Synergistic Effect of Metal Cations and Visible Light on 2D MoS₂ Nanosheet Aggregation

Aggregation significantly influences the transport, transformation, and bioavailability of engineered nanomaterials. Two-dimensional MoS₂ nanosheets are one of the most well-studied transition-metal dichalcogenide nanomaterials. Nonetheless, the aggregation behavior of this material under environmental conditions is not well understood. Here, we investigated the aggregation of single-layer MoS₂ (SL-MoS₂) nanosheets under a variety of conditions. Trends in the aggregation of SL-MoS₂ are consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) colloidal theory, and the critical coagulation concentrations of cations follow the order of trivalent (Cr³⁺) < divalent (Ca²⁺, Mg²⁺, Cd²⁺) < monovalent cations (Na⁺, K⁺). Notably, Pb²⁺ and Ag⁺ destabilize MoS₂ nanosheet suspensions much more strongly than do their divalent and monovalent counterparts. This effect is attributable to Lewis soft acid-base interactions of cations with MoS₂. Visible light irradiation synergistically promotes the aggregation of SL-MoS₂ nanosheets in the presence of cations, which was evident even in the presence of natural organic matter. The light-accelerated aggregation was ascribed to dipole-dipole interactions due to transient surface plasmon oscillation of electrons in the metallic 1T phase, which decrease the aggregation energy barrier. These results reveal the phase-dependent aggregation behaviors of engineered MoS₂ nanosheets with important implications for environmental fate and risk.