Adsorption of Eu(III), Th(IV), and U(VI) by mesoporous solid materials bearing sulfonic acid and sulfamic acid functionalities

ABSTRACT

SBA-15 mesoporous materials modified by sulfonic acid and sulfamic acid functionalities, abbreviated as SBA-15/SO₃H and SBA-15/NHSO₃H, were synthesized and applied for the removal–separation of Eu(III), Th(IV), and U(VI). SBA-15/NHSO₃H showed an excellent selectivity toward U(VI), while SBA-15/SO₃H was more efficient adsorbent for Eu(III) and Th(IV). It was found that in the presence of KNO₃ (1 mol L^?1), the separation of Eu(III)/Th(IV) from their mixtures is possible. The results of the sorption behavior indicated a high adsorption capacity toward U(VI) and Th(IV) ions (140.5 and 106.7 mg g^?1, respectively) and ultrafast kinetics (15 min) in Eu(III) adsorption.     

Synergistic Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions Using Mixtures of TODGA and Dinonylnaphthalene Sulfonic Acid

The extraction of U(VI), Th(IV), and lanthanides(III) from aqueous nitric acid solutions with mixtures of N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA) and dinonylnaphtalene sulfonic acid (HDNNS) in n-decane has been investigated. The extraction efficiency of U(VI), Th(IV), and Ln(III) ions is greatly enhanced by addition of HDNNS to an organic phase containing TODGA. The synergistic effect arises from the higher hydrophobicity of U(VI), Th(IV), and Ln(III) extracted species formed by TODGA and DNNS^? anions as compared to those formed by TODGA and NO₃^? ions as counter anions. The synergistic effect for U(VI), Th(IV), and Ln(III) extraction from aqueous nitric acid solutions with mixtures of TODGA and HDNNS becomes weaker when the acidity of the aqueous phase increases. A high synergistic enhancement is accompanied with a high selectivity of Ln(III) extraction from nitric acid solutions.     

Sequential Separation and Trace Enrichment of Thorium(IV) and Uranium(VI) on Chelating Resin Amberlite XAD-2-ortho-vanillinthiosemicarbazone (o-VTSC)

ABSTRACT

Polystyrenc-divinylbenzene-based Amberlite XAD-2 was funetionalized with ortho-vanillinthiosemicarbazone and its analytical properties were investigated. The resin was used successfully for the separation and preconcentration of thorium(IV) and uranium(VI) ions prior to their determination by spectrophotometry and by ICAP-AES and GF-AAS, respectively. The influence of several ions as interferents is discussed. The resin exhibits good chemical stability, reuseability, and a faster rate of equilibration for their determination. The proposed method has been applied to sequential chromatographic separation of thorium(IV) and uranium(VI) on river water samples with good analytical reliability such as recovery of 97–98%, relative standard deviation of 2–3%, and a detection limit of 100 ng-mL^-1. The present method is also used for their determination in monazite sand and some standard geological materials.     

Evaluation of anionic‐ and cationic‐supported hydrogel membranes for sorption of Th(IV) and U(VI) ions from nitric acid medium

Functionalized membranes were obtained by radiation‐induced graft copolymerization (RIGP) of acrylamide‐acrylic acid (AAm‐AAc) and acrylamide‐4‐vinyl pyridine (AAm‐4VP) binary monomers on both low‐density polyethylene and polypropylene films. The supporting conditions as inhibitor concentration, irradiation dose comonomer compositions and concentrations were studied and optimized. The prepared membranes were characterized using SEM, DTA‐TG, and FTIR. They proved that supporting the selected hydrogels on the base films have modified their structure and enhanced their thermal and mechanical characteristics. The sorption characteristics of Th(IV) and U(VI) on the different membranes were studied. The amount of ions sorbed at equilibrium was found to increase with increase in the degree of graft at certain conditions. The kinetics of sorption was also studied and found to obey the Lagergren and Morris–Weber kinetic models. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 320–332, 2006     

Adsorption of Th(IV) and U(VI) on functionalized SBA-15 mesoporous silica materials using fixed bed column method; breakthrough curves prediction and modeling

Removal–separation of Th(IV)/U(VI) by Schiff base functionalized SBA-15 materials SBA/SA and SBA/EnSA using fixed bed column method was investigated. The effects of flow rate and bed height were studied and the experimental breakthrough curves were obtained. The analysis of experimental data showed that the breakthrough time and exhaustion time, metal uptake capacity and total metal removal increased with reducing the flow rate, and with increasing the bed height. Thomas and Yan models were applied to the experimental data for evaluating the dynamic behavior and the characteristic parameters of the column for the process design.     

Unmodified SBA-15 adsorbents for the removal and separation of Th(IV) and U(VI) ions: the role of pore channels and surface-active sites

ABSTRACT

The removal of Th(IV) and U(VI) by calcinated, non-calcinated, and methyl grafted SBA-15 (abbreviated as SBA-15, SBA-15-NC and SBA-15-MG, correspondingly) were compared to elucidate the role of pores and surface adsorption sites on SBA-15 adsorbents. It was proposed that the contribution of pores and surface-active sites of SBA-15 increases its higher adsorption capacity with respect to the other examined adsorbents. The kinetic studies revealed that the adsorption and also desorption occurred initially on the surface and then to the pores. Adsorption/desorption of the ions into pores was occurred with slow kinetics.     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

Extraction of Lanthanides(III), U(VI), and Th(IV) from Nitric Acid Solutions with 1,5-N,N'-Bis[(diphenylphosphoryl)acetylamino]pentanes

Novel polyfunctional neutral organophosphorus ligands, namely 1,5-N,N'-bis[(diphenylphosphoryl)acetyl(alkyl)amino]pentanes [Ph₂P(O)CH₂C(O)NR]₂(CH₂)₅ (Ia, R = C₆H₁₃; Ib, R = CH₃), were studied as extractants for Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from nitric acid solutions. The effect of both HNO₃ concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined by the slope analysis method. Compared with the related bisaminopentane [Ph2P(O)CH₂C(O)NH]₂(CH₂)₅ (Ic), the replacement of hydrogen atoms at the amide nitrogens by alkyl radicals (compounds Ia,b) leads to an increase of metal ions extraction. Bis-CMPO ligands Ia-c were found to possess higher extraction efficiency towards U(VI), Th(IV), and Ln(III) than their monophosphorylated analogue Ph₂P(O)CH₂C(O)N(C₄H₉)₂.     

Equilibrium studies of the extraction of zirconium(IV) from sulfuric acid solutions with Di(2-ethylhexyl)phosphoric acid

Equilibrium studies were made at 25°C in the extraction of zirconium(IV) from sulfuric acid solutions with di(2-ethylhexyl)phosphoric acid (D2EHPA, HR) dissolved in kerosene. The reaction stoichiometry was numerically determined and the compositions of the extracted species were found to be ZrR₄ and ZrR₄(HR) at low loading ratios of D2EHPA (α < 0.09), but became ZrR₄ and ZrR₄(HR)₃ at relatively higher loading ratios (0.10 < α < 0.32). The equilibrium constants for the formation of these species were also obtained. Furthermore, numerical treatment of the experimental data excluded the existence of polynuclear complexes under the conditions studied (α < 0.32).     

Amberlite XAD-2 impregnated organophosphinic acid extractant for separation of uranium(VI) from rare earth elements

Amberlite XAD-2 resin was impregnated with Cyanex272 {bis (2,4,4-trimethylpentyl) phosphinic acid} and Cyanex302 {bis (2,4,4-trimethylpentyl) monothiophosphinic acid}. Systematic studies of Cyanex302 impregnated XAD-2 were carried out to develop optimum conditions for uranium(VI) sorption and devise its separation from rare earth elements. Amberlite XAD-2 impregnated with Cyanex302 had poor distribution coefficients for lanthanum(III) and neodymium(III) while uranium(VI) was quantitatively sorbed from 1×10–3 M HNO3 and was recovered with 1 M HCl from the solid phase. The method proposed is simple, selective and reproducible for determination of uranium(VI) with a relative standard deviation (RSD) of 0.4 %.     

