Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-5307
Main Title: Structure of the catalytic sites in Fe/N/C-catalysts for O-2-reduction in PEM fuel cells
Author(s): Kramm, Ulrike I.
Herranz, Juan
Larouche, Nicholas
Arruda, Thomas M.
Lefèvre, Michel
Jaouen, Frédéric
Bogdanoff, Peter
Fiechter, Sebastian
Abs-Wurmbach, Irmgard
Mukerjee, Sanjeev
Dodelet, Jean-Pol
Type: Article
Language Code: en
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.
URI: http://depositonce.tu-berlin.de/handle/11303/5687
http://dx.doi.org/10.14279/depositonce-5307
Issue Date: 2012
Date Available: 28-Jun-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Usage rights: Terms of German Copyright Law
Journal Title: Physical chemistry, chemical physics
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 14
Issue: 33
Publisher DOI: 10.1039/c2cp41957b
Page Start: 11673
Page End: 11688
EISSN: 1463-9076
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:Technische Universität Berlin » Fakultäten & Zentralinstitute » Fakultät 6 Planen Bauen Umwelt » Institut für Angewandte Geowissenschaften » Fachgebiet Mineralogie » Publications

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