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Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

Nature Energy volume 2, Article number: 17127 (2017) Cite this article

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Abstract

Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm−2 current density at an overpotential of ∼50–60 mV with a loading of 10–55 μg cm−2, surpassing other reported MX2 candidates without any performance-enhancing additives.

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Figure 1: Electronic origin of MX2 surface activity and the derived descriptor (εLUS) for catalysts screening.
Figure 2: HER electrocatalysis on H-TaS2 and H-NbS2.
Figure 3: Morphological evolution of H-TaS2 following cycling.
Figure 4: Chemical intactness and origin of self-optimizing behaviour.

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Acknowledgements

We thank W. Zhou (ORNL), W. I. Choi (LLNL), A. Mohite and G. Gupta (LANL) for valuable discussions. B.C.W. and Y.L. acknowledge funding from LLNL LDRD Grant 12-ERD-053, with computing support from the LLNL Institutional Computing Grand Challenge Program. T.O. and B.C.W. acknowledge additional support from the US Department of Energy (DOE) Fuel Cell Technologies Office. Y.M.W. acknowledges the UCOP funding support on mesoscopic 2D materials. A portion of this work was performed under the auspices of the US DOE by LLNL under Contract DE-AC52-07NA27344. K.P.H. acknowledges funding from PIRE-2 Grant OISE-0968405. J.W. and K.K. acknowledge funding from MURI 2D Grant W911NF-11-1-0362. Y.Y., J.Z. and J.L. acknowledge support from the Welch Foundation grant C-1716. Y.L. and B.I.Y. acknowledge support from the Office of Naval Research Grant N00014-15-1-2372 and the Army Research Office Grant W911NF-16-1-0255. This work used computing resources sponsored by the DOE Office of EERE at NREL, and the NSF XSEDE Grant ACI-1053575.

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Author notes

  1. Yuanyue Liu

    Present address: California Institute of Technology, Pasadena, California, 91125, USA

  2. Yuanyue Liu, Jingjie Wu and Ken P. Hackenberg: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science and Nano-Engineering, Rice University, Houston, Texas, 77005, USA

    Yuanyue Liu, Jingjie Wu, Ken P. Hackenberg, Jing Zhang, Yingchao Yang, Kunttal Keyshar, Robert Vajtai, Jun Lou, Pulickel M. Ajayan & Boris I. Yakobson

  2. Materials Science Division, Lawrence Livermore National Laboratory, Livermore, California, 94550, USA

    Y. Morris Wang, Tadashi Ogitsu & Brandon C. Wood

  3. Department of Chemistry and Biochemistry, San Diego State University, San Diego, California, 92182, USA

    Jing Gu

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Contributions

Y.L. conceived the idea and performed the theory calculations with guidance from T.O., B.C.W. and B.I.Y. K.P.H. synthesized the samples. J.W. performed the electrochemical testing. J.W. and K.P.H. performed a majority of the materials characterization, under the guidance of R.V., J.L. and P.M.A. Other authors provided additional sample characterization.

Corresponding authors

Correspondence to Brandon C. Wood or Boris I. Yakobson.

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Supplementary Information

Supplementary Discussion, Supplementary Figures 1–18, Supplementary Table 1 and Supplementary References. (PDF 2542 kb)

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Liu, Y., Wu, J., Hackenberg, K. et al. Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution. Nat Energy 2, 17127 (2017). https://doi.org/10.1038/nenergy.2017.127

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