Interaction of Cu_n, Ag_n and Au_n (n = 1-4) nanoparticles with ChCl:Urea deep eutectic solvent

In this study, the interaction of noble metal nanoparticles (M_n, M = Cu, Ag, and Au; n = 1-4) with ChCl:Urea deep eutectic solvent was investigated using density functional theory (DFT) method. We find that ChCl:Urea mostly interact with the M_n nanoparticles through [Cl]^- anion ([Cl]^-…M_n) and nonconventional H-bonds of C-H⋯M_n and N-H⋯M_n. NBO, QTAIM, NCI and EDA analyses show that [Cl]^-…M_n interactions are stronger than the nonconventional H-bonds interactions. Our results indicate that the nature of [Cl]^-…M_n interactions is electrostatic, while the nonconventional H-bonds of C-H⋯M_n and N-H⋯M_n are van der Waals in nature. The negative values of enthalpy (ΔH) and free energy (ΔG) for the ChCl:Urea…M_n complexes reveal that the formation of ChCl:Urea…M_n complexes is exothermic and proceeds spontaneously. The calculation of binding energy (ΔE_b) of M_n nanoparticles with ChCl:Urea shows that the strength of interaction of Au_n nanoparticles with ChCl:Urea is more favorable than Cu_n and Ag_n, following the order ChCl:Urea…Au_n > ChCl:Urea…Cu_n > ChCl:Urea…Ag_n. Furthermore, the ΔE_b, ΔH and ΔG values enhance with increasing nanoparticle size from n = 1 to n = 4, ChCl:Urea…M₄> ChCl:Urea…M₃> ChCl:Urea…M₂> ChCl:Urea…M₁ (M = Cu, Ag, and Au).