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Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution

Abstract

Efficient evolution of hydrogen through electrocatalysis at low overpotentials holds tremendous promise for clean energy. Hydrogen evolution can be easily achieved by electrolysis at large potentials that can be lowered with expensive platinum-based catalysts. Replacement of Pt with inexpensive, earth-abundant electrocatalysts would be significantly beneficial for clean and efficient hydrogen evolution. To this end, promising results have been reported using 2H (trigonal prismatic) XS2 (where X = Mo or W) nanoparticles with a high concentration of metallic edges. The key challenges for XS2 are increasing the number and catalytic activity of active sites. Here we report monolayered nanosheets of chemically exfoliated WS2 as efficient catalysts for hydrogen evolution with very low overpotentials. Analyses indicate that the enhanced electrocatalytic activity of WS2 is associated with the high concentration of the strained metallic 1T (octahedral) phase in the as-exfoliated nanosheets. Our results suggest that chemically exfoliated WS2 nanosheets are interesting catalysts for hydrogen evolution.

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Figure 1: Structure of chemically exfoliated WS2.
Figure 2: HER electrocatalytic properties of exfoliated WS2 nanosheets.
Figure 3: 1T phase stability and free-energy diagram for hydrogen evolution at equilibrium (U = 0) with tensile strain in atomically thin 1T WS2.

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Acknowledgements

M. Chhowalla acknowledges financial support from NSF DGE 0903661. H.Y. acknowledges the Japan Society for the Promotion of Science (JSPS) for financial support through Postdoctoral Fellowship for Research Abroad. G.E. acknowledges financial support from NRF Singapore. J.L. and V.B.S. acknowledge support from Army Research Office through Contract W911NF-11-1-0171. T.A. acknowledges financial assistance from NSF (CAREER CHE-1004218, DMR-0968937, NanoEHS-1134289, NSF-ACIF, and Special Creativity Grant). R.S. and D.C.B.A. acknowledge the Coordenação de Aperfeiçoamento de Pessoal de Nı´vel Superior, Brazil for fellowships. R.S. also acknowledges the Fulbright Agency, USA for financial support. T.F. acknowledges partial support from JST-PRESTO ‘New Materials Science and Element Strategy’ and JSPS, Grant-in-Aid for challenging Exploratory Research (24656028). We thank M. Salehi for the AFM images.

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M. Chhowalla conceived the idea, designed the experiments, analysed the data and wrote the manuscript. D.V. conceived the idea and designed the experiments with M. Chhowalla, synthesized the WS2 nanosheets, characterized them with AFM, Raman and XPS, performed the HER measurements and analysed the data. H.Y. assisted in the synthesis and characterization of materials. J.L. and V.S. performed the theoretical work. T.F. and M. Chen performed the TEM work. R.S., D.C.B.A. and T.A. assisted D.V. with the HER measurements. G.E. analysed the TEM and strain data as well as editing the manuscript. All of the authors have read the manuscript and agree with its content.

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Correspondence to Manish Chhowalla.

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Voiry, D., Yamaguchi, H., Li, J. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nature Mater 12, 850–855 (2013). https://doi.org/10.1038/nmat3700

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