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Catalysts 2018, 8(8), 320; https://doi.org/10.3390/catal8080320

Investigation of Earth-Abundant Oxygen Reduction Electrocatalysts for the Cathode of Passive Air-Breathing Direct Formate Fuel Cells

Institute of Chemistry of Sao Carlos, University of Sao Paulo, Av. Trabalhador Saocarlense, 400 CP 780, São Carlos SP 13566-590, Brazil
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Received: 30 June 2018 / Revised: 26 July 2018 / Accepted: 29 July 2018 / Published: 6 August 2018
(This article belongs to the Special Issue Recent Advances of Electrocatalysis in Fuel Cells)
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Abstract

The development of direct formate fuel cells encounters important obstacles related to the sluggish oxygen reduction reaction (ORR) and low tolerance to formate ions in Pt-based cathodes. In this study, electrocatalysts formed by earth-abundant elements were synthesized, and their activity and selectivity for the ORR were tested in alkaline electrolyte. The results showed that carbon-encapsulated iron-cobalt alloy nanoparticles and carbon-supported metal nitrides, characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD), do not present significant activity for the ORR, showing the same half-wave potential of Vulcan carbon. Contrarily, nitrogen-doped carbon, synthesized using imidazole as the nitrogen source, showed an increase in the half-wave potential, evidencing an influential role of nitrogen in the ORR electrocatalysis. The synthesis with the combination of Vulcan, imidazole, and iron or cobalt precursors resulted in the formation of nitrogen-coordinated iron (or cobalt) moieties, inserted in a carbon matrix, as revealed by X-ray absorption spectroscopy (XAS). Steady-state polarization curves for the ORR evidenced a synergistic effect between Fe and Co when these two metals were included in the synthesis (FeCo-N-C material), showing higher activity and higher limiting current density than the materials prepared only with Fe or Co. The FeCo-N-C material presented not only the highest activity for the ORR (approaching that of the state-of-the-art Pt/C) but also high tolerance to the presence of formate ions in the electrolyte. In addition, measurements with FeCo-N-C in the cathode of an passive air-breathing direct formate fuel cells, (natural diffusion of formate), showed peak power densities of 15.5 and 10.5 mW cm−2 using hydroxide and carbonate-based electrolytes, respectively, and high stability over 120 h of operation. View Full-Text
Keywords: oxygen reduction; non-noble metal electrocatalysts; M-N-C; direct formate fuel cells oxygen reduction; non-noble metal electrocatalysts; M-N-C; direct formate fuel cells
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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E. R. Oliveira, F.; A. Galiote, N.; H. B. Lima, F. Investigation of Earth-Abundant Oxygen Reduction Electrocatalysts for the Cathode of Passive Air-Breathing Direct Formate Fuel Cells. Catalysts 2018, 8, 320.

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