Efficient removal of U(VI) from wastewater by a sponge-like 3D porous architecture with hybrid electrospun nanofibers

Removal of uranium(VI)from nuclear wastewater is urgent due to the global nuclear energy exploitation.This study synthesized novel sponge-like 3D porous materials for enhanced uranium adsorption by combining electrospinning and fibrous freeze-shaping techniques.The materials possessed an organic-inorganic hybrid architecture based on the electrospun fibers of polyacrylonitrile(PAN)and SiO_(2).As a sup-porting material,the surface of fibrous SiO_(2) could be further functionalized by cyano groups via(3-cyanopropyl)triethoxysilane.All the cyano groups were turned into amidoxime(AO)groups to obtain a amidoxime-functionalized sponge(PAO/SiO_(2)-AO)through the subsequent ami-doximation process.The proposed sponge exhibited enhanced uranium adsorption performance with a high removal capacity of 367.12 mg/g,a large adsorption coefficient of 4.0×10^(4)mL/g,and a high removal efficiency of 97.59%.The UO_(2)^(2+)adsorption kinetics perfectly conformed to the pseudo-second-order reaction.The sorbent also exhibited an excellent selectivity for UO_(2)^(2+) with other interfering metal ions.2023 Hohai University.Production and hosting by Elsevier B.V.

A functionalized activated carbon adsorbent prepared from waste amidoxime resin by modifying with H_(3)PO_(4) and ZnCl_(2) and its excellent Cr(Ⅵ)adsorption

With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.

Branched fibrous amidoxime adsorbent with ultrafast adsorption rate and high amidoxime utilization for uranium extraction from seawater

Direct collection of uranium from low uranium systems via adsorption remains challenging.Fibrous sorbent materials with amidoxime(AO)groups are promising adsorbents for uranium extraction from seawater.However,low AO adsorption group utilization remains an issue.We herein fabricated a branched structure containing AO groups on polypropylene/polyethylene spun-laced nonwoven(PP/PE SNW)fibers using grafting polymerization induced by radiation(RIGP)to improve AO utilization.The chemical structures,thermal properties,and surface morphologies of the raw and treated PP/PE SNW fibers were studied.The results show that an adsorptive functional layer with a branching structure was successfully anchored to the fiber surface.The adsorption properties were investigated using batch adsorption experiments in simulated seawater with an initial uranium concentration of 500μg·L^(−1)(pH 4,25℃).The maximum adsorption capacity of the adsorbent material was 137.3 mg·g^(−1)within 24 h;moreover,the uranyl removal reached 96%within 240 min.The adsorbent had an AO utilization rate of 1/3.5 and was stable over a pH range of 4–10,with good selectivity and reusability,demonstrating its potential for seawater uranium extraction.

Amidoxime-based adsorbents prepared by cografting acrylic acid with acrylonitrile onto HDPE fiber for the recovery of uranium from seawater

An amidoxime-based polymeric adsorbent was prepared by pre-irradiation grafting of acrylonitrile and acrylic acid onto high-density polyethylene fibers using electron beams,followed by amidoximation.Quantitative recovery of uranium was investigated by flow-through experiment using simulated seawater and marine test in natural seawater.The maximum amount of uranium uptake was 2.51 mg/g-ads after 42 days of contact with simulated seawater and 0.13 mg/g-ads for 15 days of contact with natural seawater.A lower uranium uptake in marine test can be attributed to the short adsorption time and the contamination of marine microorganisms and iron.However,the high selectivity toward uranium against vanadium may be beneficial to harvest uranyl ion onto adsorbents and the economic feasibility for recovery of uranium from seawater.

Preparation of amidoxime-based PE/PP fibers for extraction of uranium from aqueous solution