(2S,3R)-2-羟基-3-氨基-4-苯基丁酸的合成方法进展

(2S,3R)-2羟基-3-氨基-4-苯基丁酸（AHPBA）是制备Bestatin、Phebestin和Probestin等氨肽酶N(Aminopeptide N)抑制剂的关键中间体。本文从氨基酸法（D-苯丙氨酸、L-天门冬氨酸、苹果酸二酯）、有机金属催化法（双功能铝配合物）、酶催化法（脂肪酶和全细胞酶）以及其它方法对此中间体的合成方法及路线进行综述和分析。经比较,有机催化法、酶法以及苯乙酮法因其具有经济有利、条件温和或路线简单特点,具有潜在的工业化应用前景。同时,未来人们对AHPBA的合成开发将集中在对已有工艺路线的改进与优化。     

Adsorption of Th(IV) onto Al-pillared rectorite: Effect of pH, ionic strength, temperature, soil humic acid and fulvic acid

The adsorption of Th(IV) onto Al-pillared rectorite as a function of rectorite concentration, Th concentration, pH, ionic strength, temperature, soil humic acid (HA) and fulvic acid (FA) was studied by using batch technique under ambient condition. The results indicated that the adsorption of Th(IV) onto Al-pillared rectorite strongly depended on pH and ionic strength, and the adsorption of Th(IV) increased with increasing Al-pillared rectorite concentration. The presence of HA/FA enhanced Th(IV) adsorption at low pH and reduced Th(IV) adsorption at high pH. The adsorption of Th(IV) decreased with increasing temperature, indicating that the adsorption process of Th(IV) onto Al-pillared rectorite was exothermic. The experimental data of Th(IV) adsorption were analyzed with the Freundlich and Langmuir models, showing that the Freundlich model fitted the adsorption data better than the Langmuir model. The adsorption of Th(IV) on Al-pillared rectorite may be dominated by surface complexation and cation exchange also contributed partly to Th(IV) adsorption.     

Sulfur containing poly(N‐isopropylacrylamide) copolymer hydrogels for thermosensitive extraction of gold(III) ions

Poly[N‐isopropylacrylamide‐co‐[2‐(methylthio)ethyl methacrylate]], poly(NIPA‐co‐MTEMA) gels were prepared by free radical polymerization in aqueous solution. The homogeneous and heterogeneous gels were prepared by using 10 mM MTEMA in 5.0%(v/v) ethanol at 10°C and 30 mM MTEMA in 20%(v/v) ethanol at 50°C, in 1.0 and 1.5M NIPA solution, respectively. Homogeneous and heterogeneous gels had swelling ratios at 540 ± 28% and 551 ± 37%, respectively. The extraction of Au(III) ion was studied in batch method. The optimum pHs for the extraction of Au(III) by homogeneous and heterogeneous gels were 1–3 and 1–5, respectively. The suitable extraction time was 3 h at 50°C when using a rod‐shaped copolymer (0.7 cm diameter and 1 cm length). The adsorption behavior obeyed the Langmuir and Freundlich isotherms. The maximum sorption capacities of Au(III) onto homogeneous and heterogeneous gels were 62.8 and 322 μmol/g, respectively. The desorption equilibrium was reached within 2–3 h at 10°C by 0.1M thiourea in 5%(v/v) HCl. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

2－巯基－3－（4－羟基－3－甲氧基）苯基丙烯酸的合成

使用微波辐射和超声波技术合成了２－流基－３－（４－羟基－３－甲氧基）苯基丙烯酸，通过元素分析，红外光谱，核磁共振谱确证其结构。     

Cooperative effect of 2-(dibutylcarbamoyl)benzoic acid and 2-thenoyltrifluoroacetone for the synergistic extraction of lanthanide ions

