Iron-based catalysts for the oxygen-reduction reaction in polymer electrolyte membrane fuel cells have been poorly competitive with platinum catalysts, in part because they have a comparatively low number of active sites per unit volume. We produced microporous carbon-supported iron-based catalysts with active sites believed to contain iron cations coordinated by pyridinic nitrogen functionalities in the interstices of graphitic sheets within the micropores. We found that the greatest increase in site density was obtained when a mixture of carbon support, phenanthroline, and ferrous acetate was ball-milled and then pyrolyzed twice, first in argon, then in ammonia. The current density of a cathode made with the best iron-based electrocatalyst reported here can equal that of a platinum-based cathode with a loading of 0.4 milligram of platinum per square centimeter at a cell voltage of >/=0.9 volt.

Three catalysts for the electroreduction of oxygen have been prepared by pyrolyzing between 400 and 1000 °C two iron precursors (Fe acetate or Fe porphyrin) adsorbed on a synthetic carbon made from the pyrolysis of PTCDA (perylene tetracarboxylic dianhydride) in a H 2 /NH 3 /Ar atmosphere. One Fe loading (0.2 wt %) has been used for the catalyst made from the salt precursor. Two Fe loadings (0.2 and 2.0 wt %) have been used for the catalyst made from the porphyrin precursor. These three catalysts have been analyzed by ToF SIMS and RDE (or GDE) in order to find correlations between ions detected by ToF SIMS and the catalytic activity. These correlations provide information about the number and the structure of the catalytic sites, which are active in these materials. By following the variation of FeN x C y + ions, it is found that (i) two different catalytic sites exist simultaneously in all catalysts made with the Fe salt or the Fe porphyrin; (ii) one site, named FeN 4 /C, is at the origin of three families of FeN x C y + ions: FeN 4 C y + , FeN 3 C y + , and FeN 1 C y + . The most representative ion of that site is FeN 4 C 8 + . The other site, labeled FeN 2 /C, is at the origin of the family of FeN 2 C y + ions. The most representative ion of that site is FeN 2 C 4 + ; (iii) the abundance of FeN 2 /C goes through a maximum for catalysts pyrolyzed between 700 and 900 °C. When Fe acetate is the Fe precursor, FeN 2 /C may represent up to 80% of the catalytic sites, while this falls to a maximum of about 50% when Fe porphyrin is the precursor; (iv) FeN 2 /C is more electrocatalytically active than FeN 4 /C; (v) at high porphyrin loading (2.0 wt % Fe), the catalytic sites bound to the carbon support are covered with a porous layer of pyrolyzed Fe porphyrin.

Catalytic activity for O2 electroreduction in acidic medium has been studied. Catalysts have been produced by pyrolyzing perylene tetracarboxylic dianhydride (PTCDA) combined with Fe and N precursors. The Fe precursors used in this work are either FeII acetate or Cl−FeIII Tetramethoxyphenyl porphyrin (Cl−FeTMPP). The N precursors are NH3 and/or Cl−FeTMPP. To be able to vary the catalytic activity, two synthesis procedures have been used, varying either the heat-treatment temperature or the Fe content of the pyrolyzed materials. All the catalysts have been studied by Time-of-Flight Secondary Ion Mass Spectrometry (ToF SIMS) in order to find out if the relative intensity of one or several secondary ions was following the changes observed in the catalytic activity. Only one ion, FeN2C4 +, may be considered as the signature of the catalytic site generated in this work. It has been detected in all prepared catalysts, whatever the Fe precursor or the synthesis procedure was used. It is proposed that this ion is produced under ToF SIMS analysis from part of a 1,10 phenanthrolinic-type structure, which is itself part of the catalytic site. This catalytic site is probably the same as the one obtained by the pyrolysis at high temperature (≥ 800 °C) of N4−Fe macrocycles adsorbed on carbon black. RDE and PEM fuel cell tests demonstrate that the most performing catalysts are those containing 2 wt % Fe as Cl−FeTMPP and 0.2 wt % Fe as Fe acetate. Increasing the Fe content beyond these limits mainly generates catalytically inactive Fe clusters and interferes with the characterization of the high-temperature active site.

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