The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen

Abstract

The excellent catalytic activity of metallic MoS2 edges for the hydrogen evolution reaction (HER) has led to substantial efforts towards increasing the edge concentration. The 2H basal plane is less active for the HER because it is less conducting and therefore possesses less efficient charge transfer kinetics. Here we show that the activity of the 2H basal planes of monolayer MoS2 nanosheets can be made comparable to state-of-the-art catalytic properties of metallic edges and the 1T phase by improving the electrical coupling between the substrate and the catalyst so that electron injection from the electrode and transport to the catalyst active site is facilitated. Phase-engineered low-resistance contacts on monolayer 2H-phase MoS2 basal plane lead to higher efficiency of charge injection in the nanosheets so that its intrinsic activity towards the HER can be measured. We demonstrate that onset potentials and Tafel slopes of −0.1 V and 50 mV per decade can be achieved from 2H-phase catalysts where only the basal plane is exposed. We show that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal plane. Our results provide new insights into the role of contact resistance and charge transport on the performance of two-dimensional MoS2 nanosheet catalysts for the HER.

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Figure 1: Electrochemical set-up for the HER measurement on single-layer MoS2.
Figure 2: Electrochemical measurements from individual single-layer MoS2 nanosheets.
Figure 3: Influence of the contact resistance on the HER performances of MoS2.
Figure 4: HAADF-STEM observations of sulfur vacancies in single-layer MoS2 nanosheets.

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Acknowledgements

M.C. and D.V. acknowledge financial support from NSF DGE 0903661 and ECCS 1128335. T.A. acknowledges financial assistance from NSF (CAREER CHE-1004218, DMR-0968937, NanoEHS-1134289, NSF-ACIF, and Special Creativity Grant). C.d.C.C.e.S. acknowledges the Conselho Nacional de Desenvolvimento Científico e Tecnológico-Brazil, for a fellowship. J.Y. and M.C. acknowledge financial support from Rutgers Energy Institute. A.M. acknowledges LDRD program at LANL for funding this work. M.J.L. and P.E.B. acknowledge support from the US DOE, Office of Science, BES Award No. DE-SC0005132 and NSF No. 0959905. L.B., D.E., and V.B.S. acknowledge EFMA-542879, CMMI-1363203 and CBET-1235870 from the US National Science Foundation.

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M.C. and D.V. conceived the idea and designed the experiments. D.V. performed the HER measurements and the physical characterizations of the samples. M.C. and D.V. analysed the data and wrote the manuscript. R.F. and R.K. fabricated the devices and helped D.V. with the contact resistance calculations. C.d.C.C.e.S. and J.Y. assisted D.V. with the HER measurements. D.K. and I.B. synthesized the single-layer MoS2 nanosheets. M.J.L. and P.E.B. carried out the STEM measurements on MoS2. L.D. and D.E. performed the DFT calculations. V.B.S. discussed the results of the DFT calculations with M.C. and D.V.; G.G., A.D.M. and T.A. discussed the results with M.C. and D.V.

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Correspondence to Manish Chhowalla.

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Voiry, D., Fullon, R., Yang, J. et al. The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nature Mater 15, 1003–1009 (2016). https://doi.org/10.1038/nmat4660

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