Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

Graphitic materials are essential in energy conversion and storage because of their excellent chemical and electrical properties. The strategy for obtaining functional graphitic materials involves graphite oxidation and subsequent dissolution in aqueous media, forming graphene-oxide nanosheets (GNs). Restacked GNs contain substantial intercalated water that can react with heteroatom dopants or the graphene lattice during reduction. We demonstrate that removal of intercalated water using simple solvent treatments causes significant structural reorganization, substantially affecting the oxygen reduction reaction (ORR) activity and stability of nitrogendoped graphitic systems. Amid contrasting reports describing the ORR activity of GN-based catalysts in alkaline electrolytes, we demonstrate superior activity in an acidic electrolyte with an onset potential of ∼0.9 V, a halfwave potential (E_1/2) of 0.71 V, and a selectivity for four-electron reduction of >95%. Further, durability testing showed E_1/2 retention >95% in N_2- and O_2-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.