Modified chitosan has been widely used for heavy metals removal during the last few decades. In this research, the study was focused on the effect of modified chitosan particles after grafting with heterocyclic constituent for enhancing the sorption of Cr(VI) ions. Chitosan was functionalized by 2-thioxodihydropyrimidine-4,6(1H,5H)-dione, in which the synthesized composite considered as a nanoscale size with average 5–7 nm. This explains the fast kinetics of sorption with large surface area. The prepared sorbent was characterized by Fourier-transform infrared (FTIR), elemental analysis (EA), Brunauer–Emmett–Teller (BET surface area) theory, thermogravimetric analysis (TGA), mass spectroscopy, and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) analyses. The experimental part of this work involved the application of the synthesized sorbent for the removal of Cr(VI) ions from highly contaminated tannery effluents that are characterized by a high concentration toward chromate ions with other associated toxic elements, i.e., Pb(II) and Cd (II) ions, which underscore the importance of this treatment. Under the selected conditions (K₂Cr₂O₇ salt, C_o: 100 mg L⁻¹ and pH: 4), the sorption diagram shows high Cr(VI) sorption and fast uptake kinetics. The sorption was enhanced by functionalization to 5.7 mmol Cr g⁻¹ as well as fast uptake kinetics; 30 min is sufficient for total sorption compared with 1.97 mmol Cr g⁻¹ and 60 min for the non-grafted sorbent. The Langmuir and Sips equations were fitted for the sorption isotherms, while the pseudo-first order rate equation (PFORE) was fitted for the uptake kinetics.

This work presents a novel hydrothermally aided sol-gel method for preparation of mesoporous silica nanoparticles (MSNs) with a narrow particle size distribution and varied pore sizes. The method was carried out in alkaline media in presence of polyethylene glycol (PEG) and cetyltrimethylammonium chloride (CTAC) as dual templates and permitted the synthesis of spherical mesoporous silica with a high surface area (1011.42 m²/g). The MSN materials were characterized by FTIR, Thermogravimetric (TG), Nitrogen adsorption and desorption and Field emission scanning electron microscopic analysis (FESEM). The materials feasibility as solid phase adsorbent has been demonstrated using cationic dyes; Rhodamine B (RB) and methylene blue (MB) as models. Due to the large surface area and variable pore width, the adsorption behaviors toward cationic dyes showed outstanding removal efficiency and a rapid sorption rate. The adsorption isotherms of RB and MB were well-fitted to the Langmuir and Freundlich models, while the kinetic behaviours adhered closely to the pseudo-second-order pattern. The maximum adsorption capacities were determined to be 256 mg/g for MB and 110.3 mg/g for RB. The findings suggest that MSNs hold significant potential as solid-phase nanosorbents for the extraction and purification of dye pollutants, particularly in the analysis and treatment of effluents containing cationic dyes.

Sulfonic resins are highly efficient cation exchangers widely used for metal removal from aqueous solutions. Herein, a new sulfonation process is designed for the sulfonation of algal/PEI composite (A*PEI, by reaction with 2-propylene-1-sulfonic acid and hydroxylamine-O-sulfonic acid). The new sulfonated functionalized sorbent (SA*PEI) is successfully tested in batch systems for strontium recovery first in synthetic solutions before investigating with multi-component solutions and final validation with seawater samples. The chemical modification of A*PEI triples the sorption capacity for Sr(II) at pH 4 with a removal rate of up to 7% and 58% for A*PEI and SA*PEI, respectively (with SD: 0.67 g L⁻¹). FTIR shows the strong contribution of sulfonate groups for the functionalized sorbent (in addition to amine and carboxylic groups from the support). The sorption is endothermic (increase in sorption with temperature). The sulfonation improves thermal stability and slightly enhances textural properties. This may explain the fast kinetics (which are controlled by the pseudo-first-order rate equation). The sulfonated sorbent shows a remarkable preference for Sr(II) over competitor mono-, di-, and tri-valent metal cations. Sorption properties are weakly influenced by the excess of NaCl; this can explain the outstanding sorption properties in the treatment of seawater samples. In addition, the sulfonated sorbent shows excellent stability at recycling (for at least 5 cycles), with a loss in capacity of around 2.2%. These preliminary results show the remarkable efficiency of the sorbent for Sr(II) removal from complex solutions (this could open perspectives for the treatment of contaminated seawater samples).

The development of new materials based on biopolymers (as renewable resources) is substantial for environmental challenges in the heavy metal and radionuclide ions removal contaminations. Functionalization of chitosan with sulfonic groups was achieved for improving the uranium sorption, not only from slightly acidic leachate, but also for the underground water. The prepared hydrogel based on chitosan was characterized by series of analysis tools for structure elucidation as FTIR spectroscopy, textural properties using nitrogen adsorption method, pH_PZC (by pH-drift method), thermogravimetric analysis (TGA), SEM, and SEM-EDX analyses. The sorption was performed toward uranium (VI) ions for adjustment of sorption performances. The optimum sorption was performed at pH 4 (prior to the precipitation pH). The total sorption was achieved within 25 min (relatively fast kinetics) and was fitted by pseudo-first order rate equation (PFORE) and resistance to intraparticle diffusion equation (RIDE). The maximum sorption capacity was around 1.5 mmol U g⁻¹. The sorption isotherms were fitted by Langmuir and Sips equations. Desorption was achieved using 0.3 M HCl solution and the complete desorption was performed in around 15 min of contact. The sorption desorption cycles are relatively stable during 5 cycles with limit decreasing in sorption and desorption properties (around 3 ± 0.2% and 99.8 ± 0.1%, respectively). The sorbent was used for removal of U from acid leachate solution in mining area. The sorbent showed a highly performance for U(VI) removal, which was considered as a tool material for radionuclides removing from aquatic medium.

Phosphonic acid functionalization of gellan gum and chitosan biopolymers was successfully performed. In the first step, the sorption was investigated using La(III) ions before testing for the recovery of rare earth elements (REEs) from pretreated industrial acidic leachate. The sorbent was characterized by Fourier-transform infrared (FTIR), scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET), and pH of zero charge (pH_PZC) determination. FTIR and EDX results show efficient grafting of phosphoryl groups. The sorption was determined for the crude materials before functionalization (PGEG) and after phosphorylation (TBP-PGEG). More efficient sorption was seen for phosphorylated sorbent than for the crude composite. The sorption capacity is 0.226 mmol La g⁻¹ for the PGEG while the value is 0.78 mmol La g⁻¹ for the TBP-PGEG. We infer that phosphonate groups participate in the sorption. The most effective sorption is at pH = 4. The kinetic behavior was described using pseudo first-order equations (PFORE), pseudo second-order equations (PSORE), and resistance to intraparticle diffusion (RIDE). The sorption isotherms can be better represented by Langmuir and Sips equations than by the Freundlich equation. The sorbent shows high stability performance during reuse cycles with a limit on the decrease in the sorption performances and stability in the desorption performances. We have thus developed a good tool for the recovery of REEs with a selectivity higher than that of the non-functionalized components.

A newly synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, ¹H-NMR, ¹³C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 °C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model. With a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ΔS (−0.03 kJ/mol), ΔH (−12.22 kJ/mol) and ΔG were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴⁺ (28.82), Fe³⁺ (10.64), Ti⁴⁺ (28.82), V⁵⁺ (86.46) and U⁶⁺ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.