Enhanced selective oxidation of ethylarenes using iron single atom catalysts embedded in Nitrogen-Rich graphene

• A new low temperature and environmental friendly synthesis of nitrogen rich (19 % w/w) graphene is proposed. • The selective presence (78 % w/w) of pyridinic species allow the fixation of extremely stable iron single atom catalysts (leaching below 0.02 % w/w) • The Iron SACs exhibit excellent catalytic activity in the selective oxidation of ethylarenes (TON = 13400 h −1 ) and a broad scope. • The reaction is genuinely catalytic (oxygen is the final oxidant) and the selectivity can be controlled by a proper choice of the peroxide. Heavily (19 % wt) Nitrogen doped graphene (N-G), with Nitrogen incorporated mainly as pyridinic species (77.8 %), was obtained by reacting fluorographene with ammonia under solvothermal conditions, at mild temperature (140 °C). N-G was used to stabilize single iron atoms (N-G-Fe) in two different configurations: low spin X-(Fe II N 4 )-Y and high spin X-(Fe III N 4 )-Y. The resulting N-G-Fe single atom catalysts exhibit remarkable efficacy in the selective oxidation of ethylarenes, with activity comparable or even superior to state-of-the-art materials, converting ethylbenzene to acetophenone with an initial turnover frequency of 13400 h −1 . Notably, N-G-Fe exhibits genuine catalytic activity since it is able to oxidize ethylbenzene using substoichiometric amount of peroxides, and exploiting molecular oxygen as the final oxidant. Moreover, N-G-Fe can be recycled without any metal leaching, and exhibits a broad catalytic scope. Multi-technique characterizations combined with rationally designed catalytic tests allowed us to identify the active sites and propose a plausible mechanism for the catalytic cycle