Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model

A preexisting chemisorbed defect is well-known to increase the reactivity of graphene which is normally chemically inert. Specifically, the presence of chemisorbed hydrogen atoms forming an sp³-hybridized C-H bond is known to increase the reactivity of neighboring carbon atoms toward additional hydrogenation with wide-ranging applications from materials science to astrochemistry. In this work, static DFT and DFT-based direct dynamics simulations are used to characterize the reactivity of a graphene sheet around an existing C-H bond defect. The spin density landscape shows how to guide subsequent H atom additions, always bonding most strongly to the carbon atom with greatest spin density. Molecular dynamics of an impinging H atom under thermal conditions with defect graphene was used to determine the statistics of probable reactions. The most frequent outcome is inelastic scattering (48%) and then Eley-Rideal (ER) abstraction of the chemisorbed H atom as vibrationally hot H₂ (40%), while the least likely, but probably most interesting, result is formation of a novel C-H bond (12%). The C-H bonds always form in the β sublattice. The carbon atom in the para position shows to be most reactive toward the incoming H atom, followed by the ortho carbon, in agreement with the spin density computed in the static calculations. Globally, the graphene energy surface is repulsive, but the defects create local channels into this energy surface through which reactants can move locally through and react with the activated surface without a barrier.