Nitrogen doping and CO2 adsorption on graphene: A thermodynamical study

Nitrogen-doped graphene has raised considerable interest for its possible applications as carbon dioxide adsorber and catalyst. In this paper, we provide a theoretical study of graphitic, pyridiniclike and pyrroliclike nitrogen defects in a free-standing graphene layer, focusing on their formation and adsorption behavior. Using density functional theory and thermodynamics, we analyze the various defects, highlighting the great stability of graphitic nitrogen in a wide temperature and pressure range. CO2 adsorption proves to be moderately thermodynamically disfavored around standard conditions for the most stable nitrogen defects and slightly favored for the more energetic ones. The combination of the results on defect stability and CO2 adsorption may open interesting possibilities in the design of carbon-based materials with promising adsorption performances.