"Three-dimensional environment-friendly" amino acid functionalized chitosan: Uranium adsorption performance and mechanism research.

To achieve the goals of "carbon peak and carbon neutrality" and sustainable development, we propose "Three-Dimensional Environment-Friendly" materials to balance the urgent need for the development of clean energy and the reduction of secondary environmental pollution during adsorbent preparation. In this study, three novel chitosan adsorbents (CMNSC-Leu, CMNSC-Pro, CMNSC-Phe) for uranium adsorption were designed on the basis of molecular level and successfully synthesized with three different amino acids (leucine, proline, phenylalanine) through amidation reaction in an aqueous environment using a sustainable green chitosan material. The uranium adsorption capacity of the three adsorbents was evaluated by batch adsorption, selectivity and recyclability studies. The adsorption reaction conformed to the pseudo-second-order model and was a spontaneous endothermic reaction. In particular, the maximum adsorption capacity of CMNSC-Pro for uranium was 462.7 mg·g-1 at C0 = 100 ppm. In addition, CMNSC-Pro showed better selectivity and good reusability. DFT calculation and IRI diagram were applied in this work to analyze the unique structure and adsorption process of CMNSC-Pro from the perspective of structure. Uranium was adsorbed by CMNSC-Pro via coordination, electrostatic interaction, and intraparticle diffusion. This work provided a new idea for the structural design and construction of new high-efficiency biomass adsorbents.

Synthesis of Carboxyl-Functionalized COFs with Alternate Stable ß-Ketoenamine and Benzimidazole Linkages: Unraveling Exceptional Solvent Effects for Efficient Uranium Separation.

The prevalent π-π interactions in 2D covalent organic frameworks (COFs) impart a certain flexibility to the structures, making the stacking of COF layers susceptible to external stimuli and introducing some structural disorder. Recent research indicates that the flexibility between COF layers and the associated disorder significantly influence their selective adsorption performance toward gas molecules. However, the adsorption process in a solution environment is more complex compared to gas-phase adsorption, involving interactions between adsorbents and adsorbates, as well as the solvation effects of flexible 2D COFs. Therefore, the inherent flexibility and disorder in 2D COFs under solution conditions and their impact on the adsorption performance of metal ions have not been observed yet. Herein, the synthesis of a novel carboxyl-functionalized COF featuring stable ß-ketoenamine and benzimidazole linkages, named DMTP-COOH, is presented. DMTP-COOH exhibits excellent selective adsorption capability for uranium, with significantly different adsorption capacities observed after treatment with different solvents. This notable difference in adsorption capacity is observed under varying pH, concentration, time, and even in the presence of multiple competing ions. This work represents the first observation of the significant impact of solvent soaking treatment on the selective adsorption performance of COFs for uranium under liquid conditions.

Bis-substituted amino acid functionalized chitosan aerogels: High uranium adsorption capacity and antibacterial properties.

Based on the goal of "carbon neutralization and carbon peaking", it is still challenging to develop a high adsorption performance and environmentally friendly material for uranium extraction. We proposed a new idea of "Three-Dimensional Environmental-Friendly". A series of amino acid bis-substituted chitosan aerogels (C-1, C-2, C-3, C-4 and C-5) were prepared by ice template method and selective substitution reaction in water environment. Among them, C-3 adsorbent has the antibacterial properties of gram-positive bacteria, gram-negative bacteria and marine bacteria, which is more suitable for uranium adsorption in complex environments. Also, C-3 adsorbent solves the shortcomings of poor adsorption property and easy to cause secondary pollution during modification of traditional chitosan materials. The selectivity and adsorption capacity of uranium are further improved by the unique functional groups of serine residues. At pH = 7, the maximum adsorption capacity reaches 606.32 mg/g. In addition, C-3 adsorbent have excellent selectivity and stability. The synergistic effect of coordination, electrostatic interaction and intraparticle diffusion between C-3 adsorbent and uranium may be the key to its high adsorption performance. The high performance of chitosan adsorbent provides a new idea for the design and application of green and efficient uranium adsorption materials.

