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

Author(s)

Oliveira, Francisca E. R. ^[1] ; Galiote, Nelson A. ^[1] ; Lima, Fabio H. B. ^[1]

Affiliation

^[1] Univ Sao Paulo, Inst Chem Sao Carlos, Av Trabalhador Saocarlense, 400 CP 780, BR-13566590 Sao Carlos, SP - Brazil

• Document type: Journal article
• Source: CATALYSTS; v. 8, n. 8 AUG 2018.
• Web of Science Citations: 1

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. (AU)

• FAPESP's process: 13/16930-7 - Electrocatalysis V: electrocatalytic processes of chemical and electrical energy interconversion
• Grantee: Edson Antonio Ticianelli
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 16/06197-9 - Metallic Carbonitrides and Nanoestructured Carbon Composites as Non-noble Electrocatalysts for the Oxygen Reduction Reaction
• Grantee: Nelson Alexandre Galiote Silva
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 16/13323-0 - Carbon Dioxide and Water Electrochemistry: Application in Energy Conversion and Storage
• Grantee: Fabio Henrique Barros de Lima
• Support Opportunities: Regular Research Grants