A molecular understanding of the gas-phase reduction and doping of graphene oxide

Chemical reduction of graphene oxide represents an important route towards large-scale production of graphene sheets for many applications. Thus far, gas-phase reactions have been demonstrated to efficiently reduce graphene oxide, but a molecular understanding of the reaction processes is largely lacking. Here, using molecular dynamics simulations, we compare the reduction of graphene oxide in different environments. We find that NH₃ affords more efficient reduction of hydroxyl and epoxide groups than H₂ and vacuum annealing partly due to lower energy barriers. Various reduction paths of oxygen groups in NH₃ and H₂ are quantitatively identified. Furthermore, we show that with the combination of vacancies and oxygen groups, pyridinic- or pyrrolic-like nitrogen can readily be incorporated into graphene. All of these nitrogen configurations lead to n-doping of the graphene. Our results are consistent with many previous experiments and provide insights towards doping engineering of graphene.