Extraction of Gd³⁺ and UO₂²⁺ Ions Using Polystyrene Grafted Dibenzo Crown Ether (DB18C6) with Octanol and...

Atomistic molecular dynamics (MD) simulations are performed in order to derive thermodynamic properties important to understand the extraction of gadolinium (Gd³⁺) and uranium dioxide (UO₂) with dibenzo crown ether (DBCE) in nitrobenzene (NB) and octanol (OCT) solvents. The effect of polystyrene graft length, on DBCE, on the binding behavior of Gd³⁺ and UO₂²⁺ is investigated for the first time. Our simulation results demonstrate that the binding of Gd³⁺ and UO₂²⁺ onto the oxygens of crown ethers is favorable for polystyrene grafted crown ether in the organic solvents OCT and NB. The metal ion binding free energy (ΔG_Binding) in different solvent environments is calculated using the thermodynamic integration (TI) method. ΔG_Binding becomes more favorable in both solvents, NB and OCT, with an increase in the polystyrene monomer length. The metal ion transferability from an aqueous phase to an organic phase is estimated by calculating transfer free-energy calculations (ΔG_Transfer). ΔG_Transfer is significantly favorable for both Gd³⁺ and UO₂²⁺ for the transfer from the aqueous phase to the organic phase (i.e., NB and OCT) via ion-complexation to DBCE with an increase in polystyrene length. The partition coefficient (log P) values for Gd³⁺ and UO₂²⁺ show a 5-fold increase in separation capacity with polystyrene grafted DBCE. We corroborate the observed behavior by further analyzing the structural and dynamical properties of the ions in different phases.