Search

With the rapid development of nuclear energy, the contamination of environmental water systems by uranium has become a significant threat to human health. To efficiently remove uranium from these systems, three types of silica-based polyamine resins—SiPMA-DETA (SiPMA: silica/poly methyl acrylate; DETA: diethylenetriamine), SiPMA-TETA (TETA: triethylenetetramine), and SiPMA-TEPA (TEPA: tetraethylenepentamine)—were successfully prepared, characterized, and evaluated in batch experiments. Characterization results showed that the silica-based polyamine resins were successfully prepared, and they exhibited a uniform shape and high specific surface area. SiPMA-DETA, SiPMA-TETA, and SiPMA-TEPA had nitrogen contents of 4.08%, 3.72%, and 4.26%, respectively. Batch experiments indicated that these adsorbents could efficiently remove uranium from aqueous solutions with a pH of 5–9. The adsorption kinetics of U(VI) were consistent with the pseudo-second-order model, indicating that the adsorption process was chemisorption and that adsorption equilibrium was achieved within 10 min. SiPMA-TEPA, with the longest polyamine chain, exhibited the highest adsorption capacity (>198.95 mg/g), while SiPMA-DETA, with the shortest polyamine chain, demonstrated the highest U(VI) adsorption efficiency (83%) with 100 mM Na2SO4. SiPMA-TEPA still removed over 90% of U(VI) from river water and tap water. The spectral analysis revealed that the N-containing functional groups on the ligand were bound to anionic uranium–carbonate species and possibly contributed to the adsorption efficiency. In general, this work presents three effective adsorbents for removing uranium from environmental water systems and thus significantly contributes to the field of environmental protection.

Abstract Nanobubbles have been applied in many fields, such as environmental cleaning, material production, agriculture, and medicine. However, the measured nanobubble sizes differed among the measurement methods, such as dynamic light scattering, particle trajectory, and resonance mass methods. Additionally, the measurement methods were limited with respect to the bubble concentration, refractive index of liquid, and liquid color. Here, a novel interactive force measurement method for bulk nanobubble size measurement was developed by measuring the force between two electrodes filled with bulk nanobubble-containing liquid under an electric field when the electrode distance was changed in the nm scale with piezoelectric equipment. The nanobubble size was measured with a bubble gas diameter and also an effective water thin film layer covered with a gas bubble that was estimated to be approximately 10 nm based on the difference between the median diameter of the particle trajectory method and this method. This method could also be applied to the solid particle size distribution measurement in a solution.

Crown ethers are famous for the highly selectively grab Sr(II) from concentrated nitric acid solution due to the size match, but they suffer from the high leakage into the liquid phase caused by the presence of a large number of hydrophilic groups. To reduce their leakage, two novel porous silica-based adsorbents, (DtBuCH18C6 + Dodec)/SiAaC-g-ABSA and (DtBuCH18C6 + Dodec)/SiAaC-g-3-ABSA, were prepared by vacuum impregnation with organic contents of about 55.9 wt.% and 56.1 wt.%, respectively. The two adsorbents have good reusability and structural stability, and the total organic carbon leakage rates in 2 M HNO3 solution are lower than 0.56 wt.% and 0.29 wt.%, respectively. Batch adsorption experiments revealed that the two adsorbents possessed good adsorption selectivity towards Sr, with SFSr/M over 40, except that of SFSr/Ba in 2 M HNO3 solution. The adsorption equilibrium of Sr in 2 M HNO3 solution was reached within 1 h, with saturated adsorption capacities of 36.9 mg/g and 37.5 mg/g, respectively. Furthermore, the XPS results indicate that the adsorption mechanism is the coordination of the crown ether ring with Sr. This work not only develops two novel adsorbents for the separation of Sr in nitric acid environments; it also provides a method for effectively reducing the water solubility of crown ethers.

Zirconium is recognized as one of the main impurities of the rare earth element scandium during purification. It presents significant challenges due to its similar chemical properties, making separating it difficult. This study used trialkyl phosphine oxide (TRPO) as a functional ligand, and the effects of carrier type and acidity on adsorption performance were first investigated. Among these, the novel extraction resin SiO2-P as a carrier for TRPO demonstrated more prominent separation performance in 0.2 M H2SO4 and 5 M HCl solutions. The kinetic and isotherm data were consistent with the pseudo-secondary kinetics and Langmuir model, respectively, and the adsorption process could be regarded as homogeneous monolayer adsorption subject to the dual effects of chemisorption and internal diffusion. In addition, thermodynamic analysis showed that the adsorption process of zirconium under the experimental conditions was a spontaneous endothermic process. Combined with the results of SEM-EDS, FT-IR, and XPS analyses, scandium and zirconium were successfully adsorbed by the resin and uniformly distributed on its surface, and the greater affinity of the P=O groups on the resin for zirconium was the critical factor contributing to the separation of scandium and zirconium. Finally, scandium and zirconium in sulfuric acid and hydrochloric acid media were extracted and separated by column experiments, and the purity of scandium could reach 99.8% and 99.99%, respectively.

Ruthenium is required to separate from high-level liquid waste (HLLW) because Ru is a valuable resource and is negatively influential on the vitrification process of HLLW. However, the separation of Ru is very challenging due to its complicated complexation properties. In this study, the adsorption and desorption characteristics of ruthenium on a synthesized SiPyR-N3 (weak-base anion exchange resin with pyridine functional groups) composite were investigated in nitric acid and nitrite–nitric acid systems, respectively, and the adsorption mechanism was explored. The experimental results showed that SiPyR-N3 has a significantly better adsorption effect on Ru in the nitrite–nitric acid system than in the nitric acid system, with an increase in the adsorption capacity of approximately three times. The maximum adsorption capacity of Ru is 45.6 mg/g in the nitrite–nitric acid system. The SiPyR-N3 possesses good adsorption selectivity (SFRu/other metal ions is around 100) in 0.1 M NO2−–0.1 M HNO3 solution. The adsorption processes of Ru in the two different systems are fitted with the pseudo-second-order kinetic model and Langmuir model for uptake kinetics and adsorption isotherms, respectively. The results obtained from the FT-IR, XPS, and UV absorption spectrometry indicate that NO2− was involved in the adsorption process either as a complexing species with the metal ions or as free NO2− from the solution. A 0.1 M HNO3 + 1 M thiourea mixed solution shows effective desorption performance, and the desorption efficiency can reach 92% at 328 K.

