Revealing the Origin of Cooperative Adsorption of Chains on Nanoparticle Surfaces through Coarse-Grained Simulations

This work aims to deepen our understanding of the molecular origin of the recently observed phenomenon of polymer cooperative adsorption onto faceted nanoparticle (NP) surfaces. By exploring a large parameter space for polymer/NP interactions through coarse-grained (CG) molecular dynamics (MD) simulations, it is found that consistent with experiments the presence or absence of cooperativity is related to solvent quality and relative interaction strengths between the polymer and the adsorbent. Specifically, positive cooperativity is associated with stronger polymer-polymer interaction than polymer-surface interactions and vice versa for negative cooperativity. This contrast in interaction energies manifests in positive cooperativity (i.e., increased affinity) and negative cooperativity (i.e., decreased affinity) as concentration increases. It is also found that increasing chain length strengthens cooperativity effects and that the nanoscale confinement of polymer chains to the adsorbing facet (due to weaker affinity to corners and edges) enhances positive cooperativity but weakens negative cooperativity. Moreover, adsorption onto a spherical NP shows stronger positive cooperativity but weaker negative cooperativity compared with adsorption onto a cubic NP of equal surface area. It was further found that as polymer bulk concentration increases, the free energy of adsorption decreases in positive cooperativity, increases in negative cooperativity, and is independent of concentration in noncooperative systems consistent with the phenomenological explanation of cooperativity. We further found that positive cooperativity is associated with growing fluctuations in the adsorption density at critical bulk polymer concentrations. This behavior can be attributed to the competition between enthalpic gains and entropic losses upon adsorption. Overall, our results shed light on the microscopic origin of cooperative adsorption and the role of solvent quality, which can be leveraged in, for example, controlling NP growth into target shapes and designing NP catalysts with improved performance.