Nonmainstream Out‐Plane Fluoro‐ and Amino‐Cofunctionalized Graphene for a Striking Electrocatalyst: Programming Substitutive/Reductive Defluorination toward Graphite Fluoride.

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C100F2.8, 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C100F2.8 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C100F2.8 also exhibits remarkable resistance to crossover effect and exceptional cycling stability. A remarkable NH2‐/F‐cofunctionalized graphene electrocatalyst featured with a nonmainstream out‐plane doping mode is rationally designed and synthesized by an innovative methodology, in which nonpopular graphite fluoride is employed as the starting material and reacted with NaNH2. The coexistence and the significant synergistic effect between NH2 and F make NH2‐/F‐cofunctionalized graphene more electrocatalytically active than Pt/C. [ABSTRACT FROM AUTHOR]