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[en] Highlights: • Fe-N-C catalyst has been investigated for the ORR in the presence of alcohol. • Fe-N4 and Fe-N2C2 sites preferentially adsorb O2 according to DFT calculations. • Fe-N-C overcomes Pt ORR activity with alcohol concentrations as low as 0.01 M. • The feasibility of DAFCs operation at high alcohol concentrations is demonstrated. Direct alcohol fuel cells (DAFCs) represent the best alternative to batteries for portable and auxiliary power units application due to the high energy density of short chain alcohols. Currently, the utilization of the best platinum group metal (PGM) cathode catalysts is limited, not only by a high cost and scarce resources, but also by the inefficient oxygen reduction reaction (ORR) when permeated alcohols adsorb on the catalytic active sites. In this work, a highly active Fe-N-C catalyst derived from the pyrolysis of nicarbazin (a nitrogen charge transfer organic salt) and an iron precursor has been investigated to get insights on the extraordinary tolerance to the presence of alcohols (methanol and ethanol) of such a PGM-free catalyst. Density functional theory (DFT) calculations demonstrate for the first time that Fe-N4 and Fe-N2C2 active sites preferentially adsorb oxygen with much higher energy than methanol, ethanol and products of partial ethanol oxidation (0.73–1.16 eV stronger adsorption), while nitrogen-carbon related sites (pyridinic and graphitic nitrogen) are much less selective towards ORR. Half-cell electrochemical characterization showed that the Fe-N-C catalyst overcomes Pt ORR activity in acidic medium with methanol or ethanol concentrations as low as 0.01 M. The feasibility of DAFCs operation based on high methanol (up to 17 M) and ethanol (up to 5 M) concentration thanks to the utilization of Fe-N-C cathode catalyst is demonstrated. A new strategy is proposed for DAFCs where using Pt only at the anode and Fe-N-C at the cathode allows extending the device energy density compared to PGM-based catalysts at both electrodes.