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

Nature Materials volume 15, pages 48–53 (2016)Cite this article

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A Corrigendum to this article was published on 24 February 2016

This article has been updated

Abstract

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.

References

  1. Hinnemann, B. et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127, 5308–5309 (2005).

    Article  CAS  Google Scholar 

  2. Greeley, J. et al. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nature Mater. 5, 909–913 (2006).

    Article  CAS  Google Scholar 

  3. Merki, D. & Hu, X. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energy Environ. Sci. 4, 3878–3888 (2011).

    Article  CAS  Google Scholar 

  4. Chen, W.-F., Muckerman, J. T. & Fujita, E. Recent developments intransition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem. Commun. 49, 8896–8909 (2013).

    Article  CAS  Google Scholar 

  5. Benck, J. D., Hellstern, T. R., Kibsgaard, J., Chakthranont, P. & Jaramillo, T. F. Catalyzing the hydrogen evolution reaction (HER) with molybdenum sulfide nanomaterials. ACS Catal. 4, 3957–3971 (2014).

    Article  CAS  Google Scholar 

  6. Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

    Article  CAS  Google Scholar 

  7. Li, Y. et al. MoS2 nanoparticles grown on graphene: An advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).

    Article  CAS  Google Scholar 

  8. Chang, K. et al. MoS2/graphene cocatalyst for efficient photocatalytic H2 evolution under visible light irradiation. ACS Nano 8, 7078–7087 (2014).

    Article  CAS  Google Scholar 

  9. Kong, D. et al. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett. 13, 1341–1347 (2013).

    Article  CAS  Google Scholar 

  10. Chen, Z. et al. Core–shell MoO3–MoS2 nanowires for hydrogen evolution: A functional design for electrocatalytic materials. Nano Lett. 11, 4168–4175 (2011).

    Article  CAS  Google Scholar 

  11. Xie, J. et al. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 25, 5807–5813 (2013).

    Article  CAS  Google Scholar 

  12. Kibsgaard, J., Chen, Z., Reinecke, B. N. & Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nature Mater. 11, 963–969 (2012).

    Article  CAS  Google Scholar 

  13. Bonde, J., Moses, P. G., Jaramillo, T. F., Nørskov, J. K. & Chorkendorff, I. Hydrogen evolution on nano-particulate transition metal sulfides. Faraday Discuss. 140, 219–231 (2009).

    Article  Google Scholar 

  14. Wang, H. et al. Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution. Nano Res. 8, 566–575 (2015).

    Article  CAS  Google Scholar 

  15. Lukowski, M. A. et al. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 135, 10274–10277 (2013).

    Article  CAS  Google Scholar 

  16. Voiry, D. et al. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 13, 6222–6227 (2013).

    Article  CAS  Google Scholar 

  17. Nørskov, J. K. et al. Universality in heterogeneous catalysis. J. Catal. 209, 275–278 (2002).

    Article  Google Scholar 

  18. Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).

    Article  Google Scholar 

  19. Greeley, J. & Mavrikakis, M. Alloy catalysts designed from first principles. Nature Mater. 3, 810–815 (2004).

    Article  CAS  Google Scholar 

  20. Michalsky, R., Zhang, Y.-J. & Peterson, A. A. Trends in the hydrogen evolution activity of metal carbide catalysts. ACS Catal. 4, 1274–1278 (2014).

    Article  CAS  Google Scholar 

  21. Tsai, C., Abild-Pedersen, F. & Nørskov, J. K. Tuning the MoS2 edge-site activity for hydrogen evolution via support interactions. Nano Lett. 14, 1381–1387 (2014).

    Article  CAS  Google Scholar 

  22. Tsai, C., Chan, K., Abild-Pedersen, F. & Nørskov, J. K. Theoretical insights into the hydrogen evolution activity of layered transition metal dichalcogenides. Surf. Sci. 640, 133–140 (2015).

    Article  CAS  Google Scholar 

  23. Strasser, P. et al. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. Nature Chem. 2, 454–460 (2010).

    Article  CAS  Google Scholar 

  24. Voiry, D. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nature Mater. 12, 850–855 (2013).

    Article  CAS  Google Scholar 

  25. Yildiz, B. “Stretching” the energy landscape of oxide-effects on electrocatalysis diffusion. MRS Bull. 39, 147–156 (2014).

    Article  CAS  Google Scholar 

  26. Li, H. et al. Optoelectronic crystal of artificial atoms in strain-textured MoS2 . Nature Commun. 6, 7381 (2015).

    Article  CAS  Google Scholar 

  27. Quan, M. et al. Controlled argon beam-induced desulfurization of monolayer molybdenum disulfide. J. Phys. Condens. Matter. 25, 252201 (2013).

    Article  Google Scholar 

  28. Kibsgaard, J., Jaramillo, T. F. & Besenbacher, F. Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters. Nature Chem. 6, 248–253 (2014).

    Article  CAS  Google Scholar 

  29. Jaramillo, T. F. et al. Hydrogen evolution on supported incomplete cubane-type [Mo3S4]4+ electrocatalysts. J. Phys. Chem. C 112, 17492–17498 (2008).

    Article  CAS  Google Scholar 

  30. Remskar, M. et al. Self-assembly of subnanometer-diameter single-wall MoS2 nanotubes. Science 292, 479–481 (2001).

    Article  CAS  Google Scholar 

  31. Wellendorff, J. et al. Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation. Phys. Rev. B 85, 235149 (2012).

    Article  Google Scholar 

  32. Gohda, Y., Schnur, S. & Groß, A. Influence of water on elementary reaction steps in electrocatalysis. Faraday Discuss. 140, 233–244 (2009).

    Article  Google Scholar 

  33. Kuisma, M., Ojanen, J., Enkovaara, J. & Rantala, T. T. Kohn–Sham potential with discontinuity for band gap materials. Phys. Rev. B 82, 115106 (2010).

    Article  Google Scholar 

  34. Najmaei, S. et al. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. Nature Mater. 12, 754–759 (2013).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

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.

Author information

Author notes

  1. Hong Li and Charlie Tsai: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Mechanical Engineering, Stanford University, Stanford, California 94305, USA

    Hong Li, Lili Cai, Jiheng Zhao, Hyun Soo Han & Xiaolin Zheng

  2. Department of Chemical Engineering, SUNCAT Center for Interface Science and Catalysis, Stanford University, 450 Serra Mall Stanford, California 94305, USA,

    Charlie Tsai & Jens K. Nørskov

  3. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road Menlo Park, California 94025, USA,

    Charlie Tsai, Frank Abild-Pedersen & Jens K. Nørskov

  4. Stanford Nanocharacterization Laboratory, Stanford University, California 94305, USA

    Ai Leen Koh

  5. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road Menlo Park, California 94025, USA,

    Alex W. Contryman, Alex H. Fragapane & Hari C. Manoharan

  6. Department of Applied Physics, Stanford University, Stanford, California 94305, USA

    Alex W. Contryman & Alex H. Fragapane

  7. Department of Physics, Stanford University, Stanford, California 94305, USA

    Hari C. Manoharan

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Contributions

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). https://doi.org/10.1038/nmat4465

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