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The Effect of Noncovalent Interactions on the HOR, ORR, and HER on Ru, Ir, and Ru0.50Ir0.50 Metal Surfaces in Alkaline Environments

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Abstract

The role of noncovalent interactions in the hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) on Ru, Ir, and Ru0.5Ir0.5 electrodes is studied in alkaline solution containing K+, Li+, and Ba2+ cations. We found that noncovalent interaction between hydrated cations and covalently bonded OHad increases in the same order as specific charge density of the corresponding cation (K+ < Li+ < Ba2+). This interaction is also found to cause an increase in the density of OHad·····Mn+(H2O) x clusters in the compact part of double layer. The trend in interaction strengths is inversely proportional to the activity of the HOR and ORR, which suggests that the clusters “block” the metal active sites necessary for the adsorption of H2 and O2. In the case of the HER, however, we demonstrate that the activity is directly proportional to the strength of these noncovalent interactions. To explain this behavior, we suggest that the hydrated cations affect the rate of the water dissociation step which increases in the order K+ < Li+ < Ba2+.

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Acknowledgments

This work was supported by the Office of Science, Office of Basic Energy Sciences, Division of Materials Science, U.S. Department of Energy, under contract DE-AC0-06CH11357 and the Chemical Sciences and Engineering Division at Argonne National Laboratory. RS and ND would like to thank the Argonne Postdoctoral Fellowships for the funding.

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Authors and Affiliations

  1. Chemical Science and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439, USA

    N. Danilovic & D. Myers

  2. Materials Science Division, Argonne National Laboratory, Argonne, IL, 60439, USA

    N. Danilovic, Ram Subbaraman, D. Strmcnik, A. P. Paulikas, V. R. Stamenkovic & N. M. Markovic

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  1. N. Danilovic
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  2. Ram Subbaraman
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  3. D. Strmcnik
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  6. V. R. Stamenkovic
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  7. N. M. Markovic
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Correspondence to N. M. Markovic.

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Danilovic, N., Subbaraman, R., Strmcnik, D. et al. The Effect of Noncovalent Interactions on the HOR, ORR, and HER on Ru, Ir, and Ru0.50Ir0.50 Metal Surfaces in Alkaline Environments. Electrocatalysis 3, 221–229 (2012). https://doi.org/10.1007/s12678-012-0100-7

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