Structural Evolution of Lanthanum Hydroxides during Long-Term Phosphate Mitigation: Effect of Nanoconfinement

Lanthanum (La)-based materials are effective in removing phosphate (P) from water to prevent eutrophication. Compared to their bulky analogues, La(OH)₃ nanoparticles exhibit a higher P removal efficiency and a more stable P removal ability when spatially confined inside the host. Consequently, the understanding of the nanoconfinement effects on the long-term evolution of La-P structures is crucial for their practical use in P sequestration and recycle, which, however, is still missing. Here, we describe an attempt to explore the evolution of La-P structures, the P environment, and the status of La(OH)₃ nanoparticles confined in the nanopores of the D201 resin, compared to a nonconfined analogue, over a P adsorption period of 25 days in both simulated wastewater and the real bioeffluent. A combinative use of X-ray diffraction (XRD), cross-polarization nuclear magnetic resonance (CP-NMR), and X-ray photoelectron spectroscopy (XPS) techniques confirms the transition from La-P inner-sphere complexation to the formation of LaPO₄·xH₂O and finally to LaPO₄ in both samples. Interestingly, the rate of structural transformation in the real bioeffluent is substantially reduced. Nevertheless, in both conditions, nanoconfinement results in a much faster rate and larger extent of the structural transition. Moreover, nanoconfinement also facilitates the reverse transformation of stable LaPO₄ back to La(OH)₃. Our work provides the scientific basis of nanoconfinement for the preferable use of La-based nanocomposites in P mitigation, immobilization, and recycle application.