Π-Bond Maximization of Graphene in Hydrogen Addition Reactions

Thermodynamic stability of graphene hydrides increases in an approximately linear way with the numbers of π-bonds they contain. Thus, π-bond maximization is the primary driving force for hydrogen addition reactions of graphene. The previously reported thermal preference of sp(2)/sp(3)-phase separation of graphene hydrides is a straightforward effect of π-bond maximization. Although not well applicable to hydroxylation and epoxidation, the π-bond maximization principle also holds approximately for the fluorination reactions of graphene. The findings can be used to help locate the lowest-energy structures for graphene hydrides and to estimate the hydrogenation energy without first-principles calculations.