Over the past few decades, with the rapid growth of the global population and economy, the increasing levels of various pollutants such as heavy metals, radionuclides, and organic/inorganic/biological toxins from various industries and human activities, which diffuse into aspects of the environment such as the atmosphere, soil, and natural water, have posed a serious threat to human health and the environment [...]

A crown ether-loaded hybrid adsorbent suitable for the separation and enrichment of strontium from high-level liquid waste was synthesized. 4′,4′(5″)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its modifiers dodecyl benzenesulfonic acid (DBS) and 1-dodecanol were impregnated into silica-based polymer support. The hybrid adsorbent exhibited excellent Sr(II) selectivity ability, and effective chromatographic separation and recovery of Sr(II) from simulated high-level liquid waste could be achieved with a (DtBuCH18C6 + DBS + dodec)/SiO2-P packed column. The recovery rate of Sr(II) calculated based on the mass balance was approximately 99% and over 80% for the other coexisting metal ions. An appropriate increase in the concentration of Na-DTPA eluent was favorable to improve the efficiency of the elution process because of the increased complexation capacity of [DTPA]5− to Sr(II). The developed theoretical model can simulate the dynamic breakthrough curves of the material on the basis of short column data, thereby predicting the scale-up column of the practical operation. Density functional theory calculation was used to explore the action mechanism of DBS modifiers on the Sr(II) complexation process of crown ether groups. Two Sr(II) complexation isomeric models of DtBuCH18C6 were established, and the calculation results revealed a similar complexation ability. DtBuCH18C6 could form a stable Sr(II) complexation structure with DBS coordination, which further indicated that DBS could be a ligand to promote the Sr(II) adsorption ability of crown ether materials.

Strontium is a common radionuclide in radioactive waste, and its release into the environment can cause enormous damage to the ecosystem environment. In this study, the natural mineral allophane was selected as the substrate to prepare solidified ceramic products by cold pressing/sintering to solve the problem of the final disposal of radioactive strontium. Ceramic solidified products with various crystal structures were successfully prepared, and the microscopic morphology and energy-dispersive spectroscopy images of the samples showed a uniform distribution of Sr in the solidified products. Sr2Al2SiO7 and SrAl2Si2O8, which can stably solidify strontium, were formed in the solidified products, and the structural characteristics and stability of the above-mentioned substances were analyzed from the perspective of quantum chemical calculations using density functional theory. The calculation results showed that the overall deformation resistance of Sr2Al2SiO7 was higher than that of SrAl2Si2O8. Considering the isomorphic substitution effect of CaO impurities, we inferred that a mixed-crystalline structure of Ca2−xSrxAl2SiO7 may be present in the solidified products.

Successive grafting of new sorbent bearing amino phosphonic groups based on chitosan nano magnetite particles was performed through successive coupling with formaldehyde. The produced composite was characterized by the high sorption capacity toward rare earth elements (REEs) and consists of different types of functional groups (phosphonic, hydroxyls and amine groups) that are used for enhancing the sorption properties. The chemical modification and the sorption mechanism were investigated through different analytical tools; i.e., FTIR, SEM, SEM-EDX, TGA, BET (surface area) and pHpzc. The sorption was investigated toward Nd(III) as one of the REE(III) members under ultraviolet (UV) and visible light (VL) conditions. The optimum sorption was found at pH0 4 and the sorption capacity was recorded at 0.871 and 0.779 mmol Nd g−1 under UV and VL respectively. Sorption isotherms and uptake kinetics were fitted by Langmuir and Sips and by pseudo-first order rate equation (PFORE) for the functionalized sorbent, respectively. The sorbent showed a relatively high-speed sorption kinetic (20 min). The bounded metal ions were progressively eluted using 0.2 M HCl solution with a desorption rate 10–15 min, while the loss in the total capacity after a series of sorption recycling (sorption/desorption) (five cycles) was limited (around 3%) with 100% of the desorption efficiency, indicating the high stability of the sorbent toward an acidic medium. The sorbent was used for the recovery of REEs from leach liquor residue after pretreatment for the extraction of particular elements. From these results (high loading capacity, high selectivity and high stability against acid treatments), we can see that the sorbent is a promising tool for the selective recovery of rare earth elements in the field of metal valorization.

Dielectric capacitors are widely used in electronic systems but they possess inferior energy density in comparison with other electrochemical energy storage. Here, the authors construct a diffused phase boundary to simultaneously achieve high energy storage density and efficiency in AgNbO3antiferroelectrics.

While enjoying the convenience of nuclear energy development, the environmental contamination by radionuclide leakage is of significant concern. Because of its cost-effectiveness and environmental friendliness, biochar has attracted a lot of attention in the field of radioactive water treatment. Herein, a novel teak peel modified biochar (labeled as PMBN3) was prepared and applied to remove strontium from artificial seawater. The characterisation of the prepared PMBN3 showed it contains numerous oxygen-containing functional groups (i.e. carboxyl and hydroxyl groups), laminar morphology, mesoporous structure, large specific surface area. PMBN3 exhibited great advantages in Sr(II) adsorption, such as rapid adsorption kinetics ( 0.98. The calculated thermodynamic parameters indicate that strontium adsorption on biochar occurs exothermically and spontaneously. Furthermore, for efficient removal of Sr(II), CO2 nanobubbles were blown into artificial seawater to precipitate the interfering metal ions, and followed by the adsorption of PMBN3 towards residual metal ions with the removal rate of Sr(II) over 99.7%. Finally, mechanistic studies have shown that the strontium adsorption process by PMBN3 is a multiple adsorption mechanism consisting of ion exchange between H+ (from -OH and -COOH) and Sr(II), and weak intermolecular forces between Sr(II) and the PMBN3 adsorbent. This study creatively combines chemisorption and nanobubble precipitation for strontium removal, which provides great reference value and guidance for environmental remediation.

Although Cs(I) and Sr(II) are not strategic and hazardous metal ions, their recovery from aqueous solutions is of great concern for the nuclear industry. The objective of this work consists of designing a new sorbent for the simultaneous recovery of these metals with selectivity against other metals. The strategy is based on the functionalization of algal/polyethyleneimine hydrogel beads by phosphonation. The materials are characterized by textural, thermo-degradation, FTIR, elemental, titration, and SEM-EDX analyses to confirm the chemical modification. To evaluate the validity of this modification, the sorption of Cs(I) and Sr(II) is compared with pristine support under different operating conditions: the pH effect, kinetics, and isotherms are investigated in mono-component and binary solutions, before investigating the selectivity (against competitor metals) and the possibility to reuse the sorbent. The functionalized sorbent shows a preference for Sr(II), enhanced sorption capacities, a higher stability at recycling, and greater selectivity against alkali, alkaline-earth, and heavy metal ions. Finally, the sorption properties are compared for Cs(I) and Sr(II) removal in a complex solution (seawater sample). The combination of these results confirms the superiority of phosphonated sorbent over pristine support with promising performances to be further evaluated with effluents containing radionuclides.

Both sustainable development in environment and safety of high-power systems require to develop a novel lead-free dielectric capacitor with high energy density (Wrec) at low applied electric field. In this work, a remarkably high Wrec of 2.9 J/cm3 accompanying with energy storage efficiency of 56% was achieved in Ag0.9Sr0.05NbO3 ceramic at a low applied electric field of 190 kV/cm, by improving anti-ferroelectricity and introducing relaxor behaviour. The improved anti-ferroelectric stability was attributed to the decreased tolerance factor and average electronegativity difference, while the relaxor behaviour was associated with the increased disordered local structure by Sr-doping. Moreover, the Ag0.9Sr0.05NbO3 ceramics also exhibited outstanding temperature stability in energy density with small variation less than 5% over 20–140 °C. The results indicate that the Ag0.9Sr0.05NbO3 ceramic is a promising candidate for low-electric-field driving capacitors. Keywords: Low applied electric field, Energy storage, Relaxor behaviour, Silver niobate, Anti-ferroelectric

To separate the long-lived minor actinides (MA = Am, Cm) from high-level liquid waste (HLLW), we have been studying an advanced separation process via selective adsorption that uses minimal amounts of organic solvent and compact equipment. The process consists of two separation columns packed with a CMPO (octyl(phenyl)-N,N-diisobutylcarbamoyl-methyl phosphine oxide) adsorbent for elemental group separation and a soft-donor named the R-BTP (2,6-bis-(5,6-dialkyl-1,2,4-triazine-3-yl) pyridine) adsorbent for the isolation of MA from lanthanides (Ln). In this work, the effects of nitrate ion (NO3−) on the adsorption behavior of Am(III) and a typical fission product Ln(III) onto the isoBu-BTP/SiO2-P adsorbent were studied experimentally. Then, the desorption properties of the adsorbed element were examined using different eluting agents. A hot test for the separation of MA from the fission product Ln in a genuine MA containing effluent from the irradiated MOX-fuel treatment process was carried out using a nBu-BTP/SiO2-P packed column. It was found that the separation factor between Am(III) and Ln(III)-FP is over 100 in the measured 0.5–4 M NO3−. The adsorbed elements could be effectively eluted off using a complexing agent such as DTPA or pure water. Complete separation between MA and Ln was achieved in the column results, indicating that the proposed MA separation process is feasible in principle.

The recovery of strategic metals such as rare earth elements (REEs) requires the development of new sorbents with high sorption capacities and selectivity. The bi-functionality of sorbents showed a remarkable capacity for the enhancement of binding properties. This work compares the sorption properties of magnetic chitosan (MC, prepared by dispersion of hydrothermally precipitated magnetite microparticles (synthesized through Fe(II)/Fe(III) precursors) into chitosan solution and crosslinking with glutaraldehyde) with those of the urea derivative (MC-UR) and its sulfonated derivative (MC-UR/S) for cerium (as an example of REEs). The sorbents were characterized by FTIR, TGA, elemental analysis, SEM-EDX, TEM, VSM, and titration. In a second step, the effect of pH (optimum at pH 5), the uptake kinetics (fitted by the pseudo-first-order rate equation), the sorption isotherms (modeled by the Langmuir equation) are investigated. The successive modifications of magnetic chitosan increases the maximum sorption capacity from 0.28 to 0.845 and 1.25 mmol Ce g−1 (MC, MC-UR, and MC-UR/S, respectively). The bi-functionalization strongly increases the selectivity of the sorbent for Ce(III) through multi-component equimolar solutions (especially at pH 4). The functionalization notably increases the stability at recycling (for at least 5 cycles), using 0.2 M HCl for the complete desorption of cerium from the loaded sorbent. The bi-functionalized sorbent was successfully tested for the recovery of cerium from pre-treated acidic leachates, recovered from low-grade cerium-bearing Egyptian ore.

A silica-based anion exchange resin was synthesized and used to remove 99Tc from real radioactive liquid waste. The adsorbent had a uniform particle size and exhibited good thermal stability up to 100 °C, which is promising for large-scale column experiments. In accordance with the chemical similarity with Tc, Re was used as a surrogate in this study. The N 1s high-resolution XPS spectra of the adsorbent before and after the adsorption of Re indicated that the ion exchange reaction was the controlling mechanism in the process. After γ-ray irradiation, the changing trend of the Kd was consistent, which showed that the competitive adsorption of NO3− led to a decrease in Kd. The adsorption capacity for the Re decreased slightly from 35.8 to 31.9 mg/g with the increase in the absorbed dose from 0 to 50 kGy. The separation and recovery of Re and the coexisting ions were achieved by chromatographic separation experiments, and the recovery percentage of Re was 86%. In real radioactive liquid waste, N3/SiO2 exhibited good selectivity toward 99Tc over the coexisting metals, namely, 90Sr, 137Cs, 241Am, and U, and the decontamination efficiency of 99Tc attained 65%.

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, pHPZC (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.

Utilising waste amine-oxime (WAO) resin through microwave semi-carbonization, a carbon adsorbent (CA) was obtained to remove Pb(II). After microwave treatment, the pore size of the skeleton structure, three-dimensional porous network, and lamellar pore structure of WAO was improved. The distribution coefficient (Kd) of Pb(II) onto CA is 620 mL/g, and the maximum adsorption capacity of Pb(II) is 82.67 mg/g after 20 min of WAO microwave treatment. The adsorption kinetics and adsorption isotherms conform to the quasi-second-order kinetic equation and Langmuir adsorption isotherm model, respectively. The surface of MT-WAO is negatively charged and the adsorption mechanism is mainly electrostatic interaction. Pb(II) elution in hydrochloric acid solution is more than 98%, and its recovery is high at 318 K and for 1 h.