Antimicrobial ion-imprinted chitosan-derived hydrogel with quaternary ammonium and thermoresponsive components for UO22+ adsorption.

Uranium recovery from wastewater or seawater is important for both pollution control and uranium supply. Due to the complexity of the water body, it requires that the adsorbent should not only be highly efficient for selective adsorption but also have good antimicrobial properties. In this study, an antimicrobial thermosensitive hydrogel (UITAC) for uranium adsorption was prepared by one-step ion-imprinted polymerization using chitosan as a substrate and allyl trimethylammonium chloride as the antimicrobial modifier. UITAC showed excellent antibacterial rate against Escherichia coli and Staphylococcus aureus, being 98.8 % and 89.1 %, respectively. Endothermic and exothermic peaks respectively showed up at 36.3-38.5 °C and 30.5-34.1 °C in the DSC curves. UITAC quickly achieved its adsorption equilibrium in 30.0 min at 50 °C, pH 5.0 in the 0.8 mg/mL UO22+ solution, with an adsorption capacity of 81.2 mg/g. The adsorption capacity could remain at 80 % after 5 cycles of repeated use. UITAC showed better adsorption selectivity to UO22+ than vanadium and other metal ions, with selectivity coefficients α(UO22+/Mn+) being 1.4-10.3. The pseudo-second-order kinetics and Langmuir adsorption model had a better fit for UO22+ adsorption by UITAC. The adsorption was a spontaneous process. The Gibbs Free Energy change, enthalpy change, and entropy change at 323.2 K were - 16.0 kJ/mol, 64.3 kJ/mol, and 248.4 J/mol·K, respectively. UITAC showed high potential in practical application environment.

Facile and scalable synthesis of functionalized hierarchical porous polymers for efficient uranium adsorption.

Efficient uranium capture from wastewater holds great importance for the environmental remediation and sustainable development of nuclear energy, but it is a tremendous challenge. Herein, a facile and scalable approach is reported to fabricate functionalized hierarchical porous polymers (PPN-3) decorated with high density of phosphate groups for uranium adsorption. The as-constructed hierarchical porous structure could allow rapid diffusion of uranyl ions, while abundant phosphate groups that serve as adsorption sites could provide the high affinity for uranyl. Consequently, PPN-3 shows a high uranium adsorption uptake of 923.06 mg g-1 and reaches adsorption equilibrium within simply 10 min in uranium-spiked aqueous solution. Moreover, PPN-3 affords selective adsorption of uranyl over multiple metal ions and possesses a rapid and high removal rate of U(VI) in real water systems. Furthermore, this study offers direct polymerization strategy for the cost-effective fabrication of phosphate-functionalized porous organic polymers, which may provide promising application potential for uranium extraction.

A Phosphorylated Dendrimer-Supported Biomass-Derived Magnetic Nanoparticle Adsorbent for Efficient Uranium Removal.

A novel biomass-based magnetic nanoparticle (Fe3O4-P-CMC/PAMAM) was synthesized by crosslinking carboxymethyl chitosan (CMC) and poly(amidoamine) (PAMAM), followed by phosphorylation with the incorporation of magnetic ferric oxide nanoparticles. The characterization results verified the successful functionalization and structural integrity of the adsorbents with a surface area of ca. 43 m2/g. Batch adsorption experiments revealed that the adsorbent exhibited a maximum adsorption capacity of 1513.47 mg·g-1 for U(VI) at pH 5.5 and 298.15 K, with Fe3O4-P-CMC/G1.5-2 showing the highest affinity among the series. The adsorption kinetics adhered to a pseudo-second-order model (R2 = 0.99, qe,exp = 463.81 mg·g-1, k2 = 2.15×10-2 g·mg-1·min-1), indicating a chemically driven process. Thermodynamic analysis suggested that the adsorption was endothermic and spontaneous (ΔH° = 14.71 kJ·mol-1, ΔG° = -50.63 kJ·mol-1, 298. 15 K), with increasing adsorption capacity at higher temperatures. The adsorbent demonstrated significant selectivity for U(VI) in the presence of competing cations, with Fe3O4-P-CMC/G1.5-2 showing a high selectivity coefficient. The performed desorption and reusability tests indicated that the adsorbent could be effectively regenerated using 1M HCl, maintaining its adsorption capacity after five cycles. XPS analysis highlighted the role of phosphonate and amino groups in the complexation with uranyl ions, and validated the existence of bimodal U4f peaks at 380.1 eV and 390.1 eV belonging to U 4f7/2 and U 4f5/2. The results of this study underscore the promise of the developed adsorbent as an effective and selective material for the treatment of uranium-contaminated wastewater.

