Molecular dynamics simulations of hyperbranched poly(ethylene imine)-graphene oxide nanocomposites as dye adsorbents for water purification.

Atomistically detailed molecular dynamics simulations were employed to study the adsorption capacity of graphene-oxide-based (GO) aqueous systems for the methylene blue (MB) dye in the presence of branched poly(ethylene imine) (BPEI) polymers. The polymeric component was either freely mixed or chemically attached to GO. The main focus was the elucidation of the effects originating from the presence of BPEI molecules in the association of MB with the formed GO complexes. The effect of temperature was also examined. It was found that the presence of the cationic BPEI molecules results in the formation of a distinct microenvironment characterized by a polymer-mediated interconnected morphology which promotes the development of larger-sized MB clusters. These clusters were found to form in the vicinity of the GO flakes, increasing thus the adsorption capacity of the dye molecules in the polymer-containing systems. Particularly in the system with the BPEI-functionalized GO flakes, a persistent percolated structure is formed, which results in a more restricted diffusion of the MB molecules, increasing thus significantly their residence time close to the GO surface. The clustering behavior of MB was found to be temperature-dependent in the BPEI-based models, providing useful information regarding the conditions for optimal adsorption performance of such membranes, in nanofiltration processes.