A novel amidoxime-based fibrous adsorbent,denoted as PE/PP-g-(PAAc-co-PAO), was prepared by preirradiation grafting of acrylic acid and acrylonitrile onto polyethylene-coated polypropylene skin-core(PE/PP)fibers using 60 Co γ-ray irradiation, followed by amidoximation. The original and modified PE/PP fibers were characterized by a series of characterization methods to demonstrate the attachment of amidoxime groups onto the PE/PP fibers. Breaking strength tests confirmed that the fibrous adsorbent could maintain good mechanical properties. The adsorption capacity of the PE/PP-g-(PAAc-coPAO) fibers was investigated in simulated seawater with an initial uranium concentration of 330 μg/L. The uranium adsorption capacity was 2.27 mg/g-adsorbent after 24 h in simulated seawater, and the equilibrium data were well described by the Freundlich isotherm model. The PE/PP-g-(PAAc-co-PAO) adsorbent exhibited good regeneration and recyclability during five adsorption-desorption cycles.The adsorption test was also performed in simulated radioactive effluents with uranium concentrations of 10 and100 μg/L. The effect of the pH value on the adsorption capacity was also studied. At a very low initial concentration 10 μg/L solution, the PE/PP-g-(PAAc-co-PAO)fiber could remove as much as 93.0% of the uranium, and up to 71.2% of the uranium in the simulated radioactive effluent. These results indicated that the PE/PP-g-(PAAcco-PAO) adsorbent could be used in radioactive effluents over a wide range of pH values. Therefore, the PE/PP-g-(PAAc-co-PAO) fibers, with their high uranium selectivity,good regeneration and recyclability,good mechanical properties, and low cost, are promising adsorbents for extracting uranium from aqueous solutions.

Density functional study of uranyl （VI） amidoxime complexes

Uranyl （VI） amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation （GGA）. Comparison of （acet） uranyl amidoxime complexes （[UO2（AO）n]2-n, 1≤ n≤4） with available experimental data shows an excellent agreement. In addition, the U-O（1）, U-O（3）, C（1）-N（2）, and C（3） N（4） bond lengths of [UO2（CH3AO）4]2- are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 A. The angles of N（3） O（3）-U, O（2）-N（1）-C（1）, N（3）-C（3）-N（4）, N（4）-C（3） C（4）, and C（4）-C（3）-N（3） are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex.

A core–shell amidoxime electrospun nanofiber affinity membrane for rapid recovery Au(Ⅲ) from water

An affinity membrane was prepared by coaxial electrospinning and amidoxime(AONFA),and it was applied to selectively recovery Au(Ⅲ)from an aqueous solution.The static adsorption results showed that,when p H at 5,the maximum adsorption capacity of AONFA membrane for Au(Ⅲ)was 509.3 mg·g^(-1).AONFA membrane exhibit much higher affinity and selectivity towards Au(Ⅲ)than other metal cations.The membrane could be regenerated effectively by mixture solution of thiourea and HCl,and the desorption ratio reached almost 100%after 4 hours desorption.The dead-end filtration results showed that,the membrane utilization efficiency and adsorption capacity can be improved by increasing the flow rate,while increasing the concentration shorted the breakthrough process and had little impact to adsorption capacity.We can flexibly adjust the flow rate and concentration according to the situation to obtain the maximum utilization efficiency of the membrane in filtration process.The dynamic adsorption capacity is higher than the static adsorption capacity.The adsorption mechanism for Au(Ⅲ)is electrostatic adsorption and reduction.Thus,AONFA membrane filtration was demonstrated to be a promising method for continuous recover Au(Ⅲ)from wastewater.

2-37 Desorption of Uranium from Amidoximed Silica

Previous work suggested that amidoximed silica can be used as a highly efficient adsorbent for uranium removalfrom salt lake water. In this work, desorption of uranium from amidxoximed silica was investigated.Amidoximed silica, which were loaded with uranium(VI) from salt lake water were used for desorption studies.0.1 mol / L of HNO3 Na2CO3, NaHCO3 and NaOH solution were used as desorbing solutions, respectively. The uranium desorbed into the solution was determined after shaking for certain time. Desorption efficiency wascalculated directly from the difference between the desorbed and absorbed uranium. The desorption ratio (%) wascalculated by the following equation:

2-24 Selective Uranium Extraction from Salt Lake Brine by Amidoximated Saccharomyces cerevisiae

Uranium concentration in salt lake brines is tens even thousands times higher than seawater, which makes salt lake brine being another ideal resource for uranium. However, the content of salt lake brine is very complicate, a large amount of K, Na, Ca, Mg elements coexisting with uranium. Hence, only sorbent with high uranium selectivity can be well used in uranium extraction from salt lake brine.