The detection of heavy metals in aqueous solutions has always attracted much attention from all over the world. A fluorescent probe of CdSe/CdS core-shell quantum dots (QDs) was designed to detect trace Cd2+ in aqueous solutions using the OFF–ON mode rapidly and efficiently, likely based on adsorption and desorption reactions between ethylenediaminetetraacetic acid disodium salt (EDTA) and CdSe/CdS QDs. In the OFF mode, the optical shielding function of EDTA results in fluorescence quenching owing to the strong adsorption ability of EDTA with Cd2+ on the sites of CdSe/CdS QDs surface. In the ON mode, the introduction of Cd2+ promotes the desorption of EDTA from the EDTA-CdSe/CdS QDs and restores the fluorescence intensity. There were two linear response ranges which were 0.1–20 µmol/L and 20–90 µmol/L for the EDTA-CdSe/CdS system to detect Cd2+. The detection limit was 6 nmol/L, and the standard deviation was below 4% for the detection of Cd2+ concentration in tap water.

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, Co: 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 study aims to evaluate the functionalization of chitosan biopolymer with heterocyclic moieties of 2-thioxodihydropyrimidine-4,6(1H,5H)-dione used for enhancing the sorption of Cr ions from aqueous solution. A synthesized sorbent is a nanoscale particle (around 5–7 nm), which explains the fast kinetics of sorption. The sorbent is specified using elemental analysis (EA), FTIR, BET (nitrogen sorption desorption isotherms), TGA, and SEM-EDX analyses. Sorption properties are investigated using ultraviolet emission (UV) but also using visible light (L). In the sorption diagram, the high sorption uptake and fast kinetics observed using ultraviolet conditions are shown. This work is conducted by removing Cr ions from highly contaminated tannery effluents, which have a high concentration of Cr associated with other poisonous elements such as Cd(II) and Pb(II). Under the selected conditions, complete sorption is performed during the first 60 and 45 min with a capacity of 2.05 and 2.5 mmol Cr g−1 for the crosslinked chitosan (without functionalization) in L and UV, respectively. This sorption is enhanced by functionalizing to 5.7 and 6.8 mmol Cr g−1 at the L and UV, respectively, as well as improving the sorption kinetics to 35 and 30 min for both techniques, respectively. The PFORE, and (Langmuir and Sips equations) fit the kinetics and isotherms, respectively.

Globally, there is a rising demand for water purification. This demand is driven by numerous factors, including economic growth, increasing population, water shortage, and deterioration of water quality. The current work highlights the manufacturing of environmentally friendly and highly efficient sorbent based on chitosan nanoparticles after successive crosslinking (using glutaraldehyde) and modification through grafting of 4-aminoazobenzene-3,4′-disulfonic acid (AZDS) as a source of sulfonic groups. First, the produced sorbent was thoroughly specified using FTIR, TGA, SEM, SEM-EDX, pHpzc, BET (nitrogen sorption desorption isotherms), and elemental analyses (EA). The sorbent was tested for the sorption of Fe(III) before application to highly contaminated iron water well samples. Next, the sorption was improved as the sulfonation process was conducted under the selected experimental conditions within 25 and 20 min with a maximum capacity of 2.7 and 3.0 mmol Fe g−1 in visible light and under UV, respectively. Then, the uptake kinetics for both techniques were fitted by the pseudo-first-order rate equation (PFORE), in which the effect of the resistance to intraparticle diffusion has remained an unneglected factor, while the Langmuir equation has fitted the sorption isotherms. After that, the efficient desorption was achieved by using 0.2 M hydrochloric acid solution, and the desorption process was as fast as the sorption process; 15 min was sufficient for complete desorption. The sorbent shows high selectivity for heavy metal ions compared to the representative elements. Finally, the sorbent was used for the removal of heavy metal ions from a highly contaminated water well in the Bahariya Oasis and appeared to be highly efficient for heavy metal removal even in a diluted solution. Accordingly, it can be implemented in the task of water treatment.

Designing low-cost, environment friendly, and highly active photocatalysts for water splitting is a promising path toward relieving energy issues. Herein, one-dimensional (1D) cadmium sulfide (CdS) nanorods are uniformly anchored onto two-dimensional (2D) NiO nanosheets to achieve enhanced photocatalytic hydrogen evolution. The optimized 2D/1D NiO/CdS photocatalyst exhibits a remarkable boosted hydrogen generation rate of 1,300 μmol h−1 g−1 under visible light, which is more than eight times higher than that of CdS nanorods. Moreover, the resultant 5% NiO/CdS composite displays excellent stability over four cycles for photocatalytic hydrogen production. The significantly enhanced photocatalytic activity of the 2D/1D NiO/CdS heterojunction can be attributed to the efficient separation of photogenerated charge carriers driven from the formation of p-n NiO/CdS heterojunction. This study paves a new way to develop 2D p-type NiO nanosheets-decorated n-type semiconductor photocatalysts for photocatalytic applications.

Development of bio-based sorbents (i.e., chitosan moieties) at nanoscale size for the removal of metal contaminants is the main target of this research. Grafting with thiazole heterocyclic derivative gives fast kinetics sorption, highly metal loading, and good recyclability for mining leaching solution. Different analyses tools including (thermogravimetric analysis (TGA), scanning electron microscope and energy dispersive spectroscopy (SEM-EDX), X-ray diffraction (XRD), Fourier transform infrared (FTIR), BET surface area (nitrogen sorption desorption), titration, and TEM (transmission electron microscopy)) were used to investigate the chemical and textural properties of the functionalized sorbent. The sorption was measured in normal visible light and under UV emission. The highest capacity was measured at pH 5, which reached 0.251 mmol Pb g−1 in visible light compared with 0.346 mmol Pb g−1 under UV for the pristine crosslinked chitosan (MCc). The sorption performances were improved by functionalization; (0.7814 and 1.014 mmol Pb g−1) for the functionalized sorbent (MCa-ATA) under visible light and UV, respectively. PFORE (pseudo-first-order rate equation) and RIDE (resistance to intraparticle diffusion) fit kinetics, the Sips equation is the most fit profile for the sorption isotherms for the MCc in either light and UV processes, while PFORE and RIDE for kinetics under light and UV for MCa-ATA and Sips in light and Sips and Langmuir under the UV emission. Finally, the sorbent was investigated toward a raffinate solution from ore processing and shows promising extraction tools for the most interesting elements.

