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Doped rhodium sulfide and thiospinels hydrogen evolution and oxidation electrocatalysts in strong acid electrolytes

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Abstract

Hydrogen evolution and oxidation activity of several carbon-supported rhodium thiospinels (CuRh2S4, CoRh2S4, FeRh2S4, and NiRh2S4) are evaluated in sulfuric acid and compared with Ir, Ru, and Pd-doped and undoped Rh17S15 on carbon. The metal sulfides are synthesized on carbon by reacting metal chlorides with hydrogen sulfide at 350 °C. Mixtures of Cu, Co, Fe, and Ni salts with RhCl3 formed thiospinels. The minority metals, Pd, Ru, or Ir, incorporate into the Rh17S15 structure at low concentrations (1 %). The hydrogen evolution and oxidation activities of the thiospinels in sulfuric acid are lower than pure Rh17S15/C, with NiRh2S4/C showing the highest activity of the thiospinels, and CuRh2S4/C seen to be unstable in sulfuric acid, even for short times (1 min). The hydrogen evolution and oxidation activities normalized to an estimate of the electrocatalyst area for the 1 % Pd, Ru, and Ir in Rh17S15/C are slightly lower than pure Rh17S15/C and all metal sulfides have a lower hydrogen evolution activity than platinum, even when normalizing to surface area.

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Acknowledgments

Financial support was by the National Science Foundation (EFRI-1038234). The MRL Shared Experimental Facilities are supported by the MRSEC Program of the NSF under Award No. DMR 1121053; a member of the NSF-funded Materials Research Facilities Network. We would like to thank Stephan Kraemer for the assistance with TEM.

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Authors and Affiliations

  1. Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, CA, 93106-5080, USA

    Nirala Singh, Michael Gordon & Eric McFarland

  2. Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA, 93106-9510, USA

    Horia Metiu

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  1. Nirala Singh
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  2. Michael Gordon
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  3. Horia Metiu
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  4. Eric McFarland
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Correspondence to Eric McFarland.

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Singh, N., Gordon, M., Metiu, H. et al. Doped rhodium sulfide and thiospinels hydrogen evolution and oxidation electrocatalysts in strong acid electrolytes. J Appl Electrochem 46, 497–503 (2016). https://doi.org/10.1007/s10800-016-0938-0

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  • DOI: https://doi.org/10.1007/s10800-016-0938-0

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