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Tailoring the electrochemical charge storage properties of carbonaceous support by redox properties of heteropoly acids: where does the synergy come from?

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Abstract

The synergistic effects between two Keggin-type heteropoly acids (HPAs) and carbon surface were examined and elucidated. An improved high rate capability (and potential high capacitor electrode for supercapacitors) of the hybrid materials, obtained by anchoring of α-dodecamolybdophosphoric (MoPA), α-dodecatungstophosphoric (WPA), and their mixture to activated carbon (AC), was achieved through the different mechanism of interaction. In order to elaborate this, a detailed analysis of AC-HPA composites has been performed by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, temperature-programmed desorption (TPD), Fourier-transform infrared spectroscopy (FTIR), micro Raman spectroscopy, and zeta potential measurements. The zeta potential measurements revealed positive charge of carbon surface thus indicating attractive interactions with negatively charged Keggin anion. The surface analysis has shown that WPA spontaneously reduces the carbon surface, while interaction with MoPA leads to its oxidation. As the consequence of the tailoring of the functional groups at carbon surface through HPAs’ action, the distortion of cyclic voltammograms (CVs) decreased in the following order: AC-MoPA, AC-MoPA-WPA, and AC-WPA. A prominent rectangular shape of AC-WPA, even at an extremely high scan rate of 400 mVs−1, was measured, which is rarely demonstrated for carbon-based composites. By applying the theory of electrode potentials, the HPA-AC synergistic effect was explained and discussed in terms of charge storage improvement of HPA-modified carbon.

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Funding

The research was financially supported by the Ministry of Education, Science and Technological Development of Republic of Serbia (Projects OI 172043, III45006, and III45014) and by the Slovenian Research Agency (Project P2-0091). The authors would like to thank Damjan Vengust from the Advanced Materials Department, Jožef Stefan Institute for the help with the SEM-EDS analysis.

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Authors and Affiliations

  1. Faculty of Physical Chemistry, University of Belgrade, PO Box 47, 11158, Belgrade, Serbia

    Danica Bajuk-Bogdanović, Ivanka Holclajtner-Antunović & Milica Vujković

  2. Laboratory of Physics, Vinča Institute of Nuclear Sciences, University of Belgrade, PO Box 522, 11001, Belgrade, Serbia

    Zoran Jovanović & Željko Mravik

  3. Center of Excellence for Hydrogen and Renewable Energy (CONVINCE), Vinča Institute of Nuclear Sciences, University of Belgrade, PO Box 522, 11001, Belgrade, Serbia

    Zoran Jovanović

  4. Advanced Materials Department, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana, Slovenia

    Zoran Jovanović

  5. Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11000, Belgrade, Serbia

    Jugoslav Krstić

  6. Faculty of Pharmacy, University of Belgrade, PO Box 146, 11221, Belgrade, Serbia

    Snežana Uskoković-Marković

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  1. Danica Bajuk-Bogdanović
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Correspondence to Danica Bajuk-Bogdanović.

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Bajuk-Bogdanović, D., Holclajtner-Antunović, I., Jovanović, Z. et al. Tailoring the electrochemical charge storage properties of carbonaceous support by redox properties of heteropoly acids: where does the synergy come from?. J Solid State Electrochem 23, 2747–2758 (2019). https://doi.org/10.1007/s10008-019-04369-4

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