Structure, Interaction, and Dynamics of Au/Pd Bimetallic Nanoalloys Dispersed in Aqueous Ethylpyrrolidone, a Monomeric Moiety of Polyvinylpyrrolidone

Bimetallic nanoparticles (NPs) have been shown to exhibit certain advantages over pure NPs in catalysis due to a synergistic effect. It is common to disperse NPs in a polymer matrix such as polyvinylpyrrolidone (PVP) to prevent flocculation, which imparts considerable electronic effects on the NPs. In the present study, the interactions between aqueous solutions of N-ethylpyrrolidone (EP, system chosen to model the monomeric form of PVP) and Au/Pd bimetallic NPs, which are relevant in catalysis, have been investigated using molecular dynamics simulations and density functional theory (DFT) method. The adequacy of the force fields used was assessed based on their ability to reproduce the structures and adsorption energies obtained using DFT calculations. The interactions of NPs with the environment were studied at various concentrations of aqueous solutions of EP to examine the strength of NP-EP and NP-water interactions. Free energy calculations and local mole fraction enhancement values show that that the EP adsorption on NPs is preferred over the adsorption of water. Extensive analysis of the interactions of the NPs with various concentrations of aqueous EP suggests the existence of isolated water molecules that may take part in reactions. Adsorption of unexpectedly large numbers of EP molecules was found to be possible leading to accumulation of the electron density on the Au/Pd NPs, which have previously been shown to enhance the catalytic activity of NPs. This study emphasizes the importance of including the electronic effects on the NPs due to the adsorption of stabilizing agents in modeling and demonstrates the utility of MD simulations to generate appropriate model chemistries for studying catalysis at higher level quantum chemical and density functional theory calculations.