Review Article | Published:

Artificial photosynthesis for solar water-splitting

Nature Photonics volume 6, pages 511518 (2012) | Download Citation

Abstract

Hydrogen generated from solar-driven water-splitting has the potential to be a clean, sustainable and abundant energy source. Inspired by natural photosynthesis, artificial solar water-splitting devices are now being designed and tested. Recent developments based on molecular and/or nanostructure designs have led to advances in our understanding of light-induced charge separation and subsequent catalytic water oxidation and reduction reactions. Here we review some of the recent progress towards developing artificial photosynthetic devices, together with their analogies to biological photosynthesis, including technologies that focus on the development of visible-light active hetero-nanostructures and require an understanding of the underlying interfacial carrier dynamics. Finally, we propose a vision for a future sustainable hydrogen fuel community based on artificial photosynthesis.

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References

  1. 1.

    Photosynthetic energy conversion: Natural and artificial. Chem. Soc. Rev. 38, 185–196 (2009).

  2. 2.

    et al. Comparing photosynthetic and photovoltaic efficiencies and recognizing the potential for improvement. Science 332, 805–809 (2011).

  3. 3.

    , , & Crystal structure of oxygen-evolving Photosystem II at a resolution of 1.9 Å. Nature 473, 55–60 (2011).

  4. 4.

    Crystal structure of the oxygen-evolving complex of Photosystem II. Inorg. Chem. 47, 1700–1710 (2008).

  5. 5.

    et al. A perspective on solar-driven water splitting with all-oxide hetero-nanostructures. Energ. Environ. Sci. 4, 3889–3899 (2011).

  6. 6.

    & Photocatalytic water splitting: Recent progress and future challenges. J. Phys. Chem. Lett. 1, 2655–2661 (2010).

  7. 7.

    , , & Charge recombination kinetics at an in-situ chemical bath-deposited CdS/Nanocrystalline TiO2 Interface. J. Phys. Chem. C 113, 6852–6858 (2009).

  8. 8.

    Self-assembly strategies for integrating light harvesting and charge separation in artificial photosynthetic systems. Acc. Chem. Res. 42, 1910–1921 (2009).

  9. 9.

    et al. A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science 328, 342–345 (2010).

  10. 10.

    & In-situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 321, 1072–1075 (2008).

  11. 11.

    & Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).

  12. 12.

    , & Direct observation of a hydroperoxide surface intermediate upon visible light-driven water oxidation at an Ir Oxide nanocluster catalyst by rapid-scan FT-IR spectroscopy. J. Am. Chem. Soc. 133, 12976–12979 (2011).

  13. 13.

    The artificial leaf. Acc. Chem. Res. 45, 767–776 (2012).

  14. 14.

    , , & Design principles of photosynthetic light-harvesting. Faraday Discuss. 155, 27–41 (2012).

  15. 15.

    , , , & Quantum control of energy flow in light harvesting. Nature 417, 533–535 (2002).

  16. 16.

    Structures and energetics for O2 formation in Photosystem II. Acc. Chem. Res. 42, 1871–1880 (2009).

  17. 17.

    et al. A functional model for O–O bond formation by the O2-evolving complex in Photosystem II. Science 283, 1524–1527 (1999).

  18. 18.

    & Heterogeneous photocatalyst materials for water splitting. Chem. Soc. Rev. 38, 253–278 (2009).

  19. 19.

    Recent progress on photocatalytic and photoelectrochemical water splitting under visible light irradiation. J. Photochem. Photobiol. C 11, 179–209 (2010).

  20. 20.

    , & Solar fuels via artificial photosynthesis. Acc. Chem. Res. 42, 1890–1898 (2009).

  21. 21.

    & Proton-coupled electron transfer of tyrosines in Photosystem II and model systems for artificial photosynthesis: The role of a redox-active link between catalyst and photosensitizer. Energ. Environ. Sci. 4, 2379–2388 (2011).

  22. 22.

    et al. Activating multistep charge-transfer processes in fullerene–subphthalocyanine–ferrocene molecular hybrids as a function of ππ orbital overlap. J. Am. Chem. Soc. 132, 16488–16500 (2010).

  23. 23.

    & Assemblies of artificial photosynthetic reaction centers. J. Mater. Chem. 22, 4575–4587 (2012).

  24. 24.

    , , , & Synthesis and photochemistry of a carotene–porphyrin–fullerene model photosynthetic reaction center. J. Phys. Org. Chem. 17, 724–734 (2004).

  25. 25.

    , & Realizing artificial photosynthesis. Faraday Discuss. 155, 9–26 (2012).

  26. 26.

    & Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37–38 (1972).

  27. 27.

    , & 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 (2003).

  28. 28.

    et al. Photocatalyst releasing hydrogen from water. Nature 440, 295 (2006).

  29. 29.

    , , , & Visible light-driven H2 production by hydrogenases attached to dye-sensitized TiO2 nanoparticles. J. Am. Chem. Soc. 131, 18457–18466 (2009).

  30. 30.

    , , & Semiconductor-based photocatalytic hydrogen generation. Chem. Rev. 110, 6503–6570 (2010).

  31. 31.

    et al. Photoassisted overall water splitting in a visible light-absorbing dye-sensitized photoelectrochemical cell. J. Am. Chem. Soc. 131, 926–927 (2009).

  32. 32.

    , , , & Solar-driven water oxidation by a bio-inspired manganese molecular catalyst. J. Am. Chem. Soc. 132, 2892–2894 (2010).

  33. 33.

    , , , & Efficient nonsacrificial water splitting through two-step photoexcitation by visible light using a modified oxynitride as a hydrogen evolution photocatalyst. J. Am. Chem. Soc. 132, 5858–5868 (2010).

  34. 34.

    Photoelectrochemical cells. Nature 414, 338–344 (2001).

  35. 35.

    & Visible light-induced water oxidation on mesoscopic alpha-Fe2O3 films made by ultrasonic spray pyrolysis. J. Phys. Chem. B 109, 17184–17191 (2005).

  36. 36.

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

  37. 37.

    , , & 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).

  38. 38.

    , , , & All-solid-state Z-scheme in CdS-Au-TiO2 three-component nanojunction system. Nature Mater. 5, 782–786 (2006).

  39. 39.

    et al. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science 334, 645–648 (2011).

  40. 40.

    & A monolithic photovoltaic–photoelectrochemical device for hydrogen production via water splitting. Science 280, 425–427 (1998).

  41. 41.

    , & High-efficiency photoelectrochemical hydrogen production using multijunction amorphous silicon photoelectrodes. Energy Fuels 12, 3–10 (1998).

  42. 42.

    , & Advanced nanoarchitectures for solar photocatalytic applications. Chem. Rev. 112, 1555–1614 (2012).

  43. 43.

    et al. Solar hydrogen production with semiconductor metal oxides: New directions in experiment and theory. Phys. Chem. Chem. Phys. 14, 49–70 (2012).

  44. 44.

    , , & Inorganic photocatalysts for overall water splitting. Chem. Asian J. 7, 642–657 (2012).

  45. 45.

    , , & Visible-light-driven photocatalytic water splitting on nanostructured semiconducting materials. Int. J. Nanotechnol. 8, 523–591 (2011).

  46. 46.

    & Recent developments in solar water-splitting photocatalysis. MRS Bull. 36, 17–22 (2011).

  47. 47.

    Photovoltaic hydrogen generation. Int. J. Hydrogen Energ. 33, 5911–5930 (2008).

  48. 48.

    & Advances in the application of nanotechnology in enabling a 'hydrogen economy'. J. Mater. Sci. 43, 5395–5429 (2008).

  49. 49.

    A surface science perspective on TiO2 photocatalysis. Surf. Sci. Rep. 66, 185–297 (2011).

  50. 50.

    , & Composite photoanodes for photoelectrochemical solar water splitting. Energ. Environ. Sci. 3, 1252–1261 (2010).

  51. 51.

    (ed.) On Solar Hydrogen & Nanotechnology (Wiley, 2009).

  52. 52.

    & Solar Hydrogen Energy Systems: Science and Technology for the Hydrogen Economy (Springer, 2012).

  53. 53.

    Light, Water, Hydrogen: The Solar Generation of Hydrogen by Water Photoelectrolysis (Springer, 2007).

  54. 54.

    , & (eds) Solar Hydrogen Generation: Toward a Renewable Energy Future (Springer, 2010).

