Highly efficient U(VI) capture by amidoxime/carbon nitride composites: Evidence of EXAFS and modeling

Abstract

The recovery of uranium from wastewater and safe treatment of U(VI)-containing wastewater are of great important to ensure the sustainable development of nuclear-related energy. Although abundant studies of U(VI) sorption on various adsorbents have been widely achieved, U(VI) sorption at extreme pH and trace concentration is challenging issues due to limited sorption activity of natural adsorbents. The development of novel materials with highly efficient and excellent selectivity for capturing U(VI) from nuclear-related wastewater and seawater is highly desirable. In this study, amidoxime/carbon nitride (AO/g-C₃N₄) was fabricated and captured U(VI) under a variety of water chemistry. We demonstrated that AO/g-C₃N₄ exhibited the high adsorption capacities (312 mg/g at pH 6.8), fast removal equilibrium (>98% at 10 min) and superior selectivity for U(VI) compared with the other radionuclides (e.g., 19.76 mg/g of Cs(I)). In addition, AO/g-C₃N₄ exhibited the high uranium extraction capacity from natural seawater (9.55 mg/g at saturation time of 5.5 days) compared to vanadium (1.85 mg/g). U(VI) adsorption behavior at different pH can be excellently fitted by the surface complexation modeling with three inner sphere surface complexes (i.e., SOUO₂(CO₃)₂^3-, SO(UO₂)₃(OH)₅⁰ and SOUO₂⁺ species). According to XPS (X-ray Photoelectron Spectroscopy) analysis, the strong complexation of U(VI) with AO groups retained in C₃N₄ nanosheet. The split of U-O_eq2 subshell and the occurrence of U-C shell further demonstrated inner-sphere surface complexation by EXAFS (X-Ray Absorption Fine Structure) spectra analyses. These results revealed that the high potential of AO/g-C₃N₄ materials for selective U(VI) capture from wastewater and seawater.

Keywords: Amidoxime; Carbon nitride; EXAFS; Modeling; U(VI).