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

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.

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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.

References

  1. 1

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

    CAS  Article  Google Scholar 

  2. 2

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

    CAS  Article  Google Scholar 

  3. 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).

    CAS  Article  Google Scholar 

  4. 4

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

    CAS  Article  Google Scholar 

  5. 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).

    CAS  Article  Google Scholar 

  6. 6

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

    CAS  Article  Google Scholar 

  7. 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).

    CAS  Article  Google Scholar 

  8. 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).

    CAS  Article  Google Scholar 

  9. 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).

    CAS  Article  Google Scholar 

  10. 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. 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. 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).

    CAS  Article  Google Scholar 

  13. 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).

    CAS  Article  Google Scholar 

  14. 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).

    CAS  Article  Google Scholar 

  15. 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).

    CAS  Article  Google Scholar 

  16. 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).

    CAS  Article  Google Scholar 

  17. 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).

    CAS  Article  Google Scholar 

  18. 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).

    CAS  Article  Google Scholar 

  19. 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).

    CAS  Article  Google Scholar 

  20. 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).

    CAS  Article  Google Scholar 

  21. 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).

    CAS  Article  Google Scholar 

  22. 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).

    CAS  Article  Google Scholar 

  23. 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).

    Google Scholar 

  24. 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. 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. 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).

    CAS  Article  Google Scholar 

  27. 27

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

    CAS  Article  Google Scholar 

  28. 28

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

    CAS  Article  Google Scholar 

  29. 29

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

    CAS  Article  Google Scholar 

  30. 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).

    CAS  Article  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.

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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.

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Correspondence to Kazunari Domen.

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The authors declare no competing financial interests.

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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

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