Catalytic activity of Co-Nx/C electrocatalysts for oxygen reduction reaction: a density functional theory study

First-principles DFT computations are performed to explain the origin and the mechanism of oxygen reduction reaction (ORR) on Co-N x ( x = 2, 4) based self-assembled carbon supported electrocatalysts in alkaline and acidic media. The results show that the formation of graphitic Co-N 4 defect is energetically more favorable than the formation of graphitic Co-N 2 defect. Furthermore graphitic Co-N 4 defects are predicted to be stable at all potentials ( U = 0-1.23 V) in the present study while Co-N 2 defects are predicted to be unstable at high potentials. Therefore the Co-N 4 defect is predicted to be the dominant in-plane graphitic defect in Co-N x /C electrocatalysts. O 2 chemisorbs to Co-N 4 and Co-N 2 defects indicating that both defect motifs are active for the reduction of O 2 to peroxide. However, the weak interaction between peroxide and Co-N 4 defect shows that this defect does not promote complete ORR and a second site for the reduction of peroxide is required, supporting a 2 × 2e − dual site ORR mechanism independent of pH of the electrolyte. In contrast, the much stronger interaction between peroxide and Co-N 2 defect supports a 2 × 2e − single site ORR mechanism in alkaline and acidic media. Binding geometry of O 2 on Co-N x ( x = 2, 4) defects.