CoPdx oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

The electrochemical activity of carbon-supported cobalt–palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm2 single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 °C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPdx PEMFC system with varying composition reveals that a nominal cobalt–palladium atomic ratio of 1:3, CoPd3, exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd3 has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd3 catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd3 catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt.