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Structural and Chemical Transformations of Ruthenium, Cobalt, and Iron Clathrochelates Used as Electrocatalysts for a Hydrogen Evolution Reaction in a Water Electrolyzer

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Abstract

The structural evolution of three electrocatalytic systems for hydrogen evolution reaction using iron, cobalt, and ruthenium(II) clathrochelate complexes as catalysts in a water electrolyzer is studied by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. The complexes are shown to display essentially different robustness under water electrolysis conditions in pilot-scale hydrogen generators. The iron and cobalt(II) clathrochelates preserve their cage, macrobicyclic structure, and the encapsulated metal(II) ion is  reduced  to  metal(I) cation; whereas in the case of ruthenium(II) clathrochelate, the cage complex undergoes partial decomposition to form sulfur-containing products of decomposition of the encapsulating macrobicyclic hexasulfide ligand, which results in the accumulation of the ruthenium disulfide RuS2 in used clathrochelate-containing cathode material. Taking into account our experimental data on the chemical transformation of clathrochelate electrocatalysts under the conditions of 2Н+/Н2 reaction, we discuss the possibilities for boosting the efficiency of electrocatalytic systems based on this class of coordination compounds.

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Funding

The work was supported by the Russian Science Foundation within project no. 17-13-01468 (the syntheses of cage complexes); the Russian Foundation for Basic Research within grant no. 18-29-23007 (electrocatalysis experiments; Ya.Z. Voloshin), grant no. 19-58-26022 (investigations of membrane-electrode assemblies of water electrolyzer; S.A. Grigor’ev and A.S. Pushkarev); and with partial support from the Ministry of Education and Science, Russian Federation (project AAAA-A19-119020890025-3; quantitative analysis of XANES and EXAFS spectra by Ya.V. Zubavichus). Adsorption studies were carried out within a state assignment to the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, in the area of fundamental scientific research.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    Ya. V. Zubavichus

  2. National Research Center “Kurchatov Institute”, Moscow, Russia

    S. A. Grigor’ev, A. S. Pushkarev & M. M. Borisov

  3. National Research University “Moscow Power Engineering Institute”, Moscow, Russia

    S. A. Grigor’ev

  4. Gubkin National University of Oil and Gas, Moscow, Russia

    M. G. Bugaenko, Ya. Z. Voloshin & A. G. Dedov

  5. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    Ya. Z. Voloshin

  6. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia

    A. G. Dedov

Authors
  1. Ya. V. Zubavichus
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  2. S. A. Grigor’ev
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  3. A. S. Pushkarev
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  4. M. M. Borisov
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  5. M. G. Bugaenko
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  6. Ya. Z. Voloshin
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  7. A. G. Dedov
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Corresponding authors

Correspondence to Ya. V. Zubavichus or Ya. Z. Voloshin.

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Translated by A. Kukharuk

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Zubavichus, Y.V., Grigor’ev, S.A., Pushkarev, A.S. et al. Structural and Chemical Transformations of Ruthenium, Cobalt, and Iron Clathrochelates Used as Electrocatalysts for a Hydrogen Evolution Reaction in a Water Electrolyzer. Nanotechnol Russia 15, 341–349 (2020). https://doi.org/10.1134/S1995078020030179

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  • DOI: https://doi.org/10.1134/S1995078020030179

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