The pH dependent reactions of graphene oxide with small molecule thiols

Graphene oxide (GO) is a heterogenous 2D carbon-based material composed of sp(2) and sp(3) hybridized carbon atoms and oxygen containing functionalities, i.e., alcohols and epoxides. Thus, the chemical reactivity of GO is complex and both complimentary and contrasting to the reactivity of corresponding small molecules (e.g., tertiary alcohols, epoxides, and alkenes). Understanding the reactivity of GO under different conditions and with different reagents will ensure the chemical composition can be controlled and thus electronic and optical properties dictated, and solubility tuned for desired applications. Reaction of GO nanosheets towards a variety of reagents has been reported, however controlling the reaction pathway of GO nanosheets with a single nucleophile by simple alternation of the reaction medium has not been realized. This ability to tune the reaction by modification of solution pH, for example, would aid in understanding the reactivity of GO. Herein, we report that GO undergoes two distinct reaction pathways with ethane thiol depending on the pH of the reaction media: under aprotic basic conditions GO nanosheets undergo functionalization with minimal reduction, and under superacidic conditions GO nanosheets are reduced with no functionalization.