Humic acid-nanoceria composite as a sustainable adsorbent for simultaneous removal of uranium(VI), chromium(VI), and fluoride ions from aqueous solutions.

In this article, the multifunctional behavior of novel, efficient, and cost-effective humic acid-coated nanoceria (HA@CeO2 NPs) was utilized for the sorptive removal of U(VI), Cr(VI), and F- ions at different conditions. The production cost of HA@CeO2 was $19.28/kg and was well characterized by DLS, FESEM, HRTEM, FTIR, XRD, XPS, and TGA. Batch adsorption study for U(VI) (at pH ~ 8), Cr(VI) (at pH ~ 1), and F- (at pH ~ 2) revealed that the maximum percentage of sorption was > 80% for all the cases. From the contact time experiment, it was concluded that pseudo-second-order kinetics followed, and hence, the process should be a chemisorption. The adsorption study revealed that U(VI) and Cr(VI) followed the Freundlich isotherm, whereas F- followed the Langmuir isotherm. Maximum adsorption capacity for F- was 96 mg g-1. Experiments in real water suggest that adsorption is decreased in Kaljani River water (~ 12% for Cr(VI) and ~ 11% for F-) and Kochbihar Lake water (25.04% for Cr(VI) and 20.5% for F-) because of competing ion effect. Mechanism was well established by the kinetic study as well as XPS analysis. Because of high adsorption efficiency, HA@CeO2 NPs can be used for the removal of other harmful water contaminants to make healthy aquatic life as well as purified drinking water.

Adsorption of uranyl ion on hexagonal boron nitride for remediation of real U-contaminated soil and its interpretation using random forest.

Acid leaching has been widely applied to treat contaminated soil, however, it contains several inorganic pollutants. The decommissioning of nuclear power plants introduces radioactive and soluble U(VI), a substance posing chemical toxicity to humans. Our investigation sought to ascertain the efficacy of hexagonal boron nitride (h-BN), an highly efficient adsorbent, in treating U(VI) in wastewater. The adsorption equilibrium of U(VI) by h-BN reached saturation within a mere 2 h. The adsorption of U(VI) by h-BN appears to be facilitated through electrostatic attraction, as evidenced by the observed impact of pH variations, acidic agents (i.e., HCl or H2SO4), and the presence of background ions on the adsorption performance. A reusability test demonstrated the successful completion of five cycles of adsorption/desorption, relying on the surface characteristics of h-BN as influenced by solution pH. Based on the experimental variables of initial U(VI) concentration, exposure time, temperature, pH, and the presence of background ions/organic matter, a feature importance analysis using random forest (RF) was carried out to evaluate the correlation between performances and conditions. To the best of our knowledge, this study is the first attempt to conduct the adsorption of U(VI) generated from real contaminated soil by h-BN, followed by interpretation of the correlation between performance and conditions using RF. Lastly, a. plausible adsorption mechanism between U(VI) and h-BN was explained based on the experimental results, characterizations, and a. comparison with previous adsorption studies on the removal of heavy metals by h-BN.

Dual-functional metal-organic frameworks-based hydrogel micromotor for uranium detection and removal.

