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Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction

Nature Materials volume 15, pages 197–203 (2016)Cite this article

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Abstract

Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co2+ and Mo4+ centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

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Figure 1: Effects of Sadδ− on the HER and the structure of double layer.
Figure 2: Ex situ materials characterization of as-synthesized TMSx chalcogels.
Figure 3: In situ characterization of TMSx and trends in activity for the HER on TMSx reveal that CoMoSx is a pH-universal catalyst.
Figure 4: Activity–stability relationship of TMSx for the HER in acid and alkaline environments.

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Acknowledgements

This work was supported by the Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences, US Department of Energy, under contract DE-AC02-06CH11357 (BES-DMSE). This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

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Authors and Affiliations

  1. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Jakub Staszak-Jirkovský, Christos D. Malliakas, Pietro P. Lopes, Nemanja Danilovic, Kee-Chul Chang, Bostjan Genorio, Dusan Strmcnik, Vojislav R. Stamenkovic, Mercouri G. Kanatzidis & Nenad M. Markovic

  2. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA

    Christos D. Malliakas, Subrahmanyam S. Kota & Mercouri G. Kanatzidis

  3. University of Ljubljana, Ljubljana 1000, Slovenia

    Bostjan Genorio

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Contributions

J.S.-J., C.D.M., M.G.K. and N.M.M. developed the idea and designed the experiments. J.S.-J., P.P.L. and N.D. performed the electrochemical experiments. S.S.K. synthesized the materials, C.D.M., S.S.K. and J.S.-J. characterized the materials. N.D., J.S.-J. and K.-C.C. performed the in situ experiments. J.S.-J., P.P.L., N.D., B.G., D.S., V.R.S. and N.M.M. analysed and discussed electrochemical results. J.S.-J., C.D.M., M.G.K. and N.M.M. co-wrote the paper. J.S.-J. and C.D.M. have contributed equally to this work.

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Correspondence to Mercouri G. Kanatzidis or Nenad M. Markovic.

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Staszak-Jirkovský, J., Malliakas, C., Lopes, P. et al. Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nature Mater 15, 197–203 (2016). https://doi.org/10.1038/nmat4481

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