Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Oxysulfide photocatalyst for visible-light-driven overall water splitting

Nature Materials volume 18, pages 827–832 (2019)Cite this article

Subjects

Abstract

Oxysulfide semiconductors have narrow bandgaps suitable for water splitting under visible-light irradiation, because the electronegative sulfide ions negatively shift the valence band edges of the corresponding oxides1,2. However, the instability of sulfide ions during the water oxidation is a critical obstacle to simultaneous evolution of hydrogen and oxygen3. Here, we demonstrate the activation and stabilization of Y2Ti2O5S2, with a bandgap of 1.9 eV, as a photocatalyst for overall water splitting. On loading of IrO2 and Rh/Cr2O3 as oxygen and hydrogen evolution co-catalysts, respectively, and fine-tuning of the reaction conditions, simultaneous production of stoichiometric amounts of hydrogen and oxygen was achieved on Y2Ti2O5S2 during a 20 h reaction. The discovery of the overall water splitting capabilities of Y2Ti2O5S2 extends the range of promising materials for solar hydrogen production.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Structure of Y2Ti2O5S2.
Fig. 2: Morphology of Y2Ti2O5S2.
Fig. 3: Band structure of Y2Ti2O5S2.
Fig. 4: Wavelength dependence of photocatalytic activity of Y2Ti2O5S2.
Fig. 5: Photocatalytic performance of Y2Ti2O5S2 for overall water splitting.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Ishikawa, A. et al. Oxysulfide Sm2Ti2S2O5 as a stable photocatalyst for water oxidation and reduction under visible light irradiation (λ ≤ 650 nm). J. Am. Chem. Soc. 124, 13547–13553 (2002).

    Article  CAS  Google Scholar 

  2. Ishikawa, A. et al. Oxysulfides Ln2Ti2S2O5 as stable photocatalysts for water oxidation and reduction under visible-light irradiation. J. Phys. Chem. B 108, 2637–2642 (2004).

    Article  CAS  Google Scholar 

  3. Fujito, H. et al. Layered perovskite oxychloride Bi4NbO8Cl: a stable visible light responsive photocatalyst for water splitting. J. Am. Chem. Soc. 138, 2082–2085 (2016).

    Article  CAS  Google Scholar 

  4. Shaner, M. R., Atwater, H. A., Lewis, N. S. & McFarland, E. W. A comparative technoeconomic analysis of renewable hydrogen production using solar energy. Energy Environ. Sci. 9, 2354–2371 (2016).

    Article  CAS  Google Scholar 

  5. Bala, C. R., Breen, S., Shao, Y., Ardo, S. & Weber, A. Z. Evaluating particle-suspension reactor designs for Z-scheme solar water splitting via transport and kinetic modeling. Energy Environ. Sci. 11, 115–135 (2018).

    Article  Google Scholar 

  6. Goto, Y. et al. A particulate photocatalyst water-splitting panel for large-scale solar hydrogen generation. Joule 2, 509–520 (2018).

    Article  CAS  Google Scholar 

  7. Sivula, K. & van de Krol, R. Semiconducting materials for photoelectrochemical energy conversion. Nat. Rev. Mater. 1, 15010 (2016).

    Article  CAS  Google Scholar 

  8. Tachibana, Y., Vayssieres, L. & Durrant, J. R. Artificial photosynthesis for solar water-splitting. Nat. Photon. 6, 511–518 (2012).

    Article  CAS  Google Scholar 

  9. Ellis, A. B., Kaiser, S. W., Bolts, J. M. & Wrighton, M. S. Study of n-type semiconducting cadmium chalcogenide-based photoelectrochemical cells employing polychalcogenide electrolytes. J. Am. Chem. Soc. 99, 2839–2848 (1977).

    Article  CAS  Google Scholar 

  10. Wolff, C. M. et al. All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalyst on CdS nanorods. Nat. Energy 3, 862–869 (2018).

    Article  CAS  Google Scholar 

  11. Ran, J., Zhang, J., Yu, J., Jaroniec, M. & Qiao, S. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem. Soc. Rev. 43, 7787–7812 (2014).

