Inorganic
colloidal nanoparticle (NP) properties can be tuned by
stripping stabilizing ligands using a poor solvent. However, the mechanism
behind ligand stripping is poorly understood, in part because in situ measurements of ligand stripping are challenging
at the nanoscale. Here, we investigate ethanol solvent-mediated oleylamine
ligand stripping from magnetite (Fe3O4) NPs
in different compositions of ethanol/hexane mixtures using atomistic
molecular dynamics (MD) simulations and thermogravimetric analysis
(TGA). Our study elucidates a complex interplay of ethanol interactions
with system components and indicates the existence of a threshold
concentration of ∼34 vol % ethanol, above which ligand stripping
saturates. Moreover, hydrogen bonding between ethanol and stripped
ligands inhibits subsequent readsorption of the ligands on the NP
surface. A proposed modification of the Langmuir isotherm explains
the role of the enthalpy of mixing of the ligands and solvents on
the ligand stripping mechanism. A good agreement between the MD predictions
and TGA measurements of ligand stripping from Fe3O4 NPs validates the simulation observations. Our findings demonstrate
that the ligand coverage of NPs can be controlled by using a poor
solvent below the threshold concentration and highlight the importance
of ligand–solvent interactions that modulate the properties
of colloidal NPs. The study also provides an approach for a detailed in silico study of ligand stripping and exchange from colloidal
NPs that are crucial for applications of NPs spanning self-assembly,
optoelectronics, nanomedicine, and catalysis.