Highly selective removal of thorium from acidic solutions achieved on phosphonic acid functionalized core–shell magnetic nanocomposite: Understanding adsorption and binding mechanisms

Abstract

Thorium has received widespread attention as potential nuclear fuel alternative for the next-generation thorium-based molten salt reactors. With the growth of nuclear energy, it is needful to exploit magnetic nanomaterials to remove thorium from aqueous solutions, owing to their superparamagnetism and large specific surface energy. Nevertheless, most of magnetic nanomaterials often suffered from low thorium selectivity and poor structural ability in acidic solutions. Herein, a novel core–shell magnetic nanocomposite Fe3O4@SiO2/P (AA-MMA-VPA) possessing phosphonic acid was developed by a controlled radical polymerization of vinylphosphonic acid (VPA) in the presence of Fe3O4 encapsulated by SiO2 (Fe3O4@SiO2). Due to the presence of the high content of phosphonic acid groups and the absence of any universal groups, Fe3O4@SiO2/P (AA-MMA-VPA) displayed exceptional selectivity for thorium in the presence of 11 co-existing cations. The separation factor STh/M value for Fe3O4@SiO2/P(AA-MMA-VPA) concerning all other competing cations surpassed 74.4, and the largest value for STh/M even amounted to 343.5. Further, Fe3O4@SiO2/P (AA-MMA-VPA) possessed a maximum adsorption capacity (qmax) of 485.4 mg g−1 at pH of 3.0, higher than that of other magnetic sorbents. By reason of its core–shell structure, the sorbent possessed an outstanding structure stability even after immersed into HNO3 solution at pH of 0.5 for 72 h. The sorbent could as well be magnetically recouped, and recycled at least six times without evident diminution in sorption amount. The sterling removal performance of the sorbent was assigned to the interaction of thorium with phosphonic acid, corroborated by FT-IR, XPS and DFT method. Thus, this study affords a new viewpoint for exploiting magnetic nanomaterials with sterling acidic resistance for the strongly selective entrapment of thorium from acidic media.