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Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%

Nature Energy volume 2, Article number: 17052 (2017) Cite this article

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Abstract

Multiple exciton generation (MEG) in quantum dots (QDs) has the potential to greatly increase the power conversion efficiency in solar cells and in solar-fuel production. During the MEG process, two electron–hole pairs (excitons) are created from the absorption of one high-energy photon, bypassing hot-carrier cooling via phonon emission. Here we demonstrate that extra carriers produced via MEG can be used to drive a chemical reaction with quantum efficiency above 100%. We developed a lead sulfide (PbS) QD photoelectrochemical cell that is able to drive hydrogen evolution from aqueous Na2S solution with a peak external quantum efficiency exceeding 100%. QD photoelectrodes that were measured all demonstrated MEG when the incident photon energy was larger than 2.7 times the bandgap energy. Our results demonstrate a new direction in exploring high-efficiency approaches to solar fuels.

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Figure 1: MEG PEC cell illustration.
Figure 2: PEC performance characteristics.
Figure 3: IPCE front and back illumination.
Figure 4: Absorbed photon-to-current efficiency measurements.

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Acknowledgements

We would like to thank B. To and C. Xiao from NREL for the scanning electron micrographs. A. J. Nozik, J. Luther, D. Kroupa and Y. Yang are thanked for their helpful discussions. Y.Y. would like to acknowledge the support from the startup fund at New Jersey Institute of Technology. Y.Y., R.W.C., B.D.C., G.F.P., A.R.M. and M.C.B. acknowledge support from the Center for Advanced Solar Photophysics, an Energy Frontier Research Center funded by the Office of Basic Energy Sciences within the Office of Science. J.G. and J.A.T. acknowledge the solar photochemistry programme within the division of Chemical Sciences,Geosciences, and Biosciences of the Office of Basic Energy Sciences within the Office of Science. All work is supported by the Department of Energy under contract No. DE-AC36-08GO28308 to NREL.

Author information

Affiliations

  1. Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, Colorado 80401, USA

    Yong Yan, Ryan W. Crisp, Jing Gu, Boris D. Chernomordik, Gregory F. Pach, Ashley R. Marshall, John A. Turner & Matthew C. Beard

  2. Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, USA

    Yong Yan

  3. Department of Physics, Colorado School of Mines, Golden, Colorado 80401, USA

    Ryan W. Crisp

  4. Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182, USA

    Jing Gu

  5. Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA

    Gregory F. Pach & Ashley R. Marshall

Authors
  1. Yong Yan
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  2. Ryan W. Crisp
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  3. Jing Gu
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  4. Boris D. Chernomordik
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  5. Gregory F. Pach
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  6. Ashley R. Marshall
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  7. John A. Turner
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  8. Matthew C. Beard
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Contributions

Y.Y. and M.C.B. conceived the experiments and led the project; Y.Y. and J.G. carried out the photoelectrode synthesis and characterization and photoelectrochemical investigation; R.W.C., B.D.C., G.F.P. and A.R.M. carried out quantum-dot synthesis and film preparation; Y.Y., J.A.T. and M.C.B. analysed the data; Y.Y. and M.C.B. wrote the manuscript with input and discussion from all authors.

Corresponding authors

Correspondence to Yong Yan or Matthew C. Beard.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–3, Supplementary Tables 1–3, Supplementary Note 1 (PDF 933 kb)

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Yan, Y., Crisp, R., Gu, J. et al. Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%. Nat Energy 2, 17052 (2017). https://doi.org/10.1038/nenergy.2017.52

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