Adsorption of U(Ⅳ) onto Amidoxime-functionalized Hydrothermal Carbon in the Presence of Ca-U(Ⅳ)-CO3 Complexes

The aim is collecting uranium from groundwater in which uranium mainly exists in negative species,the amidoxime-functionalized hydrothermal carbon(AO-HTC)was synthesized.From the results of N2 adsorption-desorption and SEM,AO-HTC is a small spherical surface;FT-IR and Elemental analysis showed that the amidoxime group was successfully grafted onto the surface of the material;Zeta-potential measurement showed that the amino nitrogen atom is protonated in the oxime group.The optimum pH value of AO-HTC for uranium adsorption is 6.0,and the adsorption equilibrium is reached within 80 min,which is in accordance with the pseudo-second order adsorption kinetic model.The adsorption of uranium by AO-HTC accords with the Langmuir isotherm adsorption model,and the single-layer saturated adsorption capacity is 254.13mg·g^-1.The thermodynamic parameters calculated by the adsorption isotherm indicate that AO-HTC adsorption of uranium is a spontaneous endothermic chemical process and Carbonate ion,calcium ion and humic acid concentration have great influence on uranium adsorption.The experiments results show that AO-HTC has the potential to elimination of U(Ⅳ)from groundwater.

Poly(amidoxime)-reduced graphene oxide composites as adsorbents for the enrichment of uranium from seawater

The development of efficient materials for high extraction of uranium(UO22+) from seawater is critical for nuclear energy. Poly(amidoxime)-reduced graphene oxide(PAO/rGO) composites with excellent adsorption capability for UO22+ were synthesized by in situ polymerization of acrylonitrile monomers on GO surfaces, followed by amidoximation treatment with hydroxylamine. The adsorption capacities of PAO/rGO composites for UO22+ reached as high as 872 mg/g at pH 4.0. The excellent tolerance of these composites for high salinity and their regeneration-reuse properties can be applied in the nuclear-fuel industry by high extraction of trace UO22+ ions from seawater.

Extremely stable amidoxime functionalized covalent organic frameworks for uranium extraction from seawater with high efficiency and selectivity

Uranium extraction from seawater is of strategic significance for nuclear power generation.Amidoximebased functional adsorbents play indispensable roles in the recovery of seawater uranium with high efficiency.Nevertheless,balancing the adsorption capacity and selectivity is challenging in the presence of complicated interfering ions especially vanadium.Herein,a polyarylether-based covalent organic framework functionalized with open-chain amidoxime(COF-HHTF-AO)was synthesized with remarkable chemical stability and excellent crystallinity.Impressively,the adsorption capacity of COF-HHTF-AO towards uranium in natural seawater reached up to 5.12 mg/g,which is 1.61 times higher than that for vanadium.Detailed computational calculations revealed that the higher selectivity for uranium over vanadium originated from the specific bonding nature and coordination pattern with amidoxime.Combining enhanced adsorption capacity,excellent selectivity and ultrahigh stability,COF-HHTF-AO serves as a promising adsorbent for uranium extraction from the natural seawater.

Theoretical studies on the complexation of uranyl with typical carboxylate and amidoximate ligands

Understanding of the bonding nature of uranyl and various ligands is the key for designing robust sequestering agents for uranium extraction from seawater. In this paper thermodynamic properties related to the complexation reaction of uranyl（VI） in aqueous solution （i.e. existing in the form of UO2（H20）52＋） by several typical ligands （L） including acetate （CH3CO2）, bicar- bonate （HOCO2-）, carbonate （CO32-）, CH3（NH2）CNO- （acetamidoximate, AO-） and glutarimidedioximate （denoted as GDO2-） have been investigated by using relativistic density functional theory （DFT）. The geometries, vibrational frequencies, natural net charges, and bond orders of the formed uranyl-L complexes in aqueous solution are studied. Based on the DFT analysis we show that the binding interaction between uranyl and amidoximate ligand is the strongest among the selected complexes. The thermodynamics of the complexation reaction are examined, and the calculated results show that complexation of uranyl with amidoximate ligands is most preferred thermodynamically. Besides, reaction paths of the substitution complexation of solvated uranyl by acetate and AO have been studied, respectively. We have obtained two minima along the reaction path of solvated uranyl with acetate, the monodentate-acetate complex and the bidentate-acetate one, while only one minimum involving monodentate-AO complex has been located for AO- ligand. Comparing the energy barriers of the two reaction paths, we find that complexation of uranyl with AO is more difficult in kinetics, though it is more preferable in thermodynamics. These results show that theoretical studies can help to select efficient ligands with fine-tuned thermodynamic and kinetic properties for binding uranyl in seawater.

