Glycerol-Modified Binary Layered Double Hydroxide Nanocomposites for Uranium Immobilization via Extended X-ray Absorption Fine Structure Technique and Density Functional Theory Calculation

Novel, efficient, glycerol-modified nanoscale layered double hydroxides (rods Ca/Al LDH-Gl and flocculent Ni/Al LDH-Gl) were successfully synthesized by a simple one-step hydrothermal synthesis route and showed excellent adsorption capacities for U(VI) from aqueous solutions under various environmental conditions. The advanced spectroscopy analysis confirmed the existence of abundant oxygen-containing functional groups (e.g., C-O, O-CO, and CO) on the surfaces of Ca/Al LDH-Gl and Ni/Al LDH-Gl, which could provide enough free active sites for the binding of U(VI). The maximum adsorption capacities of U(VI) calculated from the Sips model were 266.5 mg·g^-1 for Ca/Al LDH-Gl and 142.3 mg·g^-1 for Ni/Al LDH-Gl at 298.15 K, and the higher adsorption capacity of Ca/Al LDH-Gl might be due to more functional groups and abundant high-activity “Ca-O” groups. Macroscopic experiments proved that the interaction of U(VI) on Ca/Al LDH-Gl and Ni/Al LDH-Gl was due to surface complexation and electrostatic interactions. The extended X-ray absorption fine structure analysis confirmed that U(IV) did not transformation to U(VI) on solid particles, and stable inner-sphere complexes were not formed by reduction interaction but by chemical adsorption. The density functional theory (DFT) calculations further evidenced that the higher adsorption energies (i.e., E_ad = 4.00 eV for Ca/Al LDH-Gl-UO₂²⁺ and E_ad = 2.43 eV for Ca/Al LDH-Gl-UO₂CO₃) were mainly attributed to stronger hydrogen bonds and electrostatic interactions. The superior immobilization performance of Ca/Al LDH-Gl supports a potential strategy for decontamination of UO₂²⁺ from wastewater, and it may provide new insights for the efficient removal of radionuclides in environmental pollution cleanup.