DFT study of interaction of Palladium Pd_n (n = 1-6) nanoparticles with deep eutectic solvents

In this study, we use density functional theory (DFT) calculations to investigate the stability, reactivity and interactions of Palladium Pd_n (n = 1-6) nanoparticles with ChCl:U and ChCl:EG based deep eutectic solvents (DESs). We find that the DES … Pd_n complexes are stabilized by two types of binding; Pd_n-X anchoring bonds (X = N atom of -NH₂ group in urea and [Cl]^- anion) and Pd_n…H-X (X = C, N and O) unconventional H-bonds. Analyses based on AIM, NBO, NCI, and EDA suggest that the anchoring bonds, which are electrostatic in nature are stronger than the unconventional H-bonds, which are van der Waals in nature. The Energy Decomposition Analysis reveals that the charge transfer plays an important role in the stability of DES…Pd_n complexes. Thermochemical calculations, including enthalpy (ΔH) and free energy (ΔG), indicate that the formation of the DES…Pd_n complexes is exothermic and occurs spontaneously. The binding energy (ΔE_b) calculations show that the ChCl:U DES has a stronger interaction with the Pd_n nanoparticles than their ChCl:EG DES counterparts. On the other hand, a similar trend for the ΔE_b, ΔH and ΔG values of the complexes is observed with increasing nanoparticle size of Pd_n (DES…Pd₅> DES…Pd₆> DES…Pd₄> DES…Pd₃> DES…Pd₂> DES…Pd₁). Our results show that the magnitude of charge transfer (ΔQ) value in the complexes follow the order observed for the ΔE_b values. It is also observed that increasing the energy gap E_g values of the complexes decreases the ΔE_b and ΔQ values of the complexes. The reactivity parameter calculations of the complexes show that the E_g and chemical hardness (η) values of ChCl:U…Pd_n and ChCl:EG…Pd_n complexes decrease with an increase in the nanoparticle size. Additionally, the global electrophilicity index (ω) values of the DES…Pd_n complexes increase with an increase in the Pd_n nanoparticle size, while no clear trend is seen for the chemical potential (μ) values of the complexes. The urea-based DES shows better suitability towards Pd_n nanoparticles than the ethylene glycol-based DES. Overall, such DESs are potentially promising green solvents for nanoparticle synthesis and activity.