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An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

Abstract

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications1,2,3. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential4 and have fast kinetics5,6,7,8,9. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt–H bond10 is associated with the fastest reaction rate for the HER11,12. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability13,14,15. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (65 kcal mol–1)16, but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s−1 in 0.5 M H2SO4 solution; 0.75 H2 s−1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm–2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

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Figure 1: Schematic illustration of the synthesis and structure of the Ru@C2N electrocatalyst.
Figure 2: Structural characterization and high-resolution transmission electron microscopy analysis of the Ru@C2N catalyst.
Figure 3: HER activity and stability of the Ru@C2N electrocatalyst.
Figure 4: Comparison of the TOF of Ru@C2N with other catalysts.

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Acknowledgements

This work was supported by the Creative Research Initiative (CRI, 2014R1A3A2069102), BK21 Plus (10Z20130011057), Science Research Center (SRC, 2016R1A5A1009405) and Creative Materials Discovery Program (2016M3D1A1900035) programmes through the National Research Foundation (NRF) of Korea.

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J.-B.B. conceived the project and oversaw all the research phases. J.-B.B. and J.M. designed the project, and collected and analysed data. F.L. carried out all the electrochemical experiments and data analysis. I.A. and S.-J.K. were involved in the BET measurements and monomer synthesis. S.-M.J. and H.Y.J. performed the detailed TEM and HR-TEM characterizations. N.P. and M.S.O. carried out the theoretical studies. J.-B.B., J.M., F.L., N.P. and H.Y.J. wrote the paper and discussed the results. All the authors contributed to and commented on this paper.

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Correspondence to Noejung Park, Hu Young Jeong or Jong-Beom Baek.

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The authors declare no competing financial interests.

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Mahmood, J., Li, F., Jung, SM. et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nature Nanotech 12, 441–446 (2017). https://doi.org/10.1038/nnano.2016.304

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