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Proton Relay Mediated Electrocatalytic Hydrogen Evolution by an Economic Co(III) Complex

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Abstract

Bis(iminidiacetato)cobaltate(III) complex has been evaluated for electrocatalytic proton reduction. The process follows a rare pathway of protonation of ligand upon addition of a weak acid in DMF/water (9:1 v/v) medium. Thus, the complex becomes electroactive only in the presence of acid. In the presence of weak acid, a new reduction peak corresponding to CoI/Co0 reduction is observed. The electrocatalytic activity towards proton reduction reaction is exhibited by this peak. An electrochemical-chemical-electrochemical (ECE) route initiated by proton relay on ligand site has been established for the electrocatalytic process. The catalytic activity of the complex in DMF/water medium was evaluated by controlled potential electrolysis, turnover number (TON), and turnover frequency (TOF).

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Acknowledgements

We are thankful to Dr. A. K. Tyagi, Director, Chemistry Group, BARC and Dr. Awadhesh Kumar, Head, Radiation & Photochemistry Division, BARC for their keen interest and encouragement in carrying out this work. We thank Mr. Amey P. Wadawale, ChD, BARC for helping us with the single crystal XRD measurement.

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Authors and Affiliations

  1. Radiation & Photochemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India

    D. Majumder & V. S. Tripathi

  2. Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India

    S. Kolay

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Contributions

Dwipayan Majumder: carried out synthesis, electrochemical studies, and data analysis and prepared the manuscript. Siddhartha Koley: characterized the complex by elemental analysis, XRD, NMR, and IR. Vaidehi Sharan Tripathi: conceptualizing the study, data curation, and manuscript writing.

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Correspondence to V. S. Tripathi.

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Majumder, D., Kolay, S. & Tripathi, V.S. Proton Relay Mediated Electrocatalytic Hydrogen Evolution by an Economic Co(III) Complex. Electrocatalysis 14, 602–610 (2023). https://doi.org/10.1007/s12678-023-00823-0

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