 7107/Punjab/NRPU/R&D/ HEC/2017 . W. Z. thanks the Higher Education Commission of Pakistan for the award of an International Research Support Initiative Program (IRSIP) scholarship. S. M. A. A. thank the Knut and Alice Wallenberg Foundation, and Kempestiftelserna (Sweden) for financial support. The computations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at HPC2N and NSC partially funded by the Swedish Research Council through grant agreement no. 2018-05973 .
Publisher Copyright:
© 2022 The Authors
PY - 2022/8
Y1 - 2022/8
N2 - Band gap tuning of titanium based perovskite oxides through chalcogen doping is an attractive avenue for realizing visible light driven photocatalysis for hydrogen production. Unfortunately, accommodating a chalcogen atom at an O-site of BaTiO
3 is thermodynamically challenging owing to large differences in the atomic radii and electronegativities of oxygen and chalcogen atoms. In the present study we employ first-principles density functional theory calculations to examine the influence of Zr codoping on the structural, thermodynamic, opto-electronic properties and photocatalytic performance of X-doped (X = S, Se and Te) BaTiO
3 systems. The atomic structure and energetic properties are computed using SCAN meta-GGA functional of density functional theory, while the electronic and optical properties are computed using the TB-mBJ meta-GGA potential functional. Within the valid limits of the atomic chemical potentials, we find that chalcogen doping in BaTiO
3 lattice would be experimentally difficult despite a clear reduction in the electronic band gap of this system useful for application in visible light driven photocatalysis. In order to improve the synthesis feasibility of X-doped BaTiO
3 under oxygen-rich as well as oxygen-poor chemical environments, we propose Zr as a codopant at a Ti-site in X-doped BaTiO
3 which improves the thermodynamic stability and also retains the reduction in the electronic band gap of cubic BaTiO
3 caused by the presence of chalcogen atom. Our results suggest that Zr+X (X = S, Se and Te) codoped BaTiO
3 offer great opportunities as practical photocatalysts for hydrogen production through overall splitting of the water molecule.
AB - Band gap tuning of titanium based perovskite oxides through chalcogen doping is an attractive avenue for realizing visible light driven photocatalysis for hydrogen production. Unfortunately, accommodating a chalcogen atom at an O-site of BaTiO
3 is thermodynamically challenging owing to large differences in the atomic radii and electronegativities of oxygen and chalcogen atoms. In the present study we employ first-principles density functional theory calculations to examine the influence of Zr codoping on the structural, thermodynamic, opto-electronic properties and photocatalytic performance of X-doped (X = S, Se and Te) BaTiO
3 systems. The atomic structure and energetic properties are computed using SCAN meta-GGA functional of density functional theory, while the electronic and optical properties are computed using the TB-mBJ meta-GGA potential functional. Within the valid limits of the atomic chemical potentials, we find that chalcogen doping in BaTiO
3 lattice would be experimentally difficult despite a clear reduction in the electronic band gap of this system useful for application in visible light driven photocatalysis. In order to improve the synthesis feasibility of X-doped BaTiO
3 under oxygen-rich as well as oxygen-poor chemical environments, we propose Zr as a codopant at a Ti-site in X-doped BaTiO
3 which improves the thermodynamic stability and also retains the reduction in the electronic band gap of cubic BaTiO
3 caused by the presence of chalcogen atom. Our results suggest that Zr+X (X = S, Se and Te) codoped BaTiO
3 offer great opportunities as practical photocatalysts for hydrogen production through overall splitting of the water molecule.
KW - Hydrogen production
KW - Isovalent doping
KW - Perovskite oxide
KW - Photocatalytic water splitting
KW - Solar energy
UR - http://www.scopus.com/inward/record.url?scp=85132804191&partnerID=8YFLogxK
U2 - 10.1016/j.mtcomm.2022.103867
DO - 10.1016/j.mtcomm.2022.103867
M3 - Article
SN - 2352-4928
VL - 32
JO - Materials Today Communications
JF - Materials Today Communications
M1 - 103867
ER -