Amine-functionalized holey graphene as a highly active metal-free catalyst for the oxygen reduction reaction

Abstract

Amine functionalized holey graphene (AFHG), synthesized by the hydrothermal reaction of GO and ammonia and the subsequent KOH etching, has been used as a metal-free catalyst for the oxygen reduction reaction (ORR). It shows that AFHG is highly active for the ORR and exhibits higher electrocatalytic activity than graphene, nitrogen-doped graphene (NG) and amine functionalized graphene (AFG), which could be demonstrated from its higher current density and more positive half-wave and onset potentials for the ORR. Although AFHG also exhibits a slightly higher overpotential towards ORR, it is indeed more kinetically facile than the commercial JM Pt/C 40 wt%. Its higher electrochemical performance could be attributed to the presence of the electron donating group (e.g. amine) and a large number of holes in its sheet plate and the porous structure in its randomly stacked solid, which provide AFHG with higher electrical conductivity, more active edge N atoms and easier accessibility to oxygen, respectively. The stability measurements show that AFHG is more stable than graphene, NG, AFG and the JM Pt/C 40 wt% and exhibits higher immunity towards methanol crossover and CO poisoning than the JM Pt/C 40 wt%. Over 10 h of the ORR, AFHG loses only <7% of its original activity in the absence of methanol or CO, and the introduction of methanol or CO has no effect on its oxygen reduction activity, which makes it highly desirable as a metal-free catalyst for the ORR.