▎ 摘　　要

Platinum group metal-free (PGM-free) electrocatalysts for the oxygen reduction reaction (ORR) often exhibit a complex functionalized graphitic structure. Because of this complex structure, limited understanding exists about the design factors for the synthesis of high-performing materials. Graphene, a two-dimensional hexagonal structure of carbon, is amenable to structural and functional group modifications, making it an ideal analogue to study crucial properties of more complex graphitic materials utilized as electrocatalysts. In this paper, we report the synthesis of active nitrogen-doped graphene oxide catalysts for the ORR in which their activity and four-electron selectivity are enhanced using simple solvent and electrochemical treatments. The solvents, chosen based on Hansen's solubility parameters, drive a substantial change in the morphology of the functionalized graphene materials by (i) forming microporous holes in the graphitic sheets that lead to edge defects and (ii) inducing 3D structure in the graphitic sheets that promotes ORR Additionally, the cycling of these catalysts has highlighted the multiplicity of the active sites, with different durability, leading to a highly selective catalyst over time, with a minimal loss in performance. High ORR activity was demonstrated in an alkaline electrolyte with an onset potential of similar to 1.1 V and half-wave potential of 0.84 V vs RHE. Furthermore, long-term stability potential cycling showed minimal loss in half-wave potential (<3%) in both N-2-and O-2-saturated solutions with improved selectivity toward the four-electron reduction after 10000 cycles. The results described in this work provide additional understanding about graphitic electrocatalysts in alkaline media that may be utilized to further enhance the performance of PGM-free ORR electrocatalysts.