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.