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Nanoscale Carbon Modified α‑MnO2 Nanowires: Highly Active and Stable Oxygen Reduction Electrocatalysts with Low Carbon Content

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journal contribution
posted on 21.12.2017, 00:00 by Julian A. Vigil, Timothy N. Lambert, Jonathon Duay, Collin J. Delker, Thomas E. Beechem, Brian S. Swartzentruber
Carbon-coated α-MnO2 nanowires (C-MnO2 NWs) were prepared from α-MnO2 NWs by a two-step sucrose coating and pyrolysis method. This method resulted in the formation of a thin, porous, low mass-percentage amorphous carbon coating (<5 nm, ≤1.2 wt % C) on the nanowire with an increase in single-nanowire electronic conductivity of roughly 5 orders of magnitude (α-MnO2, 3.2 × 10–6 S cm–1; C-MnO2, 0.52 S cm–1) and an increase in surface Mn3+ (average oxidation state: α-MnO2, 3.88; C-MnO2, 3.66) while suppressing a phase change to Mn3O4 at high temperature. The enhanced physical and electronic properties of the C-MnO2 NWsenriched surface Mn3+ and high conductivityare manifested in the electrocatalytic activity toward the oxygen reduction reaction (ORR), where a 13-fold increase in specific activity (α-MnO2, 0.13 A m–2; C-MnO2, 1.70 A m–2) and 6-fold decrease in charge transfer resistance (α-MnO2, 6.2 kΩ; C-MnO2, 0.9 kΩ) were observed relative to the precursor α-MnO2 NWs. The C-MnO2 NWs, composed of ∼99 wt % MnO2 and ∼1 wt % carbon coating, also demonstrated an ORR onset potential within 20 mV of commercial 20% Pt/C and a chronoamperometric current/stability equal to or greater than 20% Pt/C at high overpotential (0.4 V vs RHE) and high temperature (60 °C) with no additional conductive carbon.