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Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods

Nature Materials volume 13, pages 1013–1018 (2014)Cite this article

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Abstract

Photocatalytic conversion of solar energy to fuels, such as hydrogen, is attracting enormous interest, driven by the promise of addressing both energy supply and storage1. Colloidal semiconductor nanocrystals have been at the forefront of these efforts owing to their favourable and tunable optical and electronic properties2,3,4 as well as advances in their synthesis5,6. The efficiency of the photocatalysts is often limited by the slow transfer and subsequent reactions of the photoexcited holes and the ensuing high charge recombination rates. Here we propose that employing a hydroxyl anion/radical redox couple to efficiently relay the hole from the semiconductor to the scavenger leads to a marked increase in the H2 generation rate without using expensive noble metal co-catalysts. The apparent quantum yield and the formation rate under 447 nm laser illumination exceeded 53% and 63 mmol g−1 h−1, respectively. The fast hole transfer confers long-term photostability on the system and opens new pathways to improve the oxidation side of full water splitting.

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Figure 1: Schematic of the photocatalytic generation of H2 under the proposed hole shuttle mechanism.
Figure 2: Photocatalyst characterization and H2 evolution measurements.
Figure 3: Energy diagram for the two-step oxidation reaction.
Figure 4: Effect of pH of the CdS nanocrystal dispersion.

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Acknowledgements

This work was supported by the Bavarian State Ministry of Science, Research, and Arts through the grant ‘Solar Technologies go Hybrid (SolTech)’, by the German Science Foundation (DFG) and by a grant from the Germany/Hong Kong Joint Research Scheme sponsored by the Research Grants Council of Hong Kong and the German Academic Exchange Service (DAAD, Ref. No.: G_HK004/12). A.L.R. acknowledges support by the Alexander von Humboldt Foundation. The authors thank J. Marquard for assistance in acetaldehyde detection using the GC-MS system, M. Carlson for supplying MPA-coated CdS nanorods and C. Hohmann (Nanosystems Initiative Munich) for his support in graphics design.

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  1. Frank Jäckel

    Present address: Present address: Department of Physics and Stephenson Institute for Renewable Energy, University of Liverpool, Chadwick Building, Peach Street, Liverpool L69 7ZF, UK.,

Authors and Affiliations

  1. Department of Physics and Center for NanoScience (CeNS), Photonics and Optoelectronics Group, Ludwig-Maximilians-Universität München, Amalienstr. 54, 80799 Munich, Germany

    Thomas Simon, Nicolas Bouchonville, Maximilian J. Berr, Asmir Adrović, David Volbers, Frank Jäckel, Jacek K. Stolarczyk & Jochen Feldmann

  2. Nanosystems Initiative Munich (NIM), Schellingstr. 4, 80799 Munich, Germany

    Thomas Simon, Nicolas Bouchonville, Maximilian J. Berr, Asmir Adrović, David Volbers, Markus Döblinger, Frank Jäckel, Jacek K. Stolarczyk & Jochen Feldmann

  3. Department of Physics and Materials Science and Centre for Functional Photonics, City University of Hong Kong, Tat Chee Avenue, Hong Kong

    Aleksandar Vaneski, Andrei S. Susha & Andrey L. Rogach

  4. Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13 (E), 81377 Munich, Germany

    Regina Wyrwich & Markus Döblinger

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Contributions

All authors contributed to the design of the experiments, the interpretation of the results and a discussion of the outline of the manuscript. T.S., N.B., M.J.B., A.V., A.A., D.V., R.W. and M.D. carried out the experiments. J.K.S. wrote the manuscript, with input and comments from other authors.

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Correspondence to Jacek K. Stolarczyk or Jochen Feldmann.

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Simon, T., Bouchonville, N., Berr, M. et al. Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods. Nature Mater 13, 1013–1018 (2014). https://doi.org/10.1038/nmat4049

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