▎ 摘　　要

It is mostly reported that graphene lattice doped/codoped with heteroatoms (e.g., nitrogen and boron) in an in-plane fashion exhibits an impressive oxygen reduction reaction (ORR) electrocatalytic efficiency when serving as a metal-free catalyst, but the cases that graphene sheets functionalized with heteroatoms in an out-plane scenario are rarely involved. Herein, amino (NH2)-/fluoro (F)-cofunctionalized graphene (NH2-G-F) is rationally designed and synthesized both in out-plane modes through a programmable substitutive/reductive defluorination toward bulk graphite fluoride using NaNH2. Versatile NH2-/F-(co)functionalized graphene products with tunable fluorination and amination are readily yielded and their ORR electrocatalysis is evaluated. Intriguingly, the parameter of NH2/F molar ratio is determinative for their electrocatalytic performances. Consequently, graphene product (roughly formulated in (NH2)(7.0)-C-100-F-2.8, vide infra) dually functionalized with NH2 and F and with an optimized NH2/F factor of 2.5 outperforms others-overmuch in either NH2 only or F only. Encouragingly, (NH2)(7.0)-C-100-F-2.8 even delivers a slightly better electrocatalytic activity than Pt/C catalyst. This finding implies a significant synergistic effect between NH2 and F in boosting graphene electrocatalysis. Apart from fantastic electrocatalytic activity, (NH2)(7.0)-C-100-F-2.8 also exhibits remarkable resistance to crossover effect and exceptional cycling stability.