Influence of Nitrogen Doping into Carbon on the Activation Barrier of ORR in Alkaline Medium: An Investigation Based on Eyring Analysis

The oxygen reduction reaction (ORR) is investigated on metal-free carbon (Vulcan XC-72) and nitrogen-doped (∼≤1%) carbon (N/C-900) in 0.1 M KOH. The product distribution (O₂ to OH^- and HO₂^-) as a function of overpotential (η) in the temperature range of 293-323 K is analyzed using a rotating ring-disk electrode (RRDE) assembly. The kinetic current due to reduction of O₂ to HO₂^- is estimated and used in the Eyring analysis to determine the change in enthalpy of activation (ΔH^#). It is shown that doping of carbon with nitrogen (even with ≤1 wt %) causes substantial increase in the number of active sites (almost 2-fold) and reduction in ΔH^# at any η. Moreover, ΔH^# is a stronger function of η on N/C-900 as compared to that on the carbon surface.