Graphene-edge-supported iron dual-atom for oxygen reduction electrocatalysts

Abstract

Pyrolyzed Fe–N–C-based catalysts, particularly FeN₄, are reported to show enhanced catalytic activity for some chemical reactions, particularly for the oxygen reduction reaction (ORR). Here, we present a computational study to investigate another pyrolyzed Fe–N–C-based catalyst, i.e. Fe₂N₆, adsorbed on graphene with special emphasis on the edges of graphene nanoribbons (both zig-zag and armchair configurations) as a candidate for Fe dual-atom catalysts (Fe-DACs). Utilizing density functional theory calculations along with microkinetic simulations, we investigate the influence of graphitic edges on the stability and ORR activity of Fe-DAC active sites. Our findings indicate that the presence of graphitic edges, particularly the zig-zag configuration, significantly lowers the formation energy of Fe-DAC active sites, making them more likely to form at the edges. Furthermore, several Fe-DAC active sites at graphitic edges exhibit exceptional ORR performance, surpassing the commonly employed FeN₄ active site in SAC systems and even exceeding the benchmark Pt(111) surface. Notably, the (Fe₂N₆)_o@z₁ active site demonstrates outstanding performance in both associative and dissociative mechanisms. These results highlight the role of graphitic nanopores in enhancing the catalytic behavior of Fe-DAC active sites, providing valuable insights for designing efficient non-precious metal catalysts for ORR applications.