Degradation by Hydrogen Peroxide of Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction

Fe-N-C and Co-N-C materials are promising catalysts for reducing oxygen in fuel cells. The degradation of such catalysts induced by H 2 O 2 was investigated by contacting them ex situ with various amounts of H 2 O 2 . The degradation increased with increasing amounts of H 2 O 2 . The effect was most severe for Cr-N-C followed by Fe-N-C and last by Co-N-C. Treatment with H 2 O 2 leads to diminished oxygen reduction activity at high potential and/or reduced transport properties at high current density in fuel cell. From spectroscopic characterization, it was found that 66 and 80% of the CoN x C y and FeN x C y moieties present in pristine catalysts survived the extensive H 2 O 2 treatment, respectively. In parallel, the activity for oxygen reduction was divided by ca 6–10 for Fe-N-C and by ca 3 for Co-N-C. The results suggest that the main degradation mechanism in fuel cell for such catalysts is due to a chemical reaction with H 2 O 2 that is generated during operation. The super-proportional decrease of the oxygen reduction activity with loss of FeN x C y and CoN x C y moieties suggests either that only a small fraction of such moieties are initially located on the top surface, or that their turnover frequency for oxygen reduction was drastically reduced due to surface oxidation by H 2 O 2 .