  55. 55.

    & Solar Hydrogen Generation: Transition Metal Oxides in Water Photoelectrolysis (McGraw Hill, 2012).

  56. 56.

    Photoelectrochemical cells for hydrogen generation in Electrochemical Technologies for Energy Storage and Conversion (ed. Zhang, J. Z.) 539–597 (Wiley, 2011).

  57. 57.

    On the effect of nanoparticle size on water-oxide interfacial chemistry. J. Phys. Chem. C 113, 4733–4736 (2009).

  58. 58.

    et al. TiO2–SnO2:F interfacial electronic structure investigated by soft X-ray absorption spectroscopy. Phys. Rev. B 85, 125109 (2012).

  59. 59.

    et al. Electron enrichment in 3d transition metal oxide hetero-nanostructures. Nano. Lett. 11, 3855–3861 (2011).

  60. 60.

    et al. Energy-conversion properties of vapor–liquid–solid-grown silicon wire-array photocathodes. Science 327, 185–187 (2010).

  61. 61.

    , & New benchmark for water photooxidation by nanostructured alpha-Fe2O3 films. J. Am. Chem. Soc. 128, 15714–15721 (2006).

  62. 62.

    , & Size effect on the conduction band orbital character of anatase TiO2 nanocrystals. Appl. Phys. Lett. 99, 183101 (2011).

  63. 63.

    , & Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nature Mater. 10, 911–921 (2011).

  64. 64.

    & Plasmonic solar water splitting. Energ. Environ. Sci. 5, 5133–5146 (2012).

  65. 65.

    , & Silver nanoparticle induced photocurrent enhancement at WO3 photoanodes. Angew. Chem. Int. Ed. 49, 7980–7983 (2010).

  66. 66.

    et al. One-dimensional quantum-confinement effect in α-Fe2O3 ultrafine nanorod arrays. Adv. Mater. 17, 2320–2323 (2005).

  67. 67.

    , & Understanding intermediate-band solar cells. Nature Photon. 6, 146–152 (2012).

  68. 68.

    (ed.) On Solar Hydrogen & Nanotechnology 523–558 (Wiley, 2009).

  69. 69.

    et al. Quantum dot monolayer sensitized ZnO nanowire-array photoelectrodes: True efficiency for water splitting. Angew. Chem. Int. Ed. 49, 5966–5969 (2010).

  70. 70.

    et al. A new approach to solar hydrogen production: A ZnO–ZnS solid solution nanowire array photoanode. Adv. Energy Mater. 1, 742–747 (2011).

  71. 71.

    , , & Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 331, 746–750 (2011).

  72. 72.

    et al. Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting. Nano. Lett. 11, 3026–3033 (2011).

  73. 73.

    et al. Hydrogen-treated WO3 nanoflakes show enhanced photostability. Energ. Environ. Sci. 5, 6180–6187 (2011).

  74. 74.

    High throughput combinatorial screening of semiconductor materials. Appl. Phys. A 105, 283–288 (2011).

  75. 75.

    & Combinatorial investigation of the effects of the incorporation of Ti, Si, and Al on the performance of α-Fe2O3 photoanodes. ACS Comb. Sci. 13, 399–404 (2011).

  76. 76.

    , , , & Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nature Mater. 5, 909–913 (2006).

  77. 77.

    , , & Photoelectrochemical studies of oriented nanorod thin films of hematite. J. Electrochem. Soc. 147, 2456–2461 (2000).

  78. 78.

    , , & Controlled aqueous chemical growth of oriented three-dimensional crystalline nanorod arrays: Application to iron (III) oxides. Chem. Mater. 13, 233–235 (2001).

  79. 79.

    , , , & Hematite-based solar water splitting: Challenges and opportunities. Energ. Environ. Sci. 4, 4862–4869 (2011).

  80. 80.

    , & Solar water splitting: Progress using hematite (α-Fe2O3) photoelectrodes. Chem. Sus. Chem. 4, 432–449 (2011).

  81. 81.

    , , , & New insights into water splitting at mesoporous α-Fe2O3 films: A study by modulated transmittance and impedance spectroscopies. J. Am. Chem. Soc. 134, 1228–1234 (2012).

  82. 82.

    Solar showdown in Miller-McCune (May/June 2011).

  83. 83.

    & Review of major design and scale-up considerations for solar photocatalytic reactors. Ind. Eng. Chem. Res. 48, 8890–8905 (2009).

  84. 84.

    & A review on exergy comparison of hydrogen production methods from renewable energy sources. Energ. Environ. Sci. 5, 6640–6651 (2012).

  85. 85.

    & Solar-fuel generation. Towards practical implementation. Nature Mater. 11, 100–101 (2012).

  86. 86.

    et al. Mimicking the electron donor side of Photosystem II in artificial photosynthesis. Photosynth. Res. 87, 25–40 (2006).

  87. 87.

    & Nanostructured cobalt and manganese oxide clusters as efficient water oxidation catalysts. Energ. Environ. Sci. 3, 1018–1027 (2010).

  88. 88.

    , & Kinetics of light-driven oxygen evolution at alpha-Fe2O3 electrodes. Faraday Discuss. 155, 309–322 (2012).

  89. 89.

    et al. Passivating surface states on water splitting hematite photoanodes with alumina overlayers. Chem. Sci. 2, 737–743 (2011).

  90. 90.

    Challenges and opportunities in light and electrical energy conversion. J. Phys. Chem. Lett. 2, 1351–1352 (2011).

  91. 91.

    et al. Dynamics of photogenerated holes in nanocrystalline alpha-Fe2O3 electrodes for water oxidation probed by transient absorption spectroscopy. Chem. Commun. 47, 716–718 (2011).

  92. 92.

    et al. Trap states and carrier dynamics of TiO2 studied by photoluminescence spectroscopy under weak excitation condition. Phys. Chem. Chem. Phys. 12, 7083–7090 (2010).

  93. 93.

    , , , & Subpicosecond interfacial charge separation in dye-sensitized nanocrystalline titanium dioxide films. J. Phys. Chem. 100, 20056–20062 (1996).

  94. 94.

    et al. Parameters influencing charge recombination kinetics in dye-sensitized nanocrystalline titanium dioxide films. J. Phys. Chem. B 104, 538–547 (2000).

  95. 95.

    & Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO2 semiconductor surfaces. Chem. Soc. Rev. 38, 115–164 (2009).

  96. 96.

    , , & Electrochemistry and photoelectrochemistry of iron(III) oxide. J. Chem. Soc. Faraday Trans. 179, 2027–2041 (1983).

  97. 97.

    & Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers. J. Appl. Phys. 100, 074510 (2006).

  98. 98.

    & Detailed balance limit of efficiency of p–n junction solar cells. J. Appl. Phys. 32, 510–519 (1961).

  99. 99.

    et al. Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols. J. Mater. Res. 25, 3–16 (2010).

  100. 100.

    Hydrogen Energy (Earthscan, 2010).

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Acknowledgements

Y.T. acknowledges funding support from JST, PRESTO. L.V. acknowledges support from the International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xian Jiaotong University, the Thousand Talents plan and the National Natural Science Foundation of China (no. 51121092). J.R.D. acknowledges the EPSRC and European Research Council for funding. The authors thank J. Nolan and J. Fenn, Design and Production Educational Technology Advancement Group (EduTAG), RMIT University, for their support in the illustration of Fig. 5.

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Affiliations

  1. School of Aerospace, Mechanical and Manufacturing Engineering, RMIT University, Bundoora, Victoria 3083, Australia

    • Yasuhiro Tachibana
  2. Japan Science and Technology Agency (JST), PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan

    • Yasuhiro Tachibana
  3. Center for Advanced Science and Innovation (CASI), Osaka University, 2-1 Yamada-Oka, Suita, Osaka 565-0871, Japan

    • Yasuhiro Tachibana
  4. International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xian Jiaotong University, Xi'an 710049, China

    • Lionel Vayssieres
  5. Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, UK

    • James R. Durrant

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Contributions

Y.T. and L.V. contributed equally to this work. J.R.D. wrote the section on charge carrier dynamics and assisted in drafting other aspects of the manuscript. Y.T. organized the submission.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Yasuhiro Tachibana or Lionel Vayssieres.

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DOI

https://doi.org/10.1038/nphoton.2012.175

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