A comprehensive review of recent advances in the field of oxygen reduction electrocatalysis utilizing nonprecious metal (NPM) catalysts is presented. Progress in the synthesis and characterization of pyrolyzed catalysts, based primarily on the transition metals Fe and Co with sources of N and C, is summarized. Several synthetic strategies to improve the catalytic activity for the oxygen reduction reaction (ORR) are highlighted. Recent work to explain the active-site structures and the ORR mechanism on pyrolyzed NPM catalysts is discussed. Additionally, the recent application of Cu-based catalysts for the ORR is reviewed. Suggestions and direction for future research to develop and understand NPM catalysts with enhanced ORR activity are provided.

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It is of great research interest to understand the nanostructures contributing to the activity observed in the reduction of oxygen by non-platinum group metal (PGM) electrocatalysts in acidic media. Iron- and nitrogen-containing carbon networks are often the most studied structures, among which single-atom iron-coordinated nitrogen (FeN x ) moieties have often been proposed to be the structures leading to the high activity in these non-PGM electrocatalysts. Iron nanoparticles embedded within a carbon support are also formed under certain conditions as a result of the synthetic processes in making non-PGM electrocatalysts. In this study, we present a study to understand the oxygen reduction reaction (ORR) activity of prepared iron- and nitrogen-containing non-PGM electrocatalysts obtained through the pyrolysis of metal–organic framework (MOF) precursors. We studied the structure–property relationship among nanostructures made from the MOF precursor ZIF-8 under different pyrolysis conditions. Density functional theory calculations were used to explain the effect of structural moieties on the ORR activity. Our results suggest that iron-coordinated C–N structures and iron nanoparticles act synergistically to catalyze the ORR.