The long-lasting stability of nanoparticle
(NP) suspensions in
aqueous solution is one of the main challenges in colloidal science.
The addition of surfactants is generally adopted to increase the free
energy barrier between NPs and hence to ensure a more stable condition
avoiding the NP sedimentation. However, a tailored prediction of surfactant
concentration enabling a good dispersion of NPs is still an ambitious
objective. Here, we demonstrate the efficiency of coupling steered
molecular dynamics (SMD) with the Langmuir theory of adsorption in
the low surfactant concentration regime, to predict the adsorption
isotherm of sodium-dodecyl-sulfate (SDS) on bare α-alumina NPs
suspended in aqueous solution. The resulting adsorption free energy
landscapes (FELs) are also investigated by tuning the percentage of
SDS molecules coating the target bare NP. Our findings shed light
on the competing role of enthalpic and entropic interaction contributions.
On one hand, the adsorption is highly promoted by the tail–NP
and tail–tail nonbonded interaction adhesion; on the other
hand, our results unveil the entropic nature of water and surfactant
steric effects occurring at the NP surface and preventing the adsorption.
Finally, a thorough analysis on the steering works emphasizes the
role of the NP curvature in the FEL of adsorption. In particular,
we show that, moving from a solid infinite flat surface to a nanoscale
particle, a deviation from a Markovian dynamics of adsorption occurs
in close proximity to a curved solid–liquid interface. Here,
both the NP curvature effect and nanoscale morphology promote a modification
of the thermodynamics state of adsorption with a consequent splitting
of the free energy profiles and the identification of specific sites
of adsorption. The modeling framework suggested in this Article provides
physical insights in the surfactant adsorption onto spherical NPs
and suggests some guidelines to rationally design stable NP suspensions
in aqueous solutions.