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:

Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%

Nature Materials volume 15, pages 611–615 (2016)Cite this article

Subjects

Abstract

Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen1,2,3. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction4,5. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles6,7. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. 8) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

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

Figure 1: SrTiO3:La, Rh/Au/BiVO4:Mo sheet prepared by particle transfer method.
Figure 2: Effect of reaction temperature on photocatalytic water splitting rate of the SrTiO3:La, Rh/Au/BiVO4:Mo sheet.
Figure 3: Printed photocatalyst sheet.

Similar content being viewed by others

References

  1. Chen, X., Shen, S., Guo, L. & Mao, S. Semiconductor-based photocatalytic hydrogen generation. Chem. Rev. 110, 6503–6570 (2010).

    Article  CAS  Google Scholar 

  2. Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).

    Article  CAS  Google Scholar 

  3. Pinaud, B. A. et al. Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry. Energy Environ. Sci. 6, 1983–2002 (2013).

    Article  CAS  Google Scholar 

  4. Hisatomi, T., Kubota, J. & Domen, K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem. Soc. Rev. 43, 7520–7535 (2014).

    Article  CAS  Google Scholar 

  5. Yuan, Y.-P., Ruan, L.-W., Barber, J., Joachim Loo, S. C. & Xue, C. Hetero-nanostructured suspended photocatalysts for solar-to-fuel conversion. Energy Environ. Sci. 7, 3934–3951 (2014).

    Article  CAS  Google Scholar 

  6. Maeda, K. Z-scheme water splitting using two different semiconductor photocatalysts. ACS Catal. 3, 1486–1503 (2013).

    Article  CAS  Google Scholar 

  7. Sasaki, Y., Nemoto, H., Saito, K. & Kudo, A. Solar water splitting using powdered photocatalysts driven by Z-schematic interparticle electron transfer without an electron mediator. J. Phys. Chem. C 113, 17536–17542 (2009).

    Article  CAS  Google Scholar 

  8. Wang, Q., Hisatomi, T., Ma, S. S. K., Li, Y. & Domen, K. Core/shell structured La- and Rh-codoped SrTiO3 as a hydrogen evolution photocatalyst in Z-scheme overall water splitting under visible light irradiation. Chem. Mater. 26, 4144–4150 (2014).

    Article  CAS  Google Scholar 

  9. Wang, Q. et al. Z-scheme water splitting using particulate semiconductors immobilized onto metal layers for efficient electron relay. J. Catalys. 328, 308–315 (2015).

    Article  CAS  Google Scholar 

  10. 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  Google Scholar 

  11. Sasaki, Y., Iwase, A., Kato, H. & Kudo, A. The effect of co-catalyst for Z-scheme photocatalysis systems with an Fe3+/Fe2+ electron mediator on overall water splitting under visible light irradiation. J. Catalys. 259, 133–137 (2008).

    Article  Google Scholar 

  12. Piela, P., Eickes, C., Brosha, E., Garzon, F. & Zelenay, P. Ruthenium crossover in direct methanol fuel cell with Pt-Ru black anode. J. Electrochem. Soc. 151, A2053–A2059 (2004).

    Article  CAS  Google Scholar 

  13. Luther, B. et al. Investigation of the mechanism for ohmic contact formation in Al and Ti/Al contacts to n-type GaN. Appl. Phys. Lett. 70, 57–59 (1997).

    Article  CAS  Google Scholar 

  14. Hsu, C.-Y., Lan, W.-H. & Wu, Y. S. Effect of thermal annealing of Ni/Au ohmic contact on the leakage current of GaN based light emitting diodes. Appl. Phys. Lett. 83, 2447–2449 (2003).

    Article  CAS  Google Scholar 

  15. Kudo, A., Omori, K. & Kato, H. A novel aqueous process for preparation of crystal form-controlled and highly crystalline BiVO4 powder from layered vanadates at room temperature and its photocatalytic and photophysical properties. J. Am. Chem. Soc. 121, 11459–11467 (1999).

    Article  CAS  Google Scholar 

  16. Berglund, S. P., Flaherty, D. W., Hahn, N. T., Bard, A. J. & Mullins, C. B. Photoelectrochemical oxidation of water using nanostructured BiVO4 films. J. Phys. Chem. C 115, 3794–3802 (2011).

    Article  CAS  Google Scholar 

  17. Maeda, K. et al. Noble-metal/Cr2O3 core/shell nanoparticles as a cocatalyst for photocatalytic overall water splitting. Angew. Chem. Int. Ed. 45, 7806–7809 (2006).

    Article  CAS  Google Scholar 

  18. Yoshida, M. et al. Role and function of noble-metal/Cr-layer core/shell structure cocatalysts for photocatalytic overall water splitting studied by model electrodes. J. Phys. Chem. C 113, 10151–10157 (2009).

    Article  CAS  Google Scholar 

  19. Takata, T., Pan, C., Nakabayashi, M., Shibata, N. & Domen, K. Fabrication of a core-shell-type photocatalyst via photodeposition of group IV and V transition metal oxyhydroxides: an effective surface modification method for overall water splitting. J. Am. Chem. Soc. 137, 9627–9634 (2015).

    Article  CAS  Google Scholar 

  20. Xu, J., Pan, C., Takata, T. & Domen, K. Photocatalytic overall water splitting on the perovskite-type transition metal oxynitride CaTaO2N under visible light irradiation. Chem. Commun. 51, 7191–7194 (2015).

