Untangling cooperative effects of pyridinic and graphitic nitrogen sites at metal-free N-doped carbon electrocatalysts for the oxygen reduction reaction

Abstract

Metal-free carbon electrodes with well-defined composition and smooth topography were prepared via sputter deposition followed by thermal treatment with inert and reactive gases. XPS and Raman spectroscopies show that three carbons of similar N/C content that differ in N-site composition were thus prepared: an electrode consisting of almost exclusively graphitic-N (NG), an electrode with predominantly pyridinic-N (NP) and one with ca. 1:1 NG:NP composition. These materials were used as model systems to investigate activity of N-doped carbons in the oxygen reduction reaction (ORR) using voltammetry. Results show that selectivity towards 4e-reduction of O2 is strongly influenced by the NG/NP site composition, with the material possessing nearly uniform NG/NP composition being the only one yielding a 4e-reduction. Computational studies on model graphene clusters were carried out to elucidate the effect of N-site homogeneity on the reaction pathway. Calculations show that for pure NG-doping or NP-doping of model graphene clusters, adsorption of hydroperoxide and hydroperoxyl radical intermediates, respectively, is weak thus favoring desorption prior to complete 4e-reduction to hydroxide. Clusters with mixed NG/NP sites display synergistic effects, suggesting that co-presence of these sites improves activity and selectivity by achieving high theoretical reduction potentials while facilitating retention of intermediates.