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Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiSx co-catalyst

Nature Energy volume 1, Article number: 16151 (2016) | Download Citation

Abstract

Facilitating charge separation as well as surface redox reactions is considered to be central to improving semiconductor-catalysed solar hydrogen generation. To that end, photocatalysts comprising intimately interfaced photo absorbers and co-catalysts have gained much attention. Here, we combine an efficient Cd0.5Zn0.5S (CZS) nanotwinned photocatalyst with a NiSx co-catalyst for photogeneration of hydrogen. We find that an internal quantum efficiency approaching 100% at 425 nm can be achieved for photocatalytic H2 production from water with Na2S/Na2SO3 as hole scavengers. Our results indicate that the NiSx co-catalyst is not anchored on the surface of the host CZS nanotwins and instead exists in the reaction solution as freestanding subnanometre clusters. We propose that charge transfer is accomplished via collisions between the CZS and NiSx clusters, which aids charge separation and inhibits back reaction, leading to high water reduction rates in the suspension.

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Acknowledgements

This work was supported by the National Nature Science Foundation of China (No. 51236007, No. 51502240), the Natural Science Foundation of Jiangsu Province (No. BK20150378), China Postdoctoral Science Foundation (No. 2014M560769), and the China Fundamental Research Funds for the Central Universities. We also appreciate the help of J. N. Wang, F. Xue, W. Long and P. H. Guo for assistance and thank D. W. Jing for helpful discussions and critical reading of the manuscript.

Author information

Affiliations

  1. International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China

    • Maochang Liu
    • , Yubin Chen
    • , Jinzhan Su
    • , Jinwen Shi
    • , Xixi Wang
    •  & Liejin Guo

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Contributions

L.G., M.L. and Y.C. conceived and designed the experiments. L.G. supervised the project. M.L. and Y.C. prepared the powder and film catalysts and analysed the data. M.L., J.Z.S., J.W.S. and X.W. performed the characterizations including XRD, ultraviolet–visible, TEM and so on. M.L. and L.G. prepared and revised the manuscript. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Maochang Liu or Liejin Guo.

Supplementary information

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  1. 1.

    Supplementary Information

    Supplementary Tables 1–2, Supplementary Figures 1–18.

Videos

  1. 1.

    Supplementary Video 1

    Visible-light-driven H2 evolution from a CZS twinned nanorod film photocatalyst without adding Ni2+ to the Na2S/Na2SO3 solution. The reaction conditions were the same as those used in the photocatalytic tests of the CZS powder photocatalyst. Light Source: 300 W Xenon lamp, λ ≥ 430 nm.

  2. 2.

    Supplementary Video 2

    Visible-light-driven H2 evolution from a CZS twinned nanorod film photocatalyst when 0.03 wt% Ni2+ was added to the Na2S/Na2SO3 solution. The reaction conditions were the same as those used in the photocatalytic tests of the CZS powder photocatalyst. Light Source: 300 W Xenon lamp, λ ≥ 430 nm.

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DOI

https://doi.org/10.1038/nenergy.2016.151