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Unraveling the Role of CeO2 in Stabilization of Multivalent Mn Species on α-MnO2/Mn3O4/CeO2/C Surface for Enhanced Electrocatalysis

  • Bhugendra Chutia
    Bhugendra Chutia
    Department of Chemical Sciences, Tezpur University, Tezpur, Assam 784 028, India
  • Nayab Hussain
    Nayab Hussain
    Department of Chemical Sciences, Tezpur University, Tezpur, Assam 784 028, India
  • Panchanan Puzari
    Panchanan Puzari
    Department of Chemical Sciences, Tezpur University, Tezpur, Assam 784 028, India
  • Deshetti Jampaiah
    Deshetti Jampaiah
    Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Science, RMIT University, Melbourne, Victoria 3001, Australia
  • Suresh K. Bhargava
    Suresh K. Bhargava
    Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Science, RMIT University, Melbourne, Victoria 3001, Australia
  • Ekaterina V. Matus
    Ekaterina V. Matus
    Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090, Russia
  • Ilyas Z. Ismagilov
    Ilyas Z. Ismagilov
    Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090, Russia
  • Mikhail Kerzhentsev
    Mikhail Kerzhentsev
    Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090, Russia
  • , and 
  • Pankaj Bharali*
    Pankaj Bharali
    Department of Chemical Sciences, Tezpur University, Tezpur, Assam 784 028, India
    *Tel.: +91 3712 275064. Fax: +91 3712 267005/6. Email: [email protected]
Cite this: Energy Fuels 2021, 35, 13, 10756–10769
Publication Date (Web):June 22, 2021
https://doi.org/10.1021/acs.energyfuels.1c00785
Copyright © 2021 American Chemical Society
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Abstract

A hybrid heteronanostructure of α-MnO2/Mn3O4/CeO2 with the atomic-level coupled nanointerface entrenched in Vulcan carbon is reported and explored for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). CeO2 plays an essential role in increasing the surface Mn2+/3+/4+ in α-MnO2/Mn3O4/CeO2/C for ORR/OER processes. It shows enhanced bifunctional activity, superior to that of the benchmark 20 wt % Pt/C and Pd/C catalysts. It displays an ORR onset potential of −0.13 V (vs Ag/AgCl), limiting current density of −6.63 mA cm–2 (at 1600 rpm), mass-specific current of 47.6 mA mgMO–1 with a lower Tafel slope (921.9 mV dec–1), and an inclusive 4-e transfer involved in ORR. The OER onset potential and current density are 0.58 V (vs Ag/AgCl) and 8.45 mA cm–2 (at 0.8 V). The unique hybrid structure with oxide–oxide interface in α-MnO2/Mn3O4/CeO2 is correlated to explain the mechanistic pathway. Multistate Mn(II/III/IV) and Ce(III/IV) synergistically influence in tendering superior activity with enhanced stability.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.energyfuels.1c00785.

  • Determination of electrochemically active surface area (ECSA), additional characterization and experimental data, including TEM, EDX spectra, TGA, Raman spectra, XPS spectra, LSV curves, and corresponding K–L plots for ORR, scan-rate dependent CV curves, LSV curves at 1600 rpm for OER of various electrocatalysts, tables, and references (PDF)

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Cited By


This article is cited by 1 publications.

  1. Chiranjita Goswami, Kumar Kashyap Hazarika, Yusuke Yamada, Pankaj Bharali. Nonprecious Hybrid Metal Oxide for Bifunctional Oxygen Electrodes: Endorsing the Role of Interfaces in Electrocatalytic Enhancement. Energy & Fuels 2021, 35 (16) , 13370-13381. https://doi.org/10.1021/acs.energyfuels.1c01388