The surface diffusivity of nanoparticles physically adsorbed at a solid-liquid interface.

This work proposes an analytical model considering the effects of hydrodynamic drag and kinetic barriers induced by liquid solvation forces to predict the translational diffusivity of a nanoparticle on an adsorbing surface. Small nanoparticles physically adsorbed to a well-wetted surface can retain significant in-plane mobility through thermally activated stick-slip motion, which can result in surface diffusivities comparable to the bulk diffusivity due to free-space Brownian motion. Theoretical analysis and molecular dynamics simulations in this work show that the surface diffusivity is enhanced when (i) the Hamaker constant is smaller than a critical value prescribed by the interfacial surface energy and particle dimensions, and (ii) the nanoparticle is adsorbed at specific metastable separations of molecular dimensions away from the wall.

Kinetic trapping of nanoparticles by solvent-induced interactions.

Theoretical analysis based on mean field theory indicates that solvent-induced interactions ( structural forces due to the rearrangement of wetting solvent molecules) not considered in DLVO theory can induce the kinetic trapping of nanoparticles at finite nanoscale separations from a well-wetted surface, under a range of ubiquitous physicochemical conditions for inorganic nanoparticles of common materials (, metal oxides) in water or simple molecular solvents. This work proposes a simple analytical model that is applicable to arbitrary materials and simple solvents to determine the conditions for direct particle-surface contact or kinetic trapping at finite separations, by using experimentally measurable properties (, Hamaker constants, interfacial free energies, and nanoparticle size) as input parameters. Analytical predictions of the proposed model are verified by molecular dynamics simulations and numerical solution of the Smoluchowski diffusion equation.