The synthesis and developments of magnetic chitosan nanoparticles for high efficiency removal of the cadmium ions from aquatic medium are one of the most challenging techniques. Highly adsorptive composite (MCH-ATA) was produced by the reaction of chitosan with formaldehyde and amino thiazole derivative. The sorbent was characterized by FTIR, elemental analyses (EA), SEM-EDX, TEM analysis, TGA and titration (volumetric). The modified material includes high nitrogen and sulfur contents (i.e., 4.64 and 1.35 mmol g−1, respectively), compared to the pristine material (3.5 and 0 mmol g−1, respectively). The sorption was investigated for the removal of Cd(II) ions from synthetic (prepared) solution before being tested towards naturally contaminated groundwater in an industrial area. The functionalized sorbent shows a high loading capacity (1.78 mmol Cd g−1; 200 mg Cd g−1) compared to the pristine material (0.61 mmol Cd g−1; 68.57 mg Cd g−1), while removal of about 98% of Cd with capacity (6.4 mg Cd g−1) from polymetallic contaminated groundwater. The sorbent displays fast sorption kinetics compared to the non-modified composite (MCH); 30 min is sufficient for complete sorption for MCH-ATA, while 60–90 min for the MCH. PFORE fits sorption kinetics for both sorbents, whereas the Langmuir equation fits for MCH and Langmuir and Sips for MCH-ATA for sorption isotherms. The TEM analysis confirms the nano scale size, which limits the diffusion to intraparticle sorption properties. The 0.2 M HCl solution is a successful desorbing agent for the metal ions. The sorbent was applied for the removal of cadmium ions from the contaminated underground water and appears to be a promising process for metal decontamination and water treatment.

Biomass waste is a valuable resource that can be recovered, reused, and is renewable. However, converting biomass waste to a high degree of order is a bigger challenge, and graphitization at low temperatures is even more difficult. This paper proposes an improved method (Ni element catalysis) for highly graphitizing pomelo peel at low temperatures (750 –900 °C). In this paper, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), and high-resolution transmission electron microscopy (HRTEM) were used to study the method and the effect of temperature on structural changes during graphitization. Under the improved method, pomelo peel was transformed into nano-spherical graphitized material. The degree of graphitization reached 80.23% at 900 °C, which was 31.39% higher than that of the traditional method. Furthermore, through HRTEM, the lattice fringe spacing was observed to be 0.337 nm, which is between pure graphite (0.3354 nm) and amorphous graphite (0.3440 nm). In this paper, the improved method can obtain highly graphitized nanospheres at low temperatures, thus reducing energy consumption, reducing environmental pollution, and promoting sustainable development.

Radioactive strontium 90Sr with a half-life of 29 years is one of the most concerned elements in both nuclear accidents and spent fuel reprocessing. Herein, using macroporous silica SiO2 as support, methylacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linking agent, a novel resin named SiMaC was prepared via in situ polymerization method for strontium removal. The as-preapred SiMaC was characterized by SEM-EDS, TG-DSC, and BET. Various factors such as pH, m/V, time, and initial concentration of Sr(II) were studied. The maximum adsorption capacity towards Sr(II) was as high as 142.5 mg/g at 298 K. The adsorption equilibrium was almost obtained within 30 min. Moreover, SiMaC was easily and fastly regenerated by 0.1 M HCl and exhibited no obvious decrease in adsorption capacity after five times of successive adsorption-desorption cycles. Most attractively, the uptake rate of Sr(II) reached more than 99% in real river and lake water mediums, as well as reached 76% in real seawater mediums. Finally, XPS and FTIR were used to analyze the adsorption mechanism towards Sr(II). Keywords: Strontium, Polymerization, Adsorption, Synthesis, XPS

In the process of preparing high-purity MnSO4 from industrial MnSO4 solution, it is difficult to remove Ca2+ and Mg2+ due to their closely similar properties. In this study, thermodynamic software simulation and experimental procedures were combined to remove Ca2+ and Mg2+ from industrial MnSO4 solution to obtain high-purity MnSO4. The simulation model was applied to predict the trend of the crystallization of different ions in the solution upon the addition of H2SO4, which revealed that, at a volume ratio of H2SO4 to MnSO4 solution of more than 0.2, MnSO4 started to crystallize and precipitate. The experimental results further verified the simulation results, and the yield of MnSO4 increased with the increasing ratio of H2SO4, while the removal rate of Ca2+ and Mg2+ decreased gradually. Keeping the economic aspect in mind, the 0.3 ratio of H2SO4 was selected at which the yield of MnSO4 reached 86.44%. The removal rate of Ca2+ and Mg2+ by recrystallization reached 99.68% and 99.17% respectively after six consecutive cycles. The recrystallized sample was washed twice with anhydrous ethanol (volume ratio of ethanol to MnSO4 solution of 0.5) and dried for 6 h at 120 °C, and the purity of MnSO4·H2O reached the battery grade requirements with the final yield as high as 80.54%. This study provides important guideline information for the purification of MnSO4·H2O from industrial MnSO4 solution via a cost-effective, simple and facile approach.

We investigated the influence of microwave and conventional heating pretreatments on the grinding of cassiterite associated with pollimetallic ore. The minerals that exhibited a stronger microwave absorption ability crushed first, which is the main difference between the microwave and the traditional heating pretreatments. The distribution of Fe, Pb, Zn, and Sn increased in the fine size range (−0.425 mm). The Fe and Pb grades in the size ranges of −3.2 + 2 mm and −2 + 1 mm after the microwave pretreatment (6 kW, 1 min) were lower than those of the traditional heating (12 kW, 400 °C, 20 min), indicating that the microwave selective heating was beneficial for pyrite and jamesonite. The grade and distribution of Sn decreased significantly in the size ranges of −3.2 + 2 mm and −2 + 1 mm and increased in the size ranges of −0.425 + 0.15 mm and −0.15 + 0.074 mm. Microwave heating treatment promoted the grinding of sulfide ore and reduced the cassiterite overgrinding.

ZnAl layered double hydroxides (LDHs) film was prepared on the pure Al by an in-situ growth method. In-situ observation of the growth behavior of ZnAl-LDHs-NO3 film was studied by electrochemical quartz crystal microbalance (EQCM) and open circuit potential (OCP). The characteristics of the ZnAl-LDHs-NO3 film was analyzed through the X-ray diffraction, X-ray photoelectron spectroscopy and scanning electronic microscope. The corrosion behavior of the LDHs film was investigated by the electrochemical impedance spectroscopy and polarization curves. The results indicate that the growth process of the ZnAl-LDHs-NO3 film can be divided into the dissolution of Al substrate stage, the formation of Al(OH)3 stage, the nucleation of ZnAl-LDHs-NO3 stage and the growth of ZnAl-LDHs stage. The growth mechanism of each stage is explained in detail. The ZnAl-LDHs film is composed of the interconnected two-dimensional nano-sheets, and the microcrystals grow perpendicular to the Al substrate and cover the entire Al substrate surface. The size and thickness of the ZnAl-LDHs nano-sheets gradually increase with the increasing of the growth time, meantime, the [Zn2+]/[Al3+] content ratio in the ZnAl-LDHs also increases. The ZnAl-LDHs film can significantly improve the corrosion resistance of the Al substrate. Keywords: ZnAl-LDHs, EQCM, Growth behavior, Corrosion

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 (ALPEI 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 ALPEI beads by this new method opens promising perspectives for the recovery of these strategic metals from mild acid solutions (i.e., pH ~ 4).

