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Oxysulfides Ln2Ti2S2O5 as Stable Photocatalysts for Water Oxidation and Reduction under Visible-Light Irradiation
Abstract
The series Ln 2 Ti 2 S 2 O 5 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er) is demonstrated to evolve H 2 or O 2 from aqueous solutions under visible-light (440 nm ≤ λ ≤ 650 nm) irradiation in the presence of a sacrificial electron donor (Na 2 S−Na 2 SO 3 ) or acceptor (Ag + ) without noticeable degradation. Ln 2 Ti 2 S 2 O 5 is synthesized by sulfurization under H 2 S flow, and the Sm 2 Ti 2 S 2 O 5 form is found to have the highest activity for O 2 evolution. X-ray Rietveld refinements reveal that the Ln 2 Ti 2 S 2 O 5 framework of the Pr, Nd, and Er forms is distorted from the ideal perovskite structure. The calculations of the electronic band structures of Ln 2 Ti 2 S 2 O 5 based on plane-wave based density functional theory indicated that the top of the valence band of [Gd−Er] 2 Ti 2 S 2 O 5 is made up of hybridized O2p, S3p, and Ln4f orbitals, whereas Ln4f orbitals are localized in other [Pr−Sm] 2 Ti 2 S 2 O 5 . In addition, the conduction band of [Gd−Er] 2 Ti 2 S 2 O 5 consists of S3p+Ln4f and Ti3d orbitals. The photocatalytic activity is discussed on the basis of the electronic band structure and bulk material structure.
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Shannon, R. D. (1976) · Acta Crystallographica Section A · doi:10.1107/s0567739476001551 · Cited by 66,145
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Navarro, R. M., Sánchez-Sánchez, M. C., Alvarez-Galvan, M. C., Valle, F. D., & Fierro, J. L. G. (2009) · Energy Environ. Sci. · doi:10.1039/b808138g · Cited by 444
Metadata
- Authors
- Ishikawa, A., Takata, T., Matsumura, T., Kondo, J. N., Hara, M., Kobayashi, H., & Domen, K.
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2004-01-30
- Volume
- 108
- Issue
- 8
- Pages
- 2637-2642
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2951370321
- Cited by
- 200
- References
- 1
- FWCI
- 6.52
- Type
- journal article
- Language
- en
- Open access
- closed
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- Ishikawa, A., Takata, T., Matsumura, T., Kondo, J. N., Hara, M., Kobayashi, H., & Domen, K. (2004). Oxysulfides Ln2Ti2S2O5 as Stable Photocatalysts for Water Oxidation and Reduction under Visible-Light Irradiation. The Journal of Physical Chemistry B. https://doi.org/10.1021/jp036890x
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