2-(Dibutylcarbamoyl)benzoic acid (HL) has been examined for the extraction-separation of La³⁺, Eu³⁺ and Er³⁺ from aqueous chloride solutions into organic diluents; dichloromethane, ethylacetate and carbon tetrachloride. The efficiency and the selectivity of the extraction process were significantly affected by the organic diluent. The application of a mixture of HL and 2-thenoyltrifluoroacetone (HTTA) showed a synergistic effect on the extraction of the studied lanthanides. The extracted species was found to be as ML₃(HTTA) complexes (M is La³⁺, Eu³⁺ and Er³⁺). The proposed method was applied for the extraction of lanthanides from simulated leach solution of spent Ni-MH batteries.     

Selective extraction of In(III), Ga(III) and Zn(II) using a novel extractant with phenylphosphinic acid

A new extractant, [N,N-di(2-ethylhexyl)amino]methylphenylphosphinic acid (DEAPP), was synthesized to de-velop the mutual separation techniques of In(III), Ga(III) and Zn(II). The extraction selectivity for In(III), Ga(I I) and Zn(II) with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mol·L?1 aqueous ammonium nitrate solution with DEAPP was in the following order:In(III) N Ga(III) N Zn(II). These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of In(III), Ga(III) and Zn(II). The extraction equilibria of In(I I), Ga(II ) and Zn(II) with DEAPP (=HR) were expressed by the following reactions:In3++2eHRT2?InR3eHRT+3H+, Ga3++1.5eHRT2+NO3??GaR2eHRTeNO3T+2H+, and Zn2++2eHRT2?ZnR2eHRT 2 + 2H+. The extraction equilibrium constants of In(III), Ga(III) and Zn(II) with DEAPP were determined to be Kex,M=1.7 × 104 [dm3·mol?1], 4.17 [(dm3·mol?1)0.5], and 1.55 x 10?2 [–], respectively.     

Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution

In this work, an adsorbent, which we call MnPT, was prepared by combining MnO₂, polyethylenimine and tannic acid, and exhibited efficient performance for Cu(II) and Cr(VI) removal from aqueous solution. The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation. The maximum adsorption capacities of MnPT for Cu(II) and Cr(VI) were 121.5 and 790.2 mg·g⁻¹, respectively. The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(II) and Cr(VI) co-adsorption on MnPT. Electrostatic force, solvation action, adsorbate–adsorbate lateral interaction, and complexation were involved in the spontaneous adsorption process. Physical electrostatic action was dominant in the initial stage, whereas chemical action was the driving force leading to adsorption equilibrium. It should be noted that after adsorption on the surface of MnPT, Cr(VI) reacted with some reducing functional groups (hydroxylamine-NH₂) and was converted into Cr(III). The adsorption capacity declined by 12% after recycling five times. Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents. This MnPT nanocomposite has been proven to be a low-cost, efficient, and promising adsorbent for removing heavy metal ions from wastewater.     

Low Temperature Initiation by 3-Mercaptopropionic Acid-Ce(IV) or -KMnO4 Redox System for Polymerization of Acrylamide Monomer

Polymerization of acrylamide monomer was performed at low temperatures using 3-mercaptopropionic acid-cerium(IV) sulfate and 3-mercaptopropionic acid-KMnO₄ redox systems in acid aqueous medium. Water soluble polyacrylamides containing 3-mercaptopropionic acid end groups were synthesized. The effects of mole ratio of acrylamide to initiator(n_MSA= n_Ce(IV)), polymerization time, temperature, and concentration of sulfuric acid on the yield and molecular weight of polymer were investigated. The decrease in the mole ratio of acrylamide/Ce(IV) at constant monomer concentration resulted in an increase in the yield but a decrease in molecular weight of polymer. The increase of reaction temperature from 20° to 70°C resulted in a decrease in the yield but indicated generally a constant value for the molecular weight of polymer. With increasing of polymerization time, the yield and molecular weight of polymer did not change mainly. Ce(IV) and Mn(VII) ions are reduced to Ce(III) and Mn(II) ions, respