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Issue 33, 2012
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Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells

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Abstract

Fe-based catalytic sites for the reduction of oxygen in acidic medium have been identified by 57Fe Mössbauer spectroscopy of Fe/N/C catalysts containing 0.03 to 1.55 wt% Fe, which were prepared by impregnation of iron acetate on carbon black followed by heat-treatment in NH3 at 950 °C. Four different Fe-species were detected at all iron concentrations: three doublets assigned to molecular FeN4-like sites with their ferrous ions in a low (D1), intermediate (D2) or high (D3) spin state, and two other doublets assigned to a single Fe-species (D4 and D5) consisting of surface oxidized nitride nanoparticles (FexN, with x ≤ 2.1). A fifth Fe-species appears only in those catalysts with Fe-contents ≥0.27 wt%. It is characterized by a very broad singlet, which has been assigned to incomplete FeN4-like sites that quickly dissolve in contact with an acid. Among the five Fe-species identified in these catalysts, only D1 and D3 display catalytic activity for the oxygen reduction reaction (ORR) in the acid medium, with D3 featuring a composite structure with a protonated neighbour basic nitrogen and being by far the most active species, with an estimated turn over frequency for the ORR of 11.4 e per site per s at 0.8 V vs. RHE. Moreover, all D1 sites and between 1/2 and 2/3 of the D3 sites are acid-resistant. A scheme for the mechanism of site formation upon heat-treatment is also proposed. This identification of the ORR-active sites in these catalysts is of crucial importance to design strategies to improve the catalytic activity and stability of these materials.

Graphical abstract: Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells

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Publication details

The article was received on 13 Mar 2012, accepted on 21 Jun 2012 and first published on 21 Jun 2012


Article type: Paper
DOI: 10.1039/C2CP41957B
Citation: Phys. Chem. Chem. Phys., 2012,14, 11673-11688
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    Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells

    U. I. Kramm, J. Herranz, N. Larouche, T. M. Arruda, M. Lefèvre, F. Jaouen, P. Bogdanoff, S. Fiechter, I. Abs-Wurmbach, S. Mukerjee and J. Dodelet, Phys. Chem. Chem. Phys., 2012, 14, 11673
    DOI: 10.1039/C2CP41957B

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