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Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies

A Corrigendum to this article was published on 24 February 2016

This article has been updated


As a promising non-precious catalyst for the hydrogen evolution reaction (HER; refs 1,2,3,4,5), molybdenum disulphide (MoS2) is known to contain active edge sites and an inert basal plane1,6,7,8. Activating the MoS2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bind directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔGH) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Proper combinations of S-vacancy and strain yield the optimal ΔGH = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.

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Figure 1: Theoretical calculations for the effects of S-vacancies and strain on the HER activity of MoS2.
Figure 2: Effects of S-vacancy and strain on the electronic structure of MoS2.
Figure 3: Experimental creation and quantification of S-vacancies and elastic tensile strain in monolayer 2H-MoS2.
Figure 4: Individual and combined effects of elastic tensile strain and S-vacancies on the HER activity of monolayer MoS2.
Figure 5: Correlation of the intrinsic HER activity of S-vacancy sites between experiments and calculations.

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Change history

  • 18 November 2015

    In the version of this Letter originally published, the topmost tick labels on the y axis in Figs 1b and 1c were incorrect and should have read 2.0. This is now correct in all versions of the Letter.

  • 19 January 2016

    In the version of this Letter originally published, the name of one of the co-authors was misspelled and should have been 'Hyun Soo Han'. This has been corrected in the online versions after print.


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This work was financially supported by the 2013 Global Research Outreach (GRO) Program (Award number IC2012-1318) of the Samsung Advanced Institute of Technology (SAIT) and Samsung R&D Center America, Silicon Valley (SRA-SV) under the supervision of D. Bera and A. Radspieler Jr. We acknowledge support from the Center on Nanostructuring for Efficient Energy Conversion (CNEEC) at Stanford University, an Energy Frontier Research Center funded by the US Department of Energy, Office of Basic Energy Sciences under award number DE-SC0001060. F.A.-P. and J.K.N. acknowledge financial support from the US Department of Energy (DOE), Office of Basic Energy Sciences to the SUNCAT Center for Interface Science and Catalysis. A.W.C., A.H.F. and H.C.M. acknowledge financial support from the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under contract DE-AC02-76SF00515. C.T. acknowledges support from the National Science Foundation Graduate Research Fellowship Program (GRFP) Grant DGE-114747.

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Authors and Affiliations



H.L. and X.Z. conceived the idea and designed the experiments. H.L. performed material growth, electrode fabrication and electrochemical measurements. C.T., J.K.N. and F.A.-P. carried out the theoretical calculations. A.L.K. conducted the TEM characterization. L.C. performed the XPS measurement. A.W.C., A.H.F. and H.C.M. conducted the STM/STS measurements. J.Z. and H.S.H. assisted with the electrochemical measurements. H.L., C.T. and X.Z. wrote the manuscript, and all authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Jens K. Nørskov or Xiaolin Zheng.

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The authors declare no competing financial interests.

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Li, H., Tsai, C., Koh, A. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nature Mater 15, 48–53 (2016).

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