Aggregation Behavior of Inorganic 2D Nanomaterials Beyond Graphene: Insights from Molecular Modeling and Modified...

We report the comparative aggregation behavior of three emerging inorganic 2D nanomaterials (NMs): MoS₂, WS₂, and h-BN in aquatic media. Their aqueous dispersions were subjected to aggregation under varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Moreover, Suwanee River Natural Organic Matter (SRNOM) has been used to analyze the effect of natural macromolecules on 2D NM aggregation. An increase in electrolyte concentration resulted in electrical double-layer compression of the negatively charged 2D NMs, thus displaying classical Derjaguin-Landau-Verwey-Overbeek (DLVO)-type interaction. The critical coagulation concentrations (CCC) have been estimated as 37, 60, and 19 mM NaCl and 3, 7.2, and 1.3 mM CaCl₂ for MoS₂, WS₂, and h-BN, respectively. Theoretical predictions of CCC by modified DLVO theory have been found comparable to the experimental values when dimensionality of the materials is taken into account and a molecular modeling approach was used for calculating molecular level interaction energies between individual 2D NM nanosheets. Electrostatic repulsion has been found to govern colloidal stability of MoS₂ and WS₂ while the van der Waals attraction has been found to govern that of h-BN. SRNOM stabilizes the 2D NMs significantly possibly by electrosteric repulsion. The presence of SRNOM completely stabilized MoS₂ and WS₂ at both low and high ionic strengths. While h-BN still showed appreciable aggregation in the presence of SRNOM, the aggregation rates were decreased by 2.6- and 3.7-fold at low and high ionic strengths, respectively. Overall, h-BN nanosheets will have higher aggregation potential and thus limited mobility in the natural aquatic environment when compared to MoS₂ and WS₂. These results can also be used to mechanistically explain fate, transport, transformation, organismal uptake, and toxicity of inorganic 2D NMs in the natural ecosystems.