Nanobubbles have many potential applications depending on their types. The long-term stability of different gas nanobubbles is necessary to be studied considering their applications. In the present study, five kinds of nanobubbles (N2, O2, Ar + 8%H2, air and CO2) in deionized water and a salt aqueous solution were prepared by the hydrodynamic cavitation method. The mean size and zeta potential of the nanobubbles were measured by a light scattering system, while the pH and Eh of the nanobubble suspensions were measured as a function of time. The nanobubble stability was predicted and discussed by the total potential energies between two bubbles by the extended Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. The nanobubbles, except CO2, in deionized water showed a long-term stability for 60 days, while they were not stable in the 1 mM (milli mol/L) salt aqueous solution. During the 60 days, the bubble size gradually increased and decreased in deionized water. This size change was discussed by the Ostwald ripening effect coupled with the bubble interaction evaluated by the extended DLVO theory. On the other hand, CO2 nanobubbles in deionized water were not stable and disappeared after 5 days, while the CO2 nanobubbles in 1 mM of NaCl and CaCl2 aqueous solution became stable for 2 weeks. The floating and disappearing phenomena of nanobubbles were estimated and discussed by calculating the relationship between the terminal velocity of the floating bubble and bubble size.

Efficient removal of Cd(II) and Pb(II) from contaminated water is considered a fundamental point of view. Synthetic hydrogel biopolymers based on chitosan and alginate (cost-effective and eco-friendly) were successfully designed and characterized by highly efficient removal contaminants. The sorbents are characterized by FTIR, SEM-EDX, TGA, XPS analyses and textural properties which are qualified by N2 adsorption. The sorption properties are firstly investigated by the effect of pH, sorption isotherms, uptake kinetics, and selectivity from multi-metal solution with equi-molar concentration. The sorbent with 1:3 ratios (of chitosan and alginate respectively) is the most effective for metal removal (i.e., 0.81 mmol Cd g−1 and 0.41 mmol Pb g−1). Langmuir and Sip’s models fitted better the adsorption isotherms compared to the Freundlich model. Uptake kinetics was well fitted by pseudo-first-order rate equation, while the saturation was achieved within 40 min. The sorbent shows good reproducibility through duplicate the experiments with negligible decreasing efficiency (>2.5%). The sorbent was applied for water treatment on samples collected from the industrial area (i.e., 653 and 203 times over the MCL for Cd(II) and Pb(II) respectively according to WHO). The concentration of Cd and Pb was drastically decreased in the effluents as pH increased with removal efficiency up to 99% for both elements at pH 5.8 and SD equivalent 1 g L−1 for 5 h.

The development of new materials is needed to address the environmental challenges of wastewater treatment. The phosphorylation of guar gum combined with its association to chitosan allows preparing an efficient sorbent for the removal of U(VI) from slightly acidic solutions. The incorporation of magnetite nanoparticles enhances solid/liquid. Functional groups are characterized by FTIR spectroscopy while textural properties are qualified by N2 adsorption. The optimum pH is close to 4 (deprotonation of amine and phosphonate groups). Uptake kinetics are fast (60 min of contact), fitted by a pseudo-first order rate equation. Maximum sorption capacities are close to 1.28 and 1.16 mmol U g−1 (non-magnetic and magnetic, respectively), while the sorption isotherms are fitted by Langmuir equation. Uranyl desorption (using 0.2 M HCl solutions) is achieved within 20–30 min; the sorbents can be recycled for at least five cycles (5–6% loss in sorption performance, complete desorption). In multi-component solutions, the sorbents show marked preference for U(VI) and Nd(III) over alkali-earth metals and Si(IV). The zone of exclusion method shows that magnetic sorbent has antibacterial effects against both Gram+ and Gram- bacteria, contrary to non-magnetic material (only Gram+ bacteria). The magnetic composite is highly promising as antimicrobial support and for recovery of valuable metals.

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.

The strong demand for rare-earth elements (REEs) is driven by their wide use in high-tech devices. New processes have to be developed for valorizing low-grade ores or alternative metal sources (such as wastes and spent materials). The present work contributed to the development of new sorbents for the recovery of rare earth ions from aqueous solutions. Functionalized mesoporous silica composite was synthesized by grafting diethylenetriamine onto composite support. The physical and chemical properties of the new sorbent are characterized using BET, TGA, elemental analysis, titration, FTIR, and XPS spectroscopies to identify the reactive groups (amine groups: 3.25 mmol N g−1 and 3.41 by EA and titration, respectively) and their mode of interaction with Nd(III) and Gd(III). The sorption capacity at the optimum pH (i.e., 4) reaches 0.9 mmol Nd g−1 and 1 mmol Gd g−1. Uptake kinetics are modeled by the pseudo-first-order rate equation (equilibrium time: 30–40 min). At pH close to 4–5, the sorbent shows high selectivity for rare-earth elements against alkali-earth elements. This selectivity is confirmed by the efficient recovery of REEs from acidic leachates of gibbsite ore. After elution (using 0.5 M HCl solutions), selective precipitation (using oxalate solutions), and calcination, pure rare earth oxides were obtained. The sorbent shows promising perspective due to its high and fast sorption properties for REEs, good recycling, and high selectivity.