Self-propelled micro/nanomotors have attracted great attention for environmental remediation, however, their use for radioactive waste detection and removal has not been addressed. Engineered micromotors that are able to combine fast detection and highly adsorptive capability are promising tools for radioactive waste management but remain challenging. Herein, we design self-propelled micromotors based on zeolite imidazolate framework (ZIF-8)-hydrogel composites via inverse emulsion polymerization and show their potential for efficient uranium detection and removal. The incorporation of magnetic ferroferric oxide nanoparticles enables the magnetic recycling and actuation of the single micromotors as well as formation of swarms of worm-like or tank-treading structure. Benefited from the enhanced motion, the micromotors show fast and high-capacity uranium adsorption (747.3 mg g-1), as well as fast uranium detection based on fluorescence quenching. DFT calculation confirms the strong binding between carboxyl groups and uranyl ions. The combination of poly(acrylic acid-co-acrylamide) with ZIF-8 greatly enhances the fluorescence of the micromotor, facilitating the high-resolution fluorescence detection. A low detection limit of 250 ppb is reached by the micromotors. Such self-propelled micromotors provide a new strategy for the design of smart materials in remediation of radioactive wastewater.

Prediction of Uranium Adsorption Capacity in Radioactive Wastewater Treatment with Biochar.

Recently, Japan's discharge of wastewater from the Fukushima nuclear disaster into the ocean has attracted widespread attention. To effectively address the challenge of separating uranium, the focus is on finding a healthy and environmentally friendly way to adsorb uranium using biochar. In this paper, a BP neural network is combined with each of the four meta-heuristic algorithms, namely Particle Swarm Optimization (PSO), Differential Evolution (DE), Cheetah Optimization (CO) and Fick's Law Algorithm (FLA), to construct four prediction models for the uranium adsorption capacity in the treatment of radioactive wastewater with biochar: PSO-BP, DE-BP, CO-BP, FLA-BP. The coefficient of certainty (R2), error rate and CEC test set are used to judge the accuracy of the model based on the BP neural network. The results show that the Fick's Law Algorithm (FLA) has a better search ability and convergence speed than the other algorithms. The importance of the input parameters is quantitatively assessed and ranked using XGBoost in order to analyze which parameters have a greater impact on the predictions of the model, which indicates that the parameters with the greatest impact are the initial concentration of uranium (C0, mg/L) and the mass percentage of total carbon (C, %). To sum up, four prediction models can be applied to study the adsorption of uranium by biochar materials during actual experiments, and the advantage of Fick's Law Algorithm (FLA) is more obvious. The method of model prediction can significantly reduce the radiation risk caused by uranium to human health during the actual experiment and provide some reference for the efficient treatment of uranium wastewater by biochar.

Redox-active phytic acid-based self-assembled hybrid material for enhanced uranium adsorption from highly acidic solution.

Achieving efficient uranium adsorption from highly acidic wastewater is still considered challenging. Here, an inorganic-organic hybridized self-assembly material (rPFE-10) with redox activity was constructed by phytic acid (PA), ethylenediamine (EDA), and Fe(II) via a facile one-pot route, and further applied for U(VI) removal. In the static adsorption experiment, rPFE-10 achieved the maximum U(VI) adsorption capacity of 717.1 mg/g at the optimal pH of 3.5. It also performed preeminently in a highly acidic condition of pH = 1.0, with the highest adsorption capacity of 551.2 mg/g and an equilibrium time of 30 min. Moreover, rPFE-10 exhibited a pH-responsive adsorption selectivity for U(VI) and An-Ln (S(U(VI)) and S(An-Ln)), which increased to 69 % and 94 % respectively as pH decreased from 3.0 to 1.0. Additionally, the spectral analysis revealed a reconstruction mechanism induced by multiple synergistic adsorption, in which U(VI) exchange with EDA+/2+ and Fe2+/3+ and earned suitable coordination geometry and ligand environment to coordinate with PA (mainly P-OH), while partial U(VI) is reduced by Fe(II) in framework. This work not only highlights the facile strategy for enhanced U(VI) retention in highly acidic solution, but expands the potential application of supramolecular self-assembly material in treatment of nuclear wastewater.

Polyvinyl alcohol/phytic acid/phosphorylated chitosan hydrogel electrode highly efficient electroadsorption of low concentration uranium from uranium tailings leachate.

In order to improve the removal rate of uranium and reduce the harm of radioactive pollution, a physically crosslinked polyvinyl alcohol/phosphorylated chitosan (PPP) hydrogel electrode was designed by freezing thawing method. The results show that PPP hydrogel has a good adsorption effect on uranium, and 200 mL of uranium tailings leachate is absorbed, and the treatment efficiency reaches 100 % within 15 min. PPP hydrogel can adapt to a wide range of pH conditions and exhibit excellent adsorption efficiency in the range of 3-9. At the same time, PPP hydrogel maintains an adsorption efficiency of over 85 % for 950 mg/L uranium solution. This lays the foundation for the practical application of PPP hydrogel. In addition, PPP hydrogel also exhibits good repeatability, after 7 cycles, the material still retains 95 % of its initial performance. The synergistic effect of various functional groups such as phosphate, hydroxyl, and ammonium in the material is the main mechanism of PPP's adsorption capacity for uranium. Furthermore, electrochemical adsorption method significantly enhances the adsorption performance of PPP hydrogel.

3D Composite U(VI) Adsorbents Based on Alginate Hydrogels and Oxidized Biochar Obtained from Luffa cylindrica.

3D naturally derived composites consisting of calcium alginate hydrogels (CA) and oxidized biochar obtained from Luffa cylindrica (ox-LC) were synthesized and further evaluated as adsorbents for the removal of U(VI) from aqueous media. Batch-type experiments were conducted to investigate the effect of various physicochemical parameters on the adsorption performance of materials. The maximum adsorption capacity (qmax) was 1.7 mol kg-1 (404.6 mg·g-1) at pH 3.0 for the CA/ox-LC with a 10% wt. ox-LC content. FTIR spectroscopy indicated the formation of inner-sphere complexes between U(VI) and the surface-active moieties existing on both CA and ox-LC, while thermodynamic data revealed that the adsorption process was endothermic and entropy-driven. The experimental data obtained from the adsorption experiments were well-fitted by the Langmuir and Freundlich models. Overall, the produced composites exhibited enhanced adsorption efficiency against U(VI), demonstrating their potential use as effective adsorbents for the recovery of uranium ions from industrial effluents and seawater.

Heterometallic uranyl (hydroxyethyl)iminodiacetic acid (heidi) complexes: Molecular models for U(VI) uptake in complex media.

Amidoximated absorbents (AO-PAN) effectively remove U(VI) from aqueous solution, but previous studies reported more variability for complex natural waters that contain additional confounding ions and molecules. Ternary phases containing U(VI), M(III) (M = Fe(III), Al(III), Ga(III)), and organic molecules exist under these conditions and cause heterogeneous U(VI) uptake on AO-PAN. The goal of the current study is to provide additional insights into the structural features ternary complexes using N-(2-hydroxyethyl)-iminodiacetic acid (HEIDI) as the model organic chelator and explore the relevance of these species on U(VI) capture. Three model compounds ([(UO2)(Fe)2(µ3-O)(C6NO5H8)2(H2O)4] (UFe2), ([(UO2)(Al)2(µ2-OH)(C6NO5H8)2(H2O)3] (UAl2) and [(UO2)(Ga)2(µ2-OH)(C6NO5H8)2(H2O)3] (UGa2)) were characterized by single-crystal X-ray diffraction. Raman spectra of the model compounds were compared with solution data and the ternary phases were noted in the case of Al(III) and Ga(III), but not in the Fe(III) system. U(VI) adsorption onto AO-PAN was not impacted by the presence of HEIDI or the trivalent metal species.

Synthesis of Pillar[5]arene- and Phosphazene-Linked Porous Organic Polymers for Highly Efficient Adsorption of Uranium.

It is crucial to design efficient adsorbents for uranium from natural seawater with wide adaptability, effectiveness, and environmental safety. Porous organic polymers (POPs) provide superb tunable porosity and stability among developed porous materials. In this work, two new POPs, i.e., HCCP-P5-1 and HCCP-P5-2 were rationally designed and constructed by linked with macrocyclic pillar[5]arene as the monomer and hexachlorophosphate as the core via a macrocycle-to-framework strategy. Both pillar[5]arene-containing POPs exhibited high uranium adsorption capacity compared with previously reported macrocycle-free counterparts. The isothermal adsorption curves and kinetic studies showed that the adsorption of POPs on uranium was consistent with the Langmuir model and the pseudo-second-order kinetic model. Especially, HCCP-P5-1 has reached 537.81 mg/g, which is greater than most POPs that have been reported. Meanwhile, the comparison between both HCCP-P5-1 and HCCP-P5-2 can illustrate that the adsorption capacity and stability could be adjusted by the monomer ratio. This work provides a new idea for the design and construction of uranium adsorbents from macrocycle-derived POPs.

Hierarchical Self-Assembled Polyimide Microspheres Functionalized with Amidoxime Groups for Uranium-Containing Wastewater Remediation.

Through molecule self-assembly and subsequent surface functionalization, novel uranium adsorbent AO-OB hierarchical self-assembled polyimide microspheres (AO-OBHSPIMs) were obtained by introducing the amidoxime groups into hierarchical self-assembled polyimide microspheres for the efficient and selective recovery of uranium from wastewater. The results of Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption isotherm showed that AO-OBHSPIMs were a semicrystalline polymer material with self-supporting hierarchical structure and low pore volume, and they were equipped with abundant amidoxime groups. Given the recognized selectivity of amidoxime groups and their hierarchical structure, AO-OBHSPIMs exhibited excellent selectivity to uranyl ions. Moreover, AO-OBHSPIMs exhibited good stability and recyclability and remarkable removal percentage within low-concentration solution (99.4%) and simulated uranium-containing wastewater (97.3%). AO-OBHSPIMs could be applied to fixed-bed column adsorption due to their large particle size and self-supporting hierarchical structure that can facilitate water flow. The in-depth discussion of the adsorption mechanism showed that the adsorption mainly depended on the combined action of electrostatic interactions and complexation, and the adsorption process was a spontaneous endothermic monolayer adsorption. In summary, AO-OBHSPIMs exhibited good application prospects in uranium-containing wastewater remediation.

Uranium Removal from Aqueous Solutions by Aerogel-Based Adsorbents-A Critical Review.

Aerogels are a class of lightweight, nanoporous, and nanostructured materials with diverse chemical compositions and a huge potential for applications in a broad spectrum of fields. This has led the IUPAC to include them in the top ten emerging technologies in chemistry for 2022. This review provides an overview of aerogel-based adsorbents that have been used for the removal and recovery of uranium from aqueous environments, as well as an insight into the physicochemical parameters affecting the adsorption efficiency and mechanism. Uranium removal is of particular interest regarding uranium analysis and recovery, to cover the present and future uranium needs for nuclear power energy production. Among the methods used, such as ion exchange, precipitation, and solvent extraction, adsorption-based technologies are very attractive due to their easy and low-cost implementation, as well as the wide spectrum of adsorbents available. Aerogel-based adsorbents present an extraordinary sorption capacity for hexavalent uranium that can be as high as 8.8 mol kg−1 (2088 g kg−1). The adsorption data generally follow the Langmuir isotherm model, and the kinetic data are in most cases better described by the pseudo-second-order kinetic model. An evaluation of the thermodynamic data reveals that the adsorption is generally an endothermic, entropy-driven process (ΔH0, ΔS0 > 0). Spectroscopic studies (e.g., FTIR and XPS) indicate that the adsorption is based on the formation of inner-sphere complexes between surface active moieties and the uranyl cation. Regeneration and uranium recovery by acidification and complexation using carbonate or chelating ligands (e.g., EDTA) have been found to be successful. The application of aerogel-based adsorbents to uranium removal from industrial processes and uranium-contaminated waste waters was also successful, assuming that these materials could be very attractive as adsorbents in water treatment and uranium recovery technologies. However, the selectivity of the studied materials towards hexavalent uranium is limited, suggesting further developments of aerogel materials that could be modified by surface derivatization with chelating agents (e.g., salophen and iminodiacetate) presenting high selectivity for uranyl moieties.

Theory-Guided Design of a Method to Obtain Competitive Balance between U(VI) Adsorption and Swaying Zwitterion-Induced Fouling Resistance on Natural Hemp Fibers.

