Partitioning behavior and stabilization of hydrophobically coated HfO2, ZrO2 and Hfx Zr 1-x O2 nanoparticles with natural organic matter reveal differences dependent on crystal structure.

The interactions of engineered nanomaterials with natural organic matter (NOM) exert a profound influence on the mobilities of the former in the environment. However, the influence of specific nanomaterial structural characteristics on the partitioning and colloidal stabilization of engineered nanomaterials in various ecological compartments remains underexplored. Herein, we present a systematic study of the interactions of humic acid (HA, as a model for NOM) with monodisperse, well-characterized, ligand-passivated HfO(2), ZrO(2), and solid-solution Hf(x)Zr(1-x)O(2) nanoparticles (NPs). We note that mixing with HA induces the almost complete phase transfer of hydrophobically coated monoclinic metal oxide (MO) NPs from hexane to water. Furthermore, HA is seen to impart appreciable colloidal stabilization to the NPs in the aqueous phase. In contrast, phase transfer and aqueous-phase colloidal stabilization has not been observed for tetragonal MO-NPs. A mechanistic model for the phase transfer and aqueous dispersal of MO-NPs is proposed on the basis of evidence from transmission electron microscopy, ζ-potential measurements, dynamic light scattering, Raman and infrared spectroscopies, elemental analysis, and systematic experiments on a closely related set of MO-NPs with varying composition and crystal structure. The data indicate the synergistic role of over-coating (micellar), ligand substitution (coordinative), and electrostatic processes wherein HA acts both as an amphiphilic molecule and a charged chelating ligand. The strong observed preference for the phase transfer of monoclinic instead of tetragonal NPs indicates the importance of the preferential binding of HA to specific crystallographic facets and suggests the possibility of being able to design NPs to minimize their mobilities in the aquatic environment.