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Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis

Nature Materials volume 11, pages 963–969 (2012)Cite this article

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Abstract

Controlling surface structure at the atomic scale is paramount to developing effective catalysts. For example, the edge sites of MoS2 are highly catalytically active and are thus preferred at the catalyst surface over MoS2 basal planes, which are inert. However, thermodynamics favours the presence of the basal plane, limiting the number of active sites at the surface. Herein, we engineer the surface structure of MoS2 to preferentially expose edge sites to effect improved catalysis by successfully synthesizing contiguous large-area thin films of a highly ordered double-gyroid MoS2 bicontinuous network with nanoscaled pores. The high surface curvature of this catalyst mesostructure exposes a large fraction of edge sites, which, along with its high surface area, leads to excellent activity for electrocatalytic hydrogen evolution. This work elucidates how morphological control of materials at the nanoscale can significantly impact the surface structure at the atomic scale, enabling new opportunities for enhancing surface properties for catalysis and other important technological applications.

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Figure 1
Figure 2: Structural characterization of the double-gyroid morphology.
Figure 3: Spectroscopic characterization of double-gyroid MoS2 from various Mo electrodeposition times.
Figure 4: SEM images of double-gyroid MoS2 films.
Figure 5: TEM images of double-gyroid MoS2.
Figure 6: HER activity of double-gyroid MoS2.

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Acknowledgements

All physical and electrochemical characterization was supported by the Center on Nanostructuring for Efficient Energy Conversion at Stanford University, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0001060. Early stage development of the synthetic procedure to obtain double-gyroid MoS2 was supported by the US Department of Energy, Office of Energy Efficiency & Renewable Energy, under subcontract NFT-9-88567-01 under Prime Contract No. DE-AC36-08GO28308. We thank J. Opatkiewicz for assistance with Raman spectroscopy measurements and BASF for generously providing the surfactant Pluronic P84. We also thank J. Benck and P. C. K. Vesborg for helpful discussion. J.K. gratefully acknowledges the Villum Kann Rasmussen Foundation for a postdoctoral fellowship.

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  1. Jakob Kibsgaard and Zhebo Chen: These authors contributed equally to this work

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

    Jakob Kibsgaard, Zhebo Chen, Benjamin N. Reinecke & Thomas F. Jaramillo

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Contributions

J.K. and Z.C. carried out synthesis of the double-gyroid MoS2 and performed XPS, XRD, SEM, Raman and electrochemical measurements. B.N.R. performed TEM imaging. J.K., Z.C. and T.F.J. conceived the study and wrote the manuscript.

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Correspondence to Thomas F. Jaramillo.

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Kibsgaard, J., Chen, Z., Reinecke, B. et al. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nature Mater 11, 963–969 (2012). https://doi.org/10.1038/nmat3439

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