Article | Published:

Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters

Nature Chemistry volume 6, pages 248253 (2014) | Download Citation

Abstract

Identifying and understanding the active sites responsible for reaction turnover is critical to developing improved catalysts. For the hydrogen-evolution reaction (HER), MoS2 has been identified as an active non-noble-metal-based catalyst. However, only edge sites turnover the reaction because the basal planes are catalytically inert. In an effort to develop a scalable HER catalyst with an increased number of active sites, herein we report a Mo–S catalyst (supported thiomolybdate [Mo3S13]2− nanoclusters) in which most sulfur atoms in the structure exhibit a structural motif similar to that observed at MoS2 edges. Supported sub-monolayers of [Mo3S13]2− nanoclusters exhibited excellent HER activity and stability in acid. Imaging at the atomic scale with scanning tunnelling microscopy allowed for direct characterization of these supported catalysts. The [Mo3S13]2− nanoclusters reported herein demonstrated excellent turnover frequencies, higher than those observed for other non-precious metal catalysts synthesized by a scalable route.

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Acknowledgements

J.K. gratefully acknowledges the Carlsberg Foundation for a postdoctoral fellowship. J.K. and T.F.J. acknowledge support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-SC0008685. We thank Z. Chen for helpful discussion and A. V. Malkovskiy for assistance with Raman spectroscopy measurements.

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Affiliations

  1. Interdisciplinary Nanoscience Center and Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark

    • Jakob Kibsgaard
    •  & Flemming Besenbacher
  2. Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA

    • Jakob Kibsgaard
    •  & Thomas F. Jaramillo

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Contributions

J.K. conceived the studies and performed the experimental work. J.K., T.F.J. and F.B. conducted data analysis and co-wrote the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Flemming Besenbacher.

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DOI

https://doi.org/10.1038/nchem.1853

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