Urchin-like structured magnetic hydroxyapatite for the selective separation of cerium ions from aqueous solutions

In this study, bio-inspired urchin-like structured hydroxyapatite (UHdA) and its magnetic composite (UHdA@Fe₃O₄) were developed for efficient and easy separation of cerium ions (Ce³⁺) from aquatic waste streams. UHdA and UHdA@Fe₃O₄ exhibited superior Ce³⁺ adsorption capacities of 248.39 and 230.01 mg/g-UHdA respectively, compared to a commercial HdA (141.71 mg/g-HdA) due to their hierarchical mesoporous structure and large specific surface area. The adsorption of Ce³⁺ to UHdA and UHdA@Fe₃O₄ were heterogeneous, pseudo-second-order-kinetic, and the rate-limiting step was external mass transfer and intra-particle diffusion. Moreover, thermodynamic studies revealed that the adsorption process was spontaneous and endothermic nature. The high selectivity towards Ce³⁺ in multi-ionic systems is attributed to the strong affinity between strong Lewis acid (Ce³⁺) and base (PO₄^3- and OH^-) interactions. XRD, FTIR, and XPS analysis demonstrated that the adsorption was mainly attributable to the ion exchange of Ce³⁺ with Ca²⁺ and to surface complexation. The desorption of Ce³⁺ was efficiently accomplished using 0.1 M HNO₃. The results suggest that UHdA and UHdA@Fe₃O₄ could be promising choices for the adsorption and recovery of rare earth elements.