Decorating Covalent Organic Frameworks with High-density Chelate Groups for Uranium Extraction

The extraction of uranium from aqueous solution is highly desirable for sustaining the increasing demand for environmental safety and nuclear fuel.Herein,we report a strategy using a two-step covalent modification for the synthesis of covalent organic frameworks(COFs)with high-density amidoxime chelate groups at periphery.The introduction of dense amidoxime groups plays a pivotal role in uranium adsorption.The resulting COF exhibits strong affinity with the distribution coefficient of 5.2×104 mL/g and a high adsorption capacity of 319.9 mg/g.The strategy could be expanded to identify and remove different contaminants by introducing special functional groups.

Kenaf cellulose-based poly(amidoxime) ligand for adsorption of rare earth ions

A well-known adsorbent, poly(amidoxime)ligand, was prepared from polyacrylonitrile(PAN) grafted kenaf cellulose, and subsequent characterization was performed by Fourier transform infrared spectroscopy(FTIR),field emission scanning electron microscope(FESEM) and inductively coupled plasma mass spectrometry(ICP-MS).The adsorption capacities of the prepared ligand for rare earth metals are found to be excellent, with adsorptions of La^(3+), Ce^(3+), Pr^(3+), Gd^(3+) and Nd^(3+) experimentally determined to be 262, 255, 244, 241 and 233 mg·g^(-1), respectively, at pH 6. The experimental values of the adsorption of rare earth metals are well matched with the pseudosecond-order rate equation. The reusability of the adsorbent is examined for seven cycles of sorption/desorption,demonstrating that the proposed adsorbent could be reused for over seven cycles without any significant loss in the original removal capability of the ligand.

High Photocatalytic Properties of Zinc Oxide Nanoparticles with Amidoximated Bacterial Cellulose Nanofibers as Templates

The freshly prepared water-wet amidoximated bacterial cellulose （Am-BC） serves as an effective nanoreactor to synthesis zinc oxide nanoparticles by in situ polyol method. The obtained ZnO/Am-BC nanocomposites have been characterized by field emission scanning electron microscopy （FE-SEM）, X-ray diffraction （XRD）, Fourier transformed infrared spectroscopy （FTIR） and thermogravimetric analysis （TGA）. The influence of the zinc acetate concentration on the morphologies and size ofZnO nanoparticles and the possible formation mechanism were discussed. The results indicated that uniform ZnO nanoparticles were homogeneously anchored on the Am-BC nanofibers through strong interaction between the hydroxyl and amino groups of Am-BC and ZnO nanoparticles. The loading content of ZnO nanoparticles is higher using Am-BC as a template than using the unmodified bacterial cellulose. The resultant nanocomposite synthesized at 0.05 wt% shows a high photocatalytic activity （92%） in the degradation of methyl orange.

Visualized uranium rapid monitoring system based on self-enhanced electrochemiluminescence-imaging of amidoxime functionalized polymer nanoparticles

The development of uranyl ion detection technology has exhibited its significance in public security and environmental fields for the radioactivity and chemical toxicity of uranyl ion.The WHO standard of uranyl ion makes it necessary to develop highly sensitive uranyl rapid warning system in drinking water monitoring.Herein,a visualized rapid warning system for trace uranyl ion is carried out based on electrochemiluminescence(ECL) imaging technology to give an ultra-low limit of detection(LOD) and high selectivity.Amidoxime,a bi-functional group with both uranyl ion capturing and co-reactive functions,is modified on a conjugated polymer backbone with strong ECL signal to be prepared into three-in-one polymer nanoparticles(PNPs) with self-enhanced ECL property.The captured uranyl ion can enhance the ECL signal of PNPs via resonance energy transfer process to give the LOD as 0.5 ng/L,which is much lower than the known luminescent uranyl sensors.Furthermore,ECL imaging technology is introduced into realizing visualized uranyl rapid warning,and can be successfully applied on natural water samples.This study provides a novel strategy for uranyl rapid warning,and shows its potential meaning in public security and environmental fields.