    Article  CAS  Google Scholar 

  12. Denis, S. G. & Clarke, S. J. Two alternative products from the intercalation of alkali metals into cation-defective Ruddlesden–Popper oxysulfides. Chem. Commun. 22, 2356–2357 (2001).

    Article  Google Scholar 

  13. Hyett, G. et al. Electronically driven structural distortions in lithium intercalates of the n = 2 Ruddlesden–Popper-type host Y2Ti2O5S2: synthesis, structure and properties of LixY2Ti2O5S2 (0 < x < 2). J. Am. Chem. Soc. 126, 1980–1991 (2004).

    Article  CAS  Google Scholar 

  14. Kristin, P. Materials Data on Y 2Ti 2S 2O 5 (SG:139) by Materials Project (Lawrence Berkeley National Lab, 2016); https://doi.org/10.17188/1200585

  15. Oki, H. & Takagi, H. Y2Ti2O5S2 as a high performance anode material for Li ion batteries. Solid State Ion. 276, 80–83 (2015).

    Article  CAS  Google Scholar 

  16. Rutt, O. J., Hill, T. L., Gál, Z. A., Hayward, M. A. & Clarke, S. J. The cation-deficient Ruddlesden-Popper oxysulfide Y2Ti2O5S2 as a layered sulfide: topotactic potassium intercalation to form KY2Ti2O5S2. Inorg. Chem. 42, 7906–7911 (2003).

    Article  CAS  Google Scholar 

  17. Ingo, G., Paparazzo, E., Bagnarelli, O. & Zacchetti, N. XPS studies on cerium, zirconium and yttrium valence states in plasma-sprayed coatings. Surf. Interface Anal. 16, 515–519 (1990).

    Article  CAS  Google Scholar 

  18. BaQais, A. et al. Bismuth silver oxysulfide for photoconversion applications: structural and optoelectronic properties. Chem. Mater. 29, 8679–8689 (2017).

    Article  CAS  Google Scholar 

  19. Maeda, K. et al. Noble-metal/Cr2O3 core/shell nanoparticles as a cocatalyst for photocatalytic overall water splitting. Angew. Chem. Int. Ed. 118, 7970–7973 (2006).

    Article  Google Scholar 

  20. Gu., J. et al. Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst. Nat. Mater. 15, 456–460 (2016).

    Article  CAS  Google Scholar 

  21. Vequizo, J. J. M., Hojamberdiev, M., Teshima, K. & Yamakata, A. Role of CoOx cocatalyst on Ta3N5 photocatalysts studied by transient visible to mid-infrared absorption spectroscopy. J. Photochem. Photobiol. C 358, 315–319 (2018).

    Article  CAS  Google Scholar 

  22. Kato, H., Asakura, K. & Kudo, A. Highly efficient water splitting into H2 and O2 over lanthanum-doped NaTaO3 photocatalysts with high crystallinity and surface nanostructure. J. Am. Chem. Soc. 125, 3082–3089 (2013).

    Article  Google Scholar 

  23. Sherkar, T. S. et al. Recombination in perovskite solar cells: significance of grain boundaries, interface traps and defections. ACS Energy Lett. 2, 1214–1222 (2017).

    Article  CAS  Google Scholar 

  24. Inoue, Y. Photocatalytic water splitting by RuO2-loaded metal oxides and nitrides with d 0- and d 10-related electronic configurations. Energy Environ. Sci. 2, 364–386 (2009).

    Article  CAS  Google Scholar 

  25. Kibria, M. G. et al. Visible light-driven efficient overall water splitting using p-type metal-nitride nanowire arrays. Nat. Commun. 6, 6797 (2015).

    Article  CAS  Google Scholar 

  26. Lyu, H. et al. An Al-doped SrTiO3 photocatalyst maintaining sunlight-driven overall water splitting activity for over 1,000 h of constant illumination. Chem. Sci. 10, 3196–3201 (2019).

    Article  CAS  Google Scholar 

  27. Milman, V. et al. Electronic structure, properties and phase stability of inorganic crystals: a pseudopotential plane-wave study. Int. J. Quantum Chem. 77, 895–910 (2000).