A new type of 7055-Y-Sc alloy with high strength and corrosion resistance was prepared. Eutectic Al _3 Y particles with sizes in the range of 500–600 nm were found in the as-cast structure of the 7055-Y-Sc alloys. The addition of Y significantly accelerated the precipitation of Al _3 Zr with L1 _2 structure in Al–Zr–Y alloy, and the number density of Al _3 (Zr, Y) precipitates was almost a grade higher than that of Al _3 Zr. In the process of aging at 120 ℃/12 h, the nano scale L1 _2 -type Al _3 (Sc _x Y _y ) phase nucleated uniformly within the Al matrix and nonuniformly on the dislocation. The grain size decreased from 100–200 um in 7055-Y-0Sc to 40–50 um in 7055-Y-0.25Sc, the percentage of Sc continued to increase, and the grain size remained unchanged or even increased, thereby decreasing the Vickers hardness of 7055-Y-Sc alloys from 196.4 HV to 187.9 HV. After aging, the hardness and tensile properties of 7055-Y-Sc alloy showed good performance. The effective Sc proportion of the 7055-Y-Sc alloy was 0.25%. Its tensile strength was 398.6 MPa. Its conductivity was 33.8% IACS. The current corrosion density was 6.7 × 10 ^−8 A cm ^−2 , its good strength, corrosion resistance and conductivity make the studied alloy to be a promising material.

This research investigates the influences of different contents of Sc on the microstructure, mechanical, electrical conductivities and corrosion resistance properties of 7055 alloy. The effect of Sc can increase the non-uniform nucleation of the alloy and significantly refine the casting structure of the alloy. In addition, the addition of Sc not only inhibits grain coarsening, pins GBs and restrains recovery and recrystallisation, but also maintains the effect of fibre structure during the formation of high-density nano-Al _3 (Sc, Zr) phase precipitation. Compared with pure 7055 alloys, the hardness, tensile strength, elongation, electrical conductivity and corrosion resistance of 7055 alloys with Sc are improved remarkably. After adding a little Sc, the grain size of the alloy is refined from 80um to 40um, and the properties of the alloy are improved. When Sc content is 0.25%, the tensile strength of the alloy increases from 623.1mpa to 685.9mpa, and the self-etching current density decreases from 1.56 × 10 ^−5 to 8.74 × 10 ^−7 , and the corrosion resistance is also greatly improved.

The phase evolution mechanism and purification of titanium oxycarbide (TiCxOy) synthesized via the carbothermal reduction of ilmenite are investigated. The reaction process and products of the performed carbothermal reduction are analyzed by means of X-ray diffraction (XRD), scanning electron microscopy-energy disperse spectroscopy (SEM-EDS), X-ray photoelectric spectroscopy (XPS) and enthalpy, entropy and heat capacity (HSC) thermodynamic software. According to the shapes of Ti 2p3/2 and Ti 2p1/2 peaks in XPS spectra, together with the XRD analyses, the reduction products of TiO, TiCxOy or TiC can be judged. The phase evolution mechanism involves FeTi2O5, Ti2O3, Fe, TiO, TiCxOy and TiC under enhancing the content of carbon. The phase evolution law can be written as FeTiO3 → FeTi2O5 → Ti2O3 + Fe → TiO + Fe → TiCxOy + Fe. Due to the incomplete reduction state of TiCxOy, the ΔGθ of TiCxOy is detected between TiC and TiO. TiCxOy could be attained under reduction conditions of Ti:C, 1:3–1:4 in argon atmosphere at 1550 °C after 2 h. Grinding, flotation and magnetic separation processes displayed that C, TiCxOy and Fe are not dissociated until the particle size of −38 μm. TiCxOy and Fe can be separated by an iron-bath in a high temperature. 95.56% TiCxOy can be obtained, and resistance of TiCxOy is less than 0.05 Ω.

Every year, a large quantity of vanadium-containing wastewater is discharged from industrial factories, resulting in severe environmental problems. In particular, V(V) is recognized as a potentially hazardous contaminant due to its high mobility and toxicity, and it has received considerable attention. In this study, a silica-supported primary amine resin (SiPAR) was prepared by in-situ polymerization, and the V(V) adsorption from the solution was examined. The as-prepared resin exhibited fast adsorption kinetics, and it could attain an equilibrium within 90 min for the V(V) solution concentration of 100 mg/L at an optimum pH of 4, whereas the commercial D302 resin required a treatment time of more than 3 h under the same conditions. Furthermore, the maximum adsorption capacity of the resin under optimum conditions for V(V) was calculated to be 70.57 mg/g. In addition, the kinetics and isotherm data were satisfactorily elucidated with the pseudo-second-order kinetics and Redlich−Peterson models, respectively. The silica-based resin exhibited an excellent selectivity for V(V), and the removal efficiency exceeded 97% in the presence of competitive anions at 100 mmol/L concentrations. The film mass-transfer coefficient (kf) and V(V) pore diffusivity (Dp) onto the resins were estimated by mathematical modeling. In summary, this study provided a potential adsorbent for the efficient removal of V(V) from wastewater.

For the adsorption and recovery of rare earth elements from aqueous nitric acid, solid-phase extraction resins were prepared by impregnating and immobilizing of bis(2-ethylhexyl)phosphoric acid extractant into the macroporous silica-based polymeric (SiO 2 -P) particles. It was found that bis(2-ethylhexyl)phosphoric acid/SiO 2 -P had higher adsorption distribution coefficient for heavy rare earth elements than for light rare earth elements. The adsorption capacity of Gd(III) was observed to be 0.315 mmol g −1 by bis(2-ethylhexyl)phosphoric acid/SiO 2 -P in 0.1 M HNO 3 at 298 K, which increased slightly when increasing temperature from 298 to 323 K. The adsorption isotherms of Gd(III) matched well with the Langmuir and Freundlich models. The obtained thermodynamic parameters (ΔH o and ΔG o ) showed that the adsorption of Gd(III) by bis(2-ethylhexyl)phosphoric acid/SiO 2 -P was a spontaneous and exothermic process. This study also evaluated the chemical stability of bis(2-ethylhexyl)phosphoric acid/SiO 2 -P treated with nitric acid at different temperatures and demonstrated that bis(2-ethylhexyl)phosphoric acid/SiO 2 -P had considerable stability against nitric acid and heat.

The silica-based CeO 2 adsorbent (CeO 2 /SiO 2 ) was prepared for removing fluoride from the aqueous solution. The synthesized adsorbent was characterized by scanning electron microscope, energy dispersive spectrum, X-ray diffractometer, Fourier transform infrared spectrometer, and zeta potential measurement analyses. The adsorption batch experiments in the various experimental conditions including solution pH, contact time, initial fluoride concentration, and adsorption temperature were performed and investigated. The maximum adsorption capacity of fluoride into CeO 2 /SiO 2 was 2.441 mmol/g at pH 3 and 298 K. The adsorption kinetics and isotherms were well described by the pseudo-second-order model and the Langmuir model, respectively. The fluoride adsorption reached the equilibrium in 15 min from the aqueous solution with the initial fluoride concentration of 400 mg/l at 298 K. In the temperature range of 298–338 K, the maximum adsorption capacity of fluoride decreased from 2.441 mmol/g to 2.109 mmol/l at pH 3. The adsorption thermodynamics study revealed that this process was a spontaneous, exothermic, and entropy-driving adsorption. Furthermore, the mechanism of adsorption was identified as the anion exchange and the electrostatic interaction. The desorption efficiency of fluoride-loaded CeO 2 /SiO 2 adsorbent could reach about 95% by 0.1 mol/l NaOH.

