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A metal-free polymeric photocatalyst for hydrogen production from water under visible light

Abstract

The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.

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Figure 1: Crystal structure and optical properties of graphitic carbon nitride.
Figure 2: Electronic structure of polymeric melon.
Figure 3: Stable hydrogen evolution from water by g-C3N4.
Figure 4: Wavelength-dependent hydrogen evolution from water by g-C3N4.
Figure 5: Oxygen evolution from water by g-C3N4.

References

  1. Borgarello, E. et al. Photochemical cleavage of water by photocatalysis. Nature 289, 158–160 (1981).

    Article  CAS  Google Scholar 

  2. Kim, Y. I., Salim, S., Huq, M. J. & Mallouk, T. E. Visible-light photolysis of hydrogen iodide using sensitized layered semiconductor particles. J. Am. Chem. Soc. 113, 9561–9563 (1991).

    Article  CAS  Google Scholar 

  3. Khaselev, O. & Turner, J. A. A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting. Science 280, 425–427 (1998).

    Article  CAS  Google Scholar 

  4. Sayama, K. et al. Stoichiometric water splitting into H2 and O2 using a mixture of two different photocatalysts and an IO3/I shuttle redox mediator under visible light irradiation. Chem. Commun. 2416–2417 (2001).

  5. Kato, H. & Kudo, A. Visible-light-response and photocatalytic activities of TiO2 and SrTiO3 photocatalysts codoped with antimony and chromium. J. Phys. Chem. B 106, 5029–5034 (2002).

    Article  CAS  Google Scholar 

  6. Hitoki, G. et al. An oxynitride, TaON, as an efficient water oxidation photocatalyst under visible light irradiation (λ≤500 nm). Chem. Commun. 1698–1699 (2002).

  7. 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 

  8. Tsuji, I., Kato, H., Kobayashi, H. & Kudo, A. Photocatalytic H2 evolution reaction from aqueous solutions over band structure-controlled (AgIn)(x)Zn2(1−x)S2 solid solution photocatalysts with visible-light response and their surface nanostructures. J. Am. Chem. Soc. 126, 13406–13413 (2004).

    Article  CAS  Google Scholar 

  9. Tsuji, I., Kato, H. & Kudo, A. Visible-light-induced H2 evolution from an aqueous solution containing sulfide and sulfite over a ZnS–CuInS2–AgInS2 solid-solution photocatalyst. Angew. Chem. Int. Ed. 44, 3565–3568 (2005).

    Article  CAS  Google Scholar 

  10. Maeda, K. et al. GaN:ZnO solid solution as a photocatalyst for visible-light-driven overall water splitting. J. Am. Chem. Soc. 127, 8286–8287 (2005).

    Article  CAS  Google Scholar 

  11. Maeda, K. et al. Photocatalyst releasing hydrogen from water—Enhancing catalytic performance holds promise for hydrogen production by water splitting in sunlight. Nature 440, 295 (2006).

    Article  CAS  Google Scholar 

  12. Lee, Y. et al. Zinc germanium oxynitride as a photocatalyst for overall water splitting under visible light. J. Phys. Chem. C 111, 1042–1048 (2007).

    Article  CAS  Google Scholar 

  13. Yachandra, V. K. et al. Where plants make oxygen—a structural model for the photosynthetic oxygen-evolving manganese cluster. Science 260, 675–679 (1993).

    Article  CAS  Google Scholar 

  14. de Carcer, I. A., DiPasquale, A., Rheingold, A. L. & Heinekey, D. M. Active-site models for iron hydrogenases: Reduction chemistry of dinuclear iron complexes. Inorg. Chem. 45, 8000–8002 (2006).

    Article  Google Scholar 

  15. Yanagida, S., Kabumoto, A., Mizumoto, K., Pac, C. & Yoshino, K. Poly(para)phenylene-catalyzed photoreduction of water to hydrogen. JCS-Chem. Commun. 8, 474–475 (1985).

    Article  Google Scholar 

  16. Liebig, J. About some nitrogen compounds. Ann. Pharm. 10, 10 (1834).

    Google Scholar 

  17. Groenewolt, M. & Antonietti, M. Synthesis of g-C3N4 nanoparticles in mesoporous silica host matrices. Adv. Mater. 17, 1789–1792 (2005).

    Article  CAS  Google Scholar 

  18. Goettmann, F., Fischer, A., Antonietti, M. & Thomas, A. Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel-Crafts reaction of benzene. Angew. Chem. Int. Ed. 45, 4467–4471 (2006).

    Article  CAS  Google Scholar 

  19. Clark, S. J. et al. First principles methods using CASTEP. Z. f Krist 220, 567–570 (2005).

    CAS  Google Scholar 

  20. Lotsch, B. V. et al. Unmasking melon by a complementary approach employing electron diffraction, solid-state NMR spectroscopy, and theoretical calculations-structural characterization of a carbon nitride polymer. Chem. Eur. J. 13, 4969–4980 (2007).

    Article  CAS  Google Scholar 

  21. Reuter, K. & Scheffler, M. Composition, structure, and stability of RuO2(110) as a function of oxygen pressure. Phys. Rev. B 65, 035406 (2001).

    Article  Google Scholar 

  22. Tissandier, M. D. et al. The proton’s absolute aqueous enthalpy and Gibbs free energy of solvation from cluster-ion solvation data. J. Phys. Chem. A 102, 7787–7794 (1998).

    Article  CAS  Google Scholar 

  23. Weast, R. C., Astle, M. J. & Beyer, W. H. Handbook of Physics and Chemistry 64th edn, D158 (CRC Press, 1983).

    Google Scholar 

  24. Kraeutler, B & Bard, A. J. Heterogeneous photocatalytic preparation of supported catalysts—photodeposition of platinum on TiO2 powder and other substrates. J. Am. Chem. Soc. 100, 4317–4318 (1978).

    Article  CAS  Google Scholar 

  25. Maeda, K. & Domen, K. New non-oxide photocatalysts designed for overall water splitting under visible light. J. Phys. Chem. C 111, 7851–7861 (2007).

    Article  CAS  Google Scholar 

  26. Kalyanasundaram, K. & Grätzel, M. Cyclic cleavage of water into H2 and O2 by visible light with coupled redox catalysts. Angew. Chem. Int. Ed. 18, 701–702 (1979).

    Article  Google Scholar 

  27. Borgarello, E., Kiwi, J., Pelizzetti, E., Visca, M. & Grätzel, M. Photochemical cleavage of water by photocatalysis. Nature 289, 158–160 (1981).

    Article  CAS  Google Scholar 

  28. Harriman, A., Pickering, I. J., Thomas, J. M. & Christensen, P. A. Metal oxides as heterogeneous catalysts for oxygen evolution under photochemical conditions. J. Chem. Soc. Faraday Trans. 1 84, 2795–2806 (1988).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Max Planck Society within the framework of the project ENERCHEM, and the Research and Development in a New Interdisciplinary Field Based on Nanotechnology and Materials Science programs of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. X.W. is grateful for the financial support from the National Basic Research Program of China (973 program, Grant No. 2007CB613306), NSFC (Grant Nos. 20537010 and 20603007), the New Century Excellent Talents in University of China (NCET-07-0192) and the AvH Foundation. K.M. gratefully acknowledges the support of a Japan Society for the Promotion of Science (JSPS) Fellowship. The authors thank J. Kubota, T. Hisatomi and K. Kamata (Department of Chemical System Engineering, The University of Tokyo) for assistance in the revision of this article.

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Correspondence to Xinchen Wang or Kazunari Domen.

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Wang, X., Maeda, K., Thomas, A. et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Mater 8, 76–80 (2009). https://doi.org/10.1038/nmat2317

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