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Combined effect of inherent residual chloride and bound water content and surface morphology on the intrinsic electron-transfer activity of ruthenium oxide

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Abstract

RuO2 is an unparalleled electrode with wider applications. Chloride, bound water, and surface stoichiometry are the inherent residues of RuO2 left upon the high-temperature pyrolysis of a RuCl3⋅xH2O precursor. Although the electrocatalytic properties of RuO2 for specific applications have been studied extensively, there is a paucity of studies linking the intrinsic electron-transfer (ET) activity of RuO2 with the oxide preparation temperature-dependent inherent residual parameters. This paper presents the intrinsic ET activity-oxide residue correlations for RuO2 electrodes. The ET kinetic parameters were estimated using a surface oxide-sensitive Fe3+/Fe2+ redox probe by rotating disc electrode voltammetry. Oxide powder-based electrodes (RuO2 powder-PVC/Pt-modified electrodes), which were fabricated conveniently at room temperature even with high-temperature oxides, were used instead of the traditional thermally prepared electrodes to circumvent the primary problems at the coating|support interface and inefficient chloride removal. RuO2 powders prepared at five temperatures (Tprep), i.e., 300, 400, 500, 600, and 700 °C, were used for electrode fabrication. The results showed that the electron exchange rate was highest for the 400 °C RuO2 electrode, and it was independent of the Tprep in the range 500 to 700 °C. The oxide powders were characterized using a range of techniques. The measured intrinsic ET activity and the associated structural correlation over the Tprep range 300–700 °C suggest that the best activity of the 400 °C electrode can be attributed to the optimal chloride and bound water contents in a completely formed rutile surface layer containing the catalyst sites of a particular nature with the highest electroactivity.

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Acknowledgements

K.C.P thanks the Korea Federation of Science and Technology Societies (KOFST, Republic of Korea) for the offer of Invited Scientist through the ‘Brain Pool Program’.

Funding

This study was supported by the National Research Foundation of Korea (NRF) funded by the Korea government (MEST) (Grant No. 2017R1A2A1A05001484) and the Council of Scientific and Industrial Research (CSIR), Government of India.

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Author notes

  1. Annamalai Senthil Kumar

    Present address: Nano and Bioelectrochemistry Research Laboratory, Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology University, Vellore, 632014, India

  2. Annamalai Senthil Kumar

    Present address: Institute of Biochemical and Biomedical Engineering, National Taipei University of Technology, Taipei, 10608, Taiwan, Republic of China

Authors and Affiliations

  1. Department of Physical Chemistry, University of Madras, Guindy Campus, Chennai, 600 025, India

    K. Chandrasekara Pillai & Annamalai Senthil Kumar

  2. Department of Chemical Engineering, Sunchon National University, Suncheon, 540-742, South Korea

    K. Chandrasekara Pillai & Il-Shik Moon

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  1. K. Chandrasekara Pillai
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  2. Annamalai Senthil Kumar
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Correspondence to K. Chandrasekara Pillai or Il-Shik Moon.

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Pillai, K.C., Kumar, A.S. & Moon, IS. Combined effect of inherent residual chloride and bound water content and surface morphology on the intrinsic electron-transfer activity of ruthenium oxide. J Solid State Electrochem 22, 2183–2196 (2018). https://doi.org/10.1007/s10008-018-3917-z

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  • DOI: https://doi.org/10.1007/s10008-018-3917-z

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