Three-dimensional, multi-functionalized nanocellulose/alginate hydrogel for efficient and selective phosphate scavenging: Optimization, performance, and in-depth mechanisms.

Challenges in developing adsorbents with sufficient phosphate (P) adsorption capacity, selectivity, and regeneration properties remain to be addressed. Herein, a multi-functionalized high-capacity nanocellulose/alginate hydrogel (La-NCF/SA-PEI [La: lanthanum, NCF: nanocellulose fiber, SA: sodium alginate, PEI: polyethyleneimine]) was prepared through environmentally friendly methods. The La-NCF/SA-PEI hydrogel, featuring a 3D porous structure with interwoven functional groups (amino, quaternary ammonium, and lanthanum), demonstrated a maximum P adsorption capacity of 78.0 mg/g, exceeding most La-based hydrogel adsorbents. The kinetic and isotherm fitting results confirmed the multilayer chemisorption process. Comprehensive experimental results, instrumental analysis, and computational results revealed that the ammonium phosphate complex (NH3+-O-P) and the inner-sphere complex (La-O-P) formed by La(OH)3 dominated the selective P adsorption process. Density-functional theory (DFT) was employed to calculate the bond length between phosphate and each component of the La-NCF/SA-PEI. The calculation results revealed the double-bridge adsorption between the N (apex) atom on La-NCF/SA-PEI and the O (apex) atomic site in phosphate, including electrostatic adsorption and two hydrogen bonds (bond lengths 1.001 and 1.008 Å) between the O of PO43- and the H+ of the protonated amino group. Except the remarkable P adsorption performance (both municipal sewage and aquaculture tail water), the La-NCF/SA-PEI hydrogel's high selectivity toward P, environmental compatibility, and easy separability from water underscore its significant potential for phosphate-contaminated water remediation. The multi-functionalized La-NCF/SA-PEI demonstrate promising potential for P removal applications and advanced the development of sustainable, biomass-based adsorbents design.