Mechanisms of the Aggregation of Graphene Oxide at High pH: Roles of Oxidation Debris and Metal Adsorption

In this work, aggregation of graphene oxide (GO) in synthetic surface water at high pH was elaborated, and experimental characterizations and molecular dynamics simulations were employed to uncover the mechanisms. According to previous studies, aggregation of GO is supposed to be impossible at high pH considering the deprotonation of functional groups on GO and the increased electrostatic repulsions. However, significant aggregations and a reversed trend in zeta potential at high pH were observed. One of the mechanisms was that the promoted metal adsorption at high pH can offset the negative charges generated by the deprotonation. Additionally, the stripping of oxidation debris (OD) on GO also contributes to the unexpected trend in the aggregation behavior and zeta potential. GO consists of lightly oxidized functionalized graphene (FG) sheets and highly oxidized OD. Upon the increase of pH and the deprotonation of functional groups on FG and OD, OD was stripped from FG, which decreased the electrostatic repulsions between FG sheets and accelerated the aggregation. The stripped ODs may recombine to FG edges and bridged FG sheets, which also contribute to the aggregation. Upon the stripping of OD and microstructure transformation of FG, FG-water-OD aggregates formed. According to this study, the aggregation of GO was accompanied by deprotonation of functional groups, metal adsorption, and surface property transformation triggered by the stripping of ODs and should be considered during the development of GO-related nanomaterials and the evaluation of its environmental impact.