Mechanistic Insights into the Oxygen Reduction Reaction on Metal-N-C Electrocatalysts under Fuel Cell Conditions

Three different transition metal-C-N catalysts are tested under a range of fuel cell conditions. It is found that common features of the polarisation curve can be explained by a change in electrocatalytic mechanism. Utilising a simple model to quantify the change in mechanisms, iR-free results of the fuel cell experiments are fit and found to be represented by a common set of parameters. The change in mechanism is assumed to be a switch from four-electron reduction of oxygen to water to a two-electron reduction to hydrogen peroxide followed by disproportionation of the hydrogen peroxide to water and oxygen. The data is used to estimate a mass specific exchange current density towards the oxygen reduction reaction (ORR) to water in the range 10(-11)-10(-13) Ag-1 depending on the catalyst. For the reduction of oxygen to hydrogen peroxide, the mass specific exchange current density is estimated to be in the range 10(-2)-10(-3) Ag-1. Utilising the electrokinetic model, it is shown how the mass transport losses can be extracted from the polarisation curve. For all three catalyst layers studied, these mass transport losses reach about 100 mV at a current density of 1 Acm(-2). Finally a discussion of the performance and site density requirements of the non-precious metal catalysts are provided, and it is estimated that the activity towards the ORR needs to be increased by an order of magnitude, and the site density by two/three orders of magnitude to compete with platinum as an ORR electrocatalyst.