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An autonomous photosynthetic device in which all charge carriers derive from surface plasmons


Solar conversion to electricity or to fuels based on electron–hole pair production in semiconductors is a highly evolved scientific and commercial enterprise1,2,3,4,5,6,7,8,9,10. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO2) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use11,12,13,14,15,16. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet17,18,19,20,21,22,23,24,25,26. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 1013 H2 molecules per cm2 per s under 1 sun illumination (AM 1.5 and 100 mW cm−2), with unprecedented long-term operational stability.

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Figure 1: Structure and mechanism of operation of the autonomous plasmonic solar water splitter.
Figure 2: Hydrogen production rates and wavelength response.
Figure 3: Photocurrent output and wavelength response at the plasmonic photocathode.

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  1. Fujishima, A. & Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37–38 (1972).

    Article  CAS  Google Scholar 

  2. Bard, A. J. Photoelectrochemistry. Science 207, 139–144 (1980).

    Article  CAS  Google Scholar 

  3. Heller, A. Conversion of sunlight into electrical power and photoassisted electrolysis of water in photoelectrochemical cells. Acc. Chem. Res. 14, 154–162 (1981).

    Article  CAS  Google Scholar 

  4. Nozik, A. J. & Memming, R. Physical chemistry of semiconductor liquid interfaces. J. Phys. Chem. 100, 13061–13078 (1996).

    Article  CAS  Google Scholar 

  5. 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 

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

    Article  Google Scholar 

  7. Asahi, R. et al. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293, 269–271 (2001).

    Article  CAS  Google Scholar 

  8. Khan, S. U. M., Al-Shahry, M. & Ingler, W. B. Efficient photochemical water splitting by a chemically modified n-TiO2 . Science 297, 2243–2245 (2002).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  10. Chen, X., Liu, L., Yu, P. Y. & Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 331, 746–750 (2011).

    Article  CAS  Google Scholar 

  11. Schaadt, D. M., Feng, B. & Yu, E. T. Enhanced semiconductor optical absorption via surface plasmon excitation in metal nanoparticles. Appl. Phys. Lett. 86, 063106 (2005).

    Article  Google Scholar 

  12. Neretina, S. et al. Plasmon field effects on the nonradiative relaxation of hot electrons in an electronically quantized system: CdTe–Au core shell nanowires. Nano Lett. 8, 2410–2418 (2008).

    Article  CAS  Google Scholar 

  13. Atwater, H. A. & Polman, A. Plasmonics for improved photovoltaic devices. Nature Mater. 9, 205–213 (2010).

    Article  CAS  Google Scholar 

  14. Knight, M. W., Sobhani, H., Nordlander, P. & Halas, N. J. Photodetection with active optical antennas. Science 332, 702–704 (2011).

    Article  CAS  Google Scholar 

  15. Mubeen, S. et al. Plasmonic photosensitization of a wide band gap semiconductor: converting plasmons to charge carriers. Nano Lett. 11, 5548–5552 (2011).

    Article  CAS  Google Scholar 

  16. Lee, J. et al. Plasmonic photoanodes for solar water splitting with visible light. Nano Lett. 12, 5014–5019 (2012).

    Article  CAS  Google Scholar 

  17. Subramanian, V., Wolf, E. & Kamat, P. V. Semiconductor–metal composite nanostructures. To what extent do metal nanoparticles improve the photocatalytic activity of TiO2 films? J. Phys. Chem. B 105, 11439–11446 (2001).

    Article  CAS  Google Scholar 

  18. Tian, Y. & Tatsuma, T. Plasmon-induced photoelectrochemistry at metal nanoparticles supported on nanoporous TiO2 . Chem. Commun. 1810–1811 (2004).

  19. Kowalska, E., Abe, R. & Ohtani, B. Visible light-induced photocatalytic reaction of gold-modified titanium (IV) oxide particles: action spectrum analysis. Chem. Commun. 241–243 (2009).

  20. Yu, J., Dai, G. & Huang, B. Fabrication and characterization of visible-light-driven plasmonic photocatalyst Ag/AgCl/TiO2 nanotube arrays. J. Phys. Chem. C 113, 16394–16401 (2009).

    Article  CAS  Google Scholar 

  21. Nishijima, Y. et al. Plasmon-assisted photocurrent generation from visible to near-infrared wavelength using a Au-nanorods/TiO2 electrode. J. Phys. Chem. Lett. 1, 2031–2036 (2010).

    Article  CAS  Google Scholar 

  22. Thimsen, E., Le Formal, F., Gratzel, M. & Warren, S. C. Influence of plasmonic Au nanoparticles on the photoactivity of Fe2O3 electrodes for water splitting. Nano Lett. 11, 35–43 (2011).

    Article  CAS  Google Scholar 

  23. Liu, Z. et al. Plasmon resonant enhancement of photocatalytic water splitting under visible illumination. Nano Lett. 11, 1111–1116 (2011).

    Article  CAS  Google Scholar 

  24. Gomes Silva, C. et al. Influence of excitation wavelength (UV or visible light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water. J. Am. Chem. Soc. 133, 595–602 (2011).

    Article  CAS  Google Scholar 

  25. Ingram, D. B. & Linic, S. Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface. J. Am. Chem. Soc. 133, 5202–5205 (2011).

    Article  CAS  Google Scholar 

  26. Thomann, I. et al. Plasmon enhanced solar-to-fuel energy conversion. Nano Lett. 11, 3440–3446 (2011).

    Article  CAS  Google Scholar 

  27. McFarland, E. W. & Tang, J. A photovoltaic device structure based on internal electron emission. Nature 421, 616–618 (2003).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  29. Shalaev, V. M., Douketis, C., Stuckless, J. T. & Moskovits, M. Light-induced kinetic effects in solids. Phys. Rev. B 53, 11388 (1996).

    Article  CAS  Google Scholar 

  30. Cattarin, S., Guerriero, P., Dietz, N. & Lewerenz, H. J. Electrodissolution and corrosion of CuInS2 photoanodes with lamellar morphology. Electrochim. Acta 40, 1041–1049 (1995).

    Article  CAS  Google Scholar 

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The authors acknowledge research support from the Institute for Energy Efficiency, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001009). The authors made extensive use of the MRL Central Facilities at UCSB, which are supported by the MRSEC Program of the NSF (under award no. DMR 1121053), a member of the NSF-funded Materials Research Facilities Network ( N.S. is supported by the ConvEne IGERT Program (NSF-DGE 0801627). The authors thank Wei Cheng for helpful suggestions regarding GC analysis.

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S.M., J.L., G.D.S. and M.M. conceived the concept. S.M., J.L. and M.M. designed processing and device fabrication details. S.M. and J.L. performed the experiments and N.S. assisted S.M. in performing gas analysis. S.K. and J.L. performed optical and structural studies. S.M., J.L. and M.M. wrote the manuscript and prepared the figures. All authors discussed the results and commented on the manuscript. M.M. supervised the project.

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Correspondence to Martin Moskovits.

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The authors declare no competing financial interests.

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Mubeen, S., Lee, J., Singh, N. et al. An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. Nature Nanotech 8, 247–251 (2013).

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