Relative Stability of Graphene Nanoflakes Under Environmentally Relevant Conditions

The stability of finite-sized graphene nanostructures under different conditions is contingent on the stability of the highly reactive undercoordinated atoms around the circumference. Chemical passivation is a convenient way of stabilizing the edges and corners, provided the conditions support adsorption. In this paper we examine the stabilities of hydrogen, oxygen, hydroxyl, and water functionalization of the edges of graphene nanoflakes using a combination of ab initio thermodynamics and self-consistent charge density functional tight-binding simulations. We find that the adsorption of hydrogen and oxygen on graphene nanoflakes is selective and sensitive to the edge and corner structure and the local environment. Under hydrogen-rich conditions (or in vacuo), we find that armchair edges are preferred, whereas under oxygen-rich conditions the stability of the zigzag edge is enhanced. In addition to this, we find that the types of corners play an important role, and the presence of acute 60 degrees corners is thermodynamically preferred, particularly under humid conditions. In each case, the adsorption efficiency is related to the temperature and the pressure, which may be used to stabilize one type of structure or another.