The competitive balance between uranium (VI) (U(VI)) adsorption and fouling resistance is of great significance in guaranteeing the full potential of U(VI) adsorbents in seawater, and it is faced with insufficient research. To fill the gap in this field, a molecular dynamics (MD) simulation was employed to explore the influence and to guide the design of mass-produced natural hemp fibers (HFs). Sulfobetaine (SB)- and carboxybetaine (CB)-type zwitterions containing soft side chains were constructed beside amidoxime (AO) groups on HFs (HFAS and HFAC) to form a hydration layer based on the terminal hydrophilic groups. The soft side chains were swayed by waves to form a hydration-layer area with fouling resistance and to simultaneously expel water molecules surrounding the AO groups. HFAS exhibited greater antifouling properties than that of HFAO and HFAC. The U(VI) adsorption capacity of HFAS was almost 10 times higher than that of HFAO, and the max mass rate of U:V was 4.3 after 35 days of immersion in marine water. This paper offers a theory-guided design of a method to the competitive balance between zwitterion-induced fouling resistance and seawater U(VI) adsorption on natural materials.

One-pot synthesis of brewer's spent grain-supported superabsorbent polymer for highly efficient uranium adsorption from wastewater.

High-efficient and fast adsorption of uranium is important to reduce the hazards caused by the uranium contamination of water environment due to the increased human activities. Herein, brewer's spent grain (BSG)-supported superabsorbent polymers (SAP) with different cross-linking densities are prepared as cheap and eco-friendly adsorbents for the first time via one-pot swelling and graft polymerization. A 7 wt% NaOH solution is used to swell BSG before grafting and subsequently neutralize the acrylic acid to control the reaction rate without producing alkaline wastewater. Compared with the traditional methods, swelling improves the grafting density and the utilization of raw materials due to the increased disorder degree of the BSG fibers. This results in the grafting of abundant carboxyl and amide groups onto the BSG backbone, forming a strongly hydrophilic polymer network of the BSG-SAP. Compared with the reference polymers without BSG, BSG-SAP presents higher adsorption capacity and enhanced reusability. The highly cross-linked BSG-SAP (BSG-SAP-H) shows an outstanding adsorption capacity of U(VI) (1465 mg/g at pH0 = 4.6), a fast adsorption rate (81% of equilibrium adsorption capacity in 15 min), and a high selectivity in the presence of competing ions. Adsorption mechanism studies reveal the involvement of amide groups, a bidentate binding structure between UO22+ and the carboxyl groups, and a cation exchange between Na+ and UO22+. More importantly, the adsorption capacity of BSG-SAP-H reaches 254.4 mg/g in the fixed-bed column experiment at a low initial concentration (c0(U) = 30 mg/L) and keeps 80% of the adsorption capacity after four cycles, indicating a great potential for uranium removal from wastewater. This work shows a suitable approach to explore the untreated biomass to prepare SAP with enhanced adsorption performance via a general and low-cost strategy.

Facile synthesis of low-cost MnPO4 with hollow grape-like clusters for rapid removal uranium from wastewater.

In order to deal with the environmental resource problems caused by nuclear pollution and uranium mine wastewater, it is particularly important to develop uranium removal adsorbent materials with low cost, high efficiency and controllable rapid preparation. In this work, the hollow grape-like manganese phosphate clusters (h-MnPO4) were synthesized in 4 h by in-situ etching without template at room temperature, which can quickly and effectively remove uranium ions from wastewater. Due to the reasonable hollow structure, more effective adsorption sites are exposed. The obtained sample h-MnPO4-200 reaches adsorption equilibrium in 1 h and can remove 97.20% uranyl ions (initial concentration is 100 mg L-1). Under the condition of 25 â„ƒ and pH= 4, the maximum adsorption capacity of h-MnPO4-200 for uranium was 751.88 mg g-1. The FT-IR, XPS and XRD analysis showed that -OH and PO43- groups played a key role in the adsorption process. Thanks to the synergistic adsorption mechanism of surface complexation and dissolution-precipitation, h-MnPO4-200 maintained a high removal rate in the presence of competitive anions and cations. In a word, h-MnPO4-200 can be rapidly synthesized through a facile and low-cost method and has a great application prospect in the practical emergency treatment of uranium-containing wastewater.