Ionic specificity mediates the transport and retention of graphene-based nanomaterials in saturated porous media.

Transport of graphene-based nanomaterials in porous media is closely related to background cations. This study examines the impacts of ionic specificity on the mobility of graphene oxide (GO) and reduced GO (RGOs) in saturated quartz sand. The transport of GO/RGOs as affected by monovalent cation Na followed extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, whereas in solutions containing multivalent cations Zn and Al, cation bridging effect played a dominant role in the transport inhibition. Moreover, the adverse effects of the divalent cations on GO/RGOs migration obeyed the Hofmeister series, i.e. following the order of Pb > Cd > Zn. Batch adsorption experiments and DFT calculations further confirmed that cations of higher valences, and of the same valence but with larger ionic radii (smaller hydrated radii) interacted more strongly with GO/RGOs and sand grains via forming inner-sphere complexes. Thus, more favorable retention was observed through cation bridging between particles and collectors, and also via enhanced straining caused by particles aggregation. Furthermore, the sulfide-reduced GO (SR-GO) that contained more surface O-functional groups was impacted more remarkably by strong complexing cations than the pristine GO (P-GO), while the mobility of poorly functionalized irradiation-reduced GO (IR-GO) was less affected by cation bridging effect.