Computational study of precision nitrogen doping on graphene nanoribbon edges

Nitrogen doping in graphene is important for applications spanning from electronics to metal-free electrocatalysts. Despite much experimental study, limited theoretic work has been done in understanding the mechanism of the doping process, especially from a precision perspective. Herein, we present a computational study on precision nitrogen doping on edges of graphene nanoribbons (GNRs) by combining molecular dynamics (MD) simulation at a time scale of 40 ns and density function theory (DFT) calculation. In the MD study both ammonia and acetonitrile were used as nitrogen sources. MD results revealed that the ammonia produces almost all amine-type dopants, while the acetonitrile produces a considerable amount of pyrrolic and pyridinic nitrogen dopants which are beneficial to electronics and electrocatalysts. Results also show that the concentration of pyrrolic and pyridinic dopants can be precisely controlled by the edge geometries of the GNRs. Furthermore, DFT calculation illustrated the reaction mechanism in these different types of the GNRs when using acetonitrile as the nitrogen source. The calculated energies in different reaction stages indicate the stability of dopants on various GNRs, agreeing well with the MD results. The disclosed mechanism of controllable nitrogen doping on the edges of the GNRs would provide guidance to experimental realization, paving new routes to widespread applications.