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


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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Figure 1: Photocatalytic performance of CZS-based photocatalysts.
Figure 2: Proposed mechanism involved in the Twin-Ni-I-based photocatalytic process.
Figure 3: Photocatalytic performance of CZS films.
Figure 4: Characterization of the freestanding NiSx particles.
Figure 5: Photocatalytic performance and characterization of the Twin-Pt-I photocatalyst.


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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.

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Authors and Affiliations



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.

Corresponding authors

Correspondence to Maochang Liu or Liejin Guo.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Tables 1–2, Supplementary Figures 1–18. (PDF 1422 kb)

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. (AVI 8028 kb)

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. (AVI 8073 kb)

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Liu, M., Chen, Y., Su, J. et al. Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiSx co-catalyst. Nat Energy 1, 16151 (2016).

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