    Article  CAS  Google Scholar 

  21. Dionigi, F. et al. Gas phase photocatalytic water splitting with Rh2−yCryO3/GaN:ZnO in μ-reactors. Energy Environ. Sci. 4, 2937–2942 (2011).

    Article  CAS  Google Scholar 

  22. Hisatomi, T., Minegishi, T. & Domen, K. Kinetic assessment and numerical modeling of photocatalytic water splitting toward efficient solar hydrogen production. Bull. Chem. Soc. Jpn 85, 647–655 (2012).

    Article  CAS  Google Scholar 

  23. Wohlgemuth, J. H., Cunningham, D. W., Monus, P., Miller, J. & Nguyen, A. Long term reliability of photovoltaic modules. In Conference Record of the 2006 IEEE 4th World Conference on Photovoltaic Energy Conversion Vol. 2, 2050–2053 (IEEE, 2006).

    Chapter  Google Scholar 

  24. Kurtz, S. et al. Evaluation of high-temperature exposure of photovoltaic modules. Prog. Photovolt. Res. Appl. 19, 954–965 (2011).

    Article  Google Scholar 

  25. Pihosh, Y. et al. Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency. Sci. Rep. 5, 11141 (2015).

    Article  Google Scholar 

  26. Kato, H., Sasaki, Y., Shirakura, N. & Kudo, A. Synthesis of highly active rhodium-doped SrTiO3 powders in Z-scheme systems for visible-light-driven photocatalytic overall water splitting. J. Mater. Chem. A 1, 12327–12333 (2013).

    Article  CAS  Google Scholar 

  27. Liao, L. et al. Efficient solar water-splitting using a nanocrystalline CoO photocatalyst. Nature Nanotech. 9, 69–73 (2014).

    Article  CAS  Google Scholar 

  28. Liu, J. et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 347, 970–974 (2015).

    Article  CAS  Google Scholar 

  29. Caro, J. & Noack, M. Zeolite membranes—Recent deveopments and progress. Micropor. Mesopor. Mater. 115, 215–233 (2008).

    Article  CAS  Google Scholar 

  30. Li, H., Haas-Santo, K., Schygulla, U. & Dittmeyer, R. Inorganic microporous membranes for H2 and CO2 separation—Review of experimental and modeling progress. Chem. Eng. Sci. 127, 401–417 (2015).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Artificial Photosynthesis Project of the New Energy and Industrial Technology Development Organization (NEDO), by Grants-in-Aids for Specially Promoted Research (No. 23000009) and for Young Scientists (A) (No. 15H05494), and the A3 Foresight Program of Japan Society for the Promotion of Science (JSPS). A part of this work was conducted at Research Hub for Advanced Nano Characterization, The University of Tokyo, with the support of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. T.T. performed work at GREEN, NIMS supported through the Development of Environmental Technology using Nanotechnology from the Ministry of Education, Culture, Sports, Science and Technology (MEXT). I.D.S. and Y.L. performed work at the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under Award Number DE-SC0004993.

Author information

Authors and Affiliations

  1. Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

    Qian Wang, Takashi Hisatomi, Qingxin Jia, Miao Zhong, Chizhong Wang, Zhenhua Pan, Taro Yamada & Kazunari Domen

  2. Japan Technological Research Association of Artificial Photosynthetic Chemical Process (ARPChem), 5-1-5 Kashiwanoha, Kashiwa-shi, Chiba 277-8589, Japan

    Qian Wang, Takashi Hisatomi, Qingxin Jia, Hiromasa Tokudome, Miao Zhong, Taro Yamada & Kazunari Domen

  3. Research Institute, TOTO Ltd., 2-8-1 Honson, Chigasaki, Kanagawa 253-8577, Japan

    Hiromasa Tokudome

  4. Global Research Center for Environment and Energy Based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba-shi, Ibaraki 305-0044, Japan

    Tsuyoshi Takata

  5. Institute of Engineering Innovation, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan

    Mamiko Nakabayashi & Naoya Shibata

  6. Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA

    Yanbo Li & Ian D. Sharp

  7. Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan

    Akihiko Kudo

Authors
  1. Qian Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Takashi Hisatomi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qingxin Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hiromasa Tokudome
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Miao Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chizhong 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. Tsuyoshi Takata
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Mamiko Nakabayashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Naoya Shibata
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Yanbo Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Ian D. Sharp
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Akihiko Kudo
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Taro Yamada
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Kazunari Domen
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Q.W., T.H., Y.L. and K.D. conceived the photocatalyst sheet design. Q.W. prepared SrTiO3:La, Rh and the photocatalyst sheet, conducted XRD, DRS, XPS and SEM characterizations and the water splitting reactions. T.H. and K.D. supervised the experimental work. Q.J. prepared the BiVO4:Mo particles. H.T. prepared the printed photocatalyst sheets. M.Z. and C.W. performed the photoelectrochemical measurements. Q.W., Z.P. and T.T. conducted the surface modification with a-TiO2. M.N. and N.S. conducted the SEM–EDX elemental mapping measurements. Q.W., Y.L. and I.D.S. carried out the electron beam evaporation. Q.W., T.H., Q.J., H.T., Y.L., A.K., T.Y. and K.D. discussed the results. Q.W. and T.H. wrote the manuscript with contributions from the other co-authors.

Corresponding author

Correspondence to Kazunari Domen.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 3109 kb)

Supplementary Movie 1

Supplementary Movie 1 (MOV 4943 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Q., Hisatomi, T., Jia, Q. et al. Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nature Mater 15, 611–615 (2016). https://doi.org/10.1038/nmat4589

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4589

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