Heteroaggregation between graphene oxide and titanium dioxide particles of different shapes in aqueous phase

Graphene oxide (GO) inevitably interacts with engineered and/or natural nanoparticles (NPs) after releasing into aquatic environments. It is observed that GO could form heteroaggregates with differently shaped TiO₂ NP_S at pHs 4.0 and 7.0 rather than pH 10.0. Optimal pHs for the maximal heteroaggregation were around 6.63 and 4.92 for TiO₂ spheres and fibers, respectively, which was dominated by electrostatic attraction. The optimal concentration ratio for TiO₂ spheres was 10 times higher than TiO₂ fibers, due to cross-linking configuration and stronger van der Waals force of TiO₂ fibers with GO. Pre-homoaggregation of TiO₂ NPs could promote subsequent heteroaggregation while the promotion was negligible at high ionic strength (e.g., > critical coagulant concentrations), and a longer pre-homoaggregation time showed a stronger promotion (750 s > 150 s > 0 s). Natural organic matter (NOM) obviously inhibited GO-TiO₂ heteroaggregation at pH 4.0 compared with pH 7.0 due to stronger steric hindrance. Moreover, strong disturbance (e.g., sonication) could break down the heteroaggregates, and the disaggregation and re-aggregation processes were shape-independent. This work provides new insights into the role of NPs shapes and homoaggregation on the interaction of GO with both engineered and natural particles/minerals, and the fate of GO in aquatic environments.