    Article  CAS  Google Scholar 

  28. Materials Studio CASTEP (Accelrys, 2001).

  29. Minegishi, T., Nishimura, N., Kubota, J. & Domen, K. Photoelectrochemical properties of LaTiO2N electrodes prepared by particle transfer for sunlight-driven water splitting. Chem. Sci. 4, 1120–1124 (2013).

    Article  CAS  Google Scholar 

  30. Le, P.-T. C. et al. Photoelectrochemical properties of crystalline perovskite lanthanum titanium oxynitride films under visible light. J. Phys. Chem. C 113, 6156–6162 (2009).

    Article  Google Scholar 

Download references

Acknowledgements

Q.W. thanks Y. Kuromiya, K. Kato and M. Yamaguchi at The University of Tokyo for performing ICP-AES and elemental analysis, and assisting with the isotopic labelling experiment. S.S. thanks Z. Song at Anhui University for assisting with the theoretical calculations. This work was financially supported by the Artificial Photosynthesis Project of the New Energy and Industrial Technology Development Organization (NEDO) and a Grant-in-Aid for Scientific Research(A) (no. 16H02417) from the Japan Society for the Promotion of Science. M.N. and N.S. performed work at the Advanced Characterization Nanotechnology Platform of the University of Tokyo, supported through the ‘Nanotechnology Platform’ of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

Author information

Author notes

  1. Qian Wang

    Present address: Department of Chemistry, University of Cambridge, Cambridge, UK

Authors and Affiliations

  1. Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Tokyo, Japan

    Qian Wang, Zhenhua Pan, Taro Yamada & Kazunari Domen

  2. Institute of Engineering Innovation, The University of Tokyo, Tokyo, Japan

    Mamiko Nakabayashi & Naoya Shibata

  3. Center for Energy & Environmental Science, Shinshu University, Nagano, Japan

    Takashi Hisatomi, Zheng Wang, Tsuyoshi Takata & Kazunari Domen

  4. School of Chemistry and Chemical Engineering, Anhui University, Anhui, China

    Song Sun

  5. National Synchrotron Radiation Laboratory, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science & Technology of China, Anhui, China

    Song Sun

  6. Mitsubishi Chemical Corporation, Yokohama R&D center, Kanagawa, Japan

    Seiji Akiyama

  7. Japan Technological Research Association of Artificial Photosynthetic Chemical Process (ARPChem), Tokyo, Japan

    Seiji Akiyama & Xiong Xiao

  8. Department of Applied Chemistry, School of Science and Technology, Meiji University, Kanagawa, Japan

    Xiong Xiao & Tomoaki Watanabe

Authors
  1. Qian Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mamiko Nakabayashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Takashi Hisatomi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Song Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Seiji Akiyama
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhenhua Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xiong Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Tomoaki Watanabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Taro Yamada
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Naoya Shibata
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Tsuyoshi Takata
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Kazunari Domen
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Q.W. and K.D. designed the research. Q.W. prepared Y2Ti2O5S2 powder and conducted XRD, DRS, XPS, PESA and SEM characterizations, and the water-splitting reactions. Q.W. and T.Y. carried out the isotopic labelling experiment. M.N. and N.S. conducted cross-sectional cutting of particles along with the STEM, STEM-EDS, TEM-EDS, HRTEM and SAED analyses. S.S. performed the theoretical calculations. S.A. carried out the TG analysis. Q.W. and Z.P. fabricated the electrodes by the particle transfer method and conducted the Mott–Schottky measurements. X.X. and T.W. prepared the electrodes using the roll press method. Z.P. and X.X. carried out the photoelectrochemical measurements. T.Y. supervised the elemental analysis. K.D. and T.H. supervised the experimental work. Q.W., T.H., Z.W., T.Y., T.T. and K.D. discussed the results. Q.W., T.H. and K.D. wrote the manuscript with contributions from the other authors.

Corresponding author

Correspondence to Kazunari Domen.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–20, Supplementary Table 1, Supplementary references 1–26

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Q., Nakabayashi, M., Hisatomi, T. et al. Oxysulfide photocatalyst for visible-light-driven overall water splitting. Nat. Mater. 18, 827–832 (2019). https://doi.org/10.1038/s41563-019-0399-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-019-0399-z

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing