Oxygen reduction by Fe-based catalysts in PEM fuel cell conditions: Activity and selectivity of the
Fe-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cell conditions have been prepared by adsorbing two Fe precursors on various commercial and developmental carbon supports. The resulting materials have been pyrolyzed at 900 °C in an atmosphere rich in NH3. The Fe precursors were: iron acetate (FeAc) and iron tetramethoxy phenylporphyrin chloride (ClFeTMPP). The nominal Fe content was 2000 ppm (0.2 wt.%). The carbon supports were HS300, Printex XE-2, Norit SX-Ultra, Ketjenblack, EC-600JD, Acetylene Black, Vulcan XC-72R, Black Pearls 2000, and two developmental carbon black powders, RC1 and RC2 from Sid Richardson Carbon Corporation. The catalyst activity for ORR has been analyzed in fuel cell tests at 80 °C as well as by cyclic voltammetry in O2 saturated H2SO4 at pH 1 and 25 °C, while their selectivity was determined by rotating ring-disk electrode in the same electrolyte. A large effect of the carbon support was found on the activity and on the selectivity of the catalysts made with both Fe precursors. The most important parameter in both cases is the nitrogen content of the catalyst surface. High nitrogen content improves both activity towards ORR and selectivity towards the reduction of oxygen to water (4e− reaction). A possible interpretation of the activity and selectivity results is to explain them in terms of two Fe-based catalytic sites: FeN2/C and FeN4/C. Increasing the relative amount of FeN2/C improves both activity and selectivity of the catalysts towards the 4e− reaction, while most of the peroxide formation may be attributed to FeN4/C. When FeAc is used as Fe precursor, iron oxide and/or hydroxide are also formed. The latter materials have low catalytic activity for ORR and reduce O2mainly to H2O2.