There is a need for developing new sorbents that incorporate renewable resources for the treatment of metal-containing solutions. Algal-polyethyleneimine beads (APEI) (reinforced with alginate) are functionalized by grafting amidoxime groups (AO-APEI). Physicochemical characteristics of the new material are characterized using FTIR, XPS, TGA, SEM, SEM-EDX, and BET. AO-APEI beads are tested for the recovery of Sr(II) from synthetic solutions after pH optimization (≈ pH 6). Uptake kinetics is fast (equilibrium ≈ 60–90 min). Sorption isotherm (fitted by the Langmuir equation) shows remarkable sorption capacity (≈ 189 mg Sr g⁻¹). Sr(II) is desorbed using 0.2 M HCl/0.5 M CaCl₂ solution; sorbent recycling over five cycles shows high stability in terms of sorption/desorption performances. The presence of competitor cations is studied in relation to the pH; the selectivity for Sr(II) is correlated to the softness parameter. Finally, the recovery of Sr(II) is carried out in complex solutions (seawater samples): AO-APEI is remarkably selective over highly concentrated metal cations such as Na(I), K(I), Mg(II), and Ca(II), with weaker selectivity over B(I) and As(V). AO-APEI appears to be a promising material for selective recovery of strontium from complex solutions (including seawater).

High-tech applications require increasing amounts of rare earth elements (REE). Their recovery from low-grade minerals and their recycling from secondary sources (as waste materials) are of critical importance. There is increasing attention paid to the development of new sorbents for REE recovery from dilute solutions. A new generation of composite sorbents based on brown algal biomass (alginate) and polyethylenimine (PEI) was recently developed (A_LPEI hydrogel beads). The phosphorylation of the beads strongly improves the affinity of the sorbents for REEs (such as La and Tb): by 4.5 to 6.9 times compared with raw beads. The synthesis procedure (epicholorhydrin-activation, phosphorylation and de-esterification) is investigated by XPS and FTIR for characterizing the grafting route but also for interpreting the binding mechanism (contribution of N-bearing from PEI, O-bearing from alginate and P-bearing groups). Metal ions can be readily eluted using an acidic calcium chloride solution, which regenerates the sorbent: the FTIR spectra are hardly changed after five successive cycles of sorption and desorption. The materials are also characterized by elemental, textural and thermogravimetric analyses. The phosphorylation of A_LPEI beads by this new method opens promising perspectives for the recovery of these strategic metals from mild acid solutions (i.e., pH ~ 4).

With the target of recovering rare earth elements (REEs) from acidic leachates, a new functionalized hydrogel was designed, based on the phosphorylation of algal/polyethyleneimine beads. The functionalization strongly increased the sorption efficiency of the raw material for Pr(III) and Tm(III). Diverse techniques were used for characterizing this new material and correlating the sorption performances and mechanisms to the physicochemical structure of the sorbent. First, the work characterized the sorption properties from synthetic solutions with the usual procedures (study of pH effect, uptake kinetics, sorption isotherms, metal desorption and sorbent recycling, and selectivity from multi-element solutions). Optimum pH was found close to 5; sorption isotherms were fitted by the Langmuir equation (maximum sorption capacities close to 2.14 mmol Pr g⁻¹ and 1.57 mmol Tm g⁻¹). Fast uptake kinetics were modeled by the pseudo-second order rate equation. The sorbent was highly selective for REEs against alkali-earth and base metals. The sorbent was remarkably stable for sorption and desorption operation (using 0.2 M HCl/0.5 M CaCl₂ solutions). The sorbent was successfully applied to the leachates of Egyptian ore (pug leaching) after a series of pre-treatments (precipitation steps), sorption, and elution. The selective precipitation of REEs using oxalic acid allows for the recovery of a pure REE precipitate.