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Oxygen reduction on nanocrystalline ruthenia – local structure effects†
Sanjeev Mukerjee,Valery Petrykin,Zdeněk Bastl,Niels Bendtsen Halck,Jan Rossmeisl,Petr Krtil
RSC Advances Pub Date : 11/25/2014 00:00:00 , DOI:10.1039/C4RA10001H
Abstract

Nanocrystalline ruthenium dioxide and doped ruthenia of the composition Ru1−xMxO2 (M = Co, Ni, Zn) with 0 ≤ x ≤ 0.2 were prepared by the spray-freezing freeze-drying technique. The oxygen reduction activity and selectivity of the prepared materials were evaluated in alkaline media using the RRDE methodology. All ruthenium based oxides show a strong preference for a 2-electron oxygen reduction pathway at low overpotentials. The catalysts' selectivity shifts towards the 4-electron reduction pathway at high overpotentials (i.e. at potentials below 0.4 V vs. RHE). This trend is particularly noticeable on non-doped and Zn-doped catalysts; the materials containing Ni and Co produce a significant fraction of hydrogen peroxide even at high overpotentials. The suppression of the 4-electron reduction pathway on Ni and Co-doped catalysts can be accounted for by the presence of the Ni and Co cations in the cus binding sites as shown by the DFT-based analyses on non-doped and doped catalysts.

Graphical abstract: Oxygen reduction on nanocrystalline ruthenia – local structure effects
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