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).

Diethylenetriaminepentaacetic acid (DTPA), a multi-dentate acidic chelating agent containing five carboxyl and three amine groups all capable of protonation, is a pentabasic acid. To separate minor actinide [MA(III)] and rare earth [RE(III)] elements effectively from a HNO 3 solution containing DTPA generated in the MAREC process, a functional polymeric composite impregnated with a novel macroporous silica-based diglycolamide compound, N,N,N′,N′ -tetraoctyl-3-oxapentane-1,5-diamide (TODGA), was prepared. Thus, the impregnated functional polymeric composite (TODGA/SiO 2 -P) was obtained by impregnating and immobilizing TODGA molecules in the pores of the SiO 2 -polymer (SiO 2 -P) particles (ca. 50 μm diameter) via a vacuum sucking technique. The effects of H + ions within the concentration range 0.01–3.0 M and of NO 3 − ions within the range 0.1–3.115 M on the adsorption of RE(III) ions onto TODGA/SiO 2 -P were investigated at 298 K. It was found that in the presence of 0.05 M DTPA, the DTPA species strongly affected the adsorption of RE(III) ions. The adsorption capability of TODGA/SiO 2 -P depended on the competitive reactions of RE(III) ions with two species, viz. H 4 DTPA − and H 2 DTPA 3− . The distribution coefficient (K d ) for RE(III) ions increased with increasing NO 3 − concentration, with one RE(III) ion reacting with two NO 3 − ions. The adsorption mechanism of RE(III) ions towards the TODGA/SiO 2 -P polymeric composite in HNO 3 solution containing 0.05 M DTPA was suggested as: RE 3 + + H 4 DTPA - + 2 NO 3 - + 3 TODGA / SiO 2 - P ⇋ RE ( H 4 DTPA ) ( NO 3 ) 2 ⋅ 3 TODGA / SiO 2 - P The formation of H 4 DTPA − and RE(H 4 DTPA)(NO 3 ) 2 which are both capable of adsorbing with TODGA/SiO 2 -P was the main reason why RE(III) ions exhibited such significant adsorption in the presence of 0.05 M DTPA.

The leakage behaviour of a neutral chelating agent, i.e. octyl(phenyl)- N,N -di-isobutylcarbamoylmethylphosphine oxide (CMPO), from its macroporous silica-based (CMPO/SiO 2 -P) extraction resin (a novel polymeric adsorption material developed in the MAREC process) and the recovery of CMPO by some selected polymer- and silica-based porous adsorbents were investigated by column operation in 0.01 M HNO 3 at 25°C or 50°C. The concentration of CMPO in the effluent leaking from CMPO/SiO 2 -P was determined as ca. 48 ppm at 25°C and ca. 37 ppm at 50°C. The corresponding elution volumes and the amounts of CMPO leaking were 8700.9 BV/g and 239.3 mg/g at 25°C and 11 842.9 BV/g and 359.4 mg/g at 50°C, respectively. The adsorption experiment showed that a polymer-based porous material, SEPABEADS® SP-825, was capable of recovering CMPO effectively from 0.01 M HNO 3 . Its adsorption ability towards CMPO was considerably greater than those of macroporous silica-based SiO 2 -P particles, polymer-based Amberlite™ XAD-7 and activated carbon. The bed volume and the amount of CMPO adsorbed by SEPABEADS® SP-825 at the breakthrough point at 25°C were 13 549.2 BV/g and 498.7 mg/g, respectively, thereby demonstrating that SEPABEADS® SP-825 was promising for the recovery of CMPO from Am(III)- and Cm(III)-containing solutions in the MAREC process.

To separate Mo(VI) and Zr(IV) ions from a 0.5 M oxalic acid solution and from each other, a novel macroporous silica-based N,N,N′,N′- tetraoctyl-3-oxapentane-1,5-diamide (TODGA) chelating polymeric adsorbent (TODGA/SiO 2 -P) was synthesized by introducing the TODGA molecule into ca. 50-μm diameter SiO 2 -P particles by impregnation. The adsorption of Mo(VI) and Zr(IV) ions onto TODGA/SiO 2 -P was investigated by examining the influence of nitric acid and oxalic acid concentrations. It was found that the adsorption was strongly affected by increasing the HNO 3 concentration from 0.5 M to 9.0 M either with or without the addition of 0.5 M H 2 C 2 O 4 . In the absence of 0.5 M H 2 C 2 O 4 , the distribution coefficients (K d ) of both Mo(VI) and Zr(IV) ions decreased with an increase in the HNO 3 concentration from 0.5 M to 3.0 M, increased slowly when the concentration of HNO 3 was increased further from 3.0 M to 6.0 M, and then increased gradually above 6.0 M concentration. Furthermore, the adsorption of Zn(IV) ions onto TODGA/SiO 2 -P was considerably greater than that of Mo(VI) ions. In the presence of 0.5 M H 2 C 2 O 4 , Zr(IV) ions showed no adsorption at HNO 3 concentrations below 4.0 M, being partly adsorbed in the presence of 4.0–6.0 M HNO 3 and fully adsorbed when the HNO 3 concentration was greater than 6.0 M. In contrast, Mo(VI) ions showed a much lower adsorption at HNO 3 concentrations below 2.0 M and no adsorption above this acid level. In the presence of HNO 3 at a concentration above 6.0 M and containing 0.5 M H 2 C 2 O 4 , the adsorption of Zr(IV) ions overlapped that from a similar HNO 3 solution which did not include 0.5 M H 2 C 2 O 4 . This was attributed to complete protonation of the C 2 O 2− 2 anion. On the basis of batch experiments, Mo(VI) and Zr(IV) ions were separated from a 6.5 M HNO 3 solution containing 0.5 M H 2 C 2 O 4 by means of a column packed with TODGA/SiO 2 -P at 50°C. The separate components, Mo(VI) and Zr(IV), could be effectively separated from each other by eluting with some selected eluants. The recovery percentage was 100.5% for Mo(VI) ions and 96.8% for Zr(IV) ions.