Adsorption of Hydrated Pr³⁺ and NH₄⁺/Mg²⁺ Ions onto the (001) Surface of Montmorillonite: A DFT Analysis with Experimental Verification

Abstract

Montmorillonite is a major mineral present in ion-adsorption rare earth ores, and the microscopic adsorption states of rare earth ions on its surface are of a great significance for the efficient exploitation of ion-adsorption rare earth ores. In this article, density functional theory calculations were used to investigate the adsorption mechanisms and bonding characteristics of hydrated Pr, Mg and NH4 ions on the (001) surface of montmorillonite. Pr3+ exhibited a directed tendency geometry with Pr(H2O)103+, which was adsorbed onto montmorillonite by hydrogen bonding with an adsorption energy of −1182 kJ/mol, and one coordinated H2O ligand was separated from the first hydration layer of Pr. Both hydrated Mg and NH4 ions were adsorbed onto the montmorillonite surface through hydrogen bonds, and the adsorption energies were −206 and −188 kJ/mol, respectively, indicating that the adsorption stability of the hydrated Mg ion was slightly higher than that of the hydrated NH4 ion, but both were lower than that of hydrated Pr (−1182 kJ/mol). Hence, higher concentrations of Mg and NH4 ions than rare earth ions would be necessary in the leaching process of ion-adsorption rare earth ores. Additionally, desorption experiments revealed that the recovery of Pr3+ by Mg2+ with a concentration of 38 mmol/L is 80%, while it is only 65% with the same concentration of NH4+, and the concentrations of Mg2+ and NH4+ were much higher than that of Pr3+ in lixivium, which is consistent with the DFT calculations.

Keywords

• DFT
• Pr³⁺
• Mg²⁺
• NH₄⁺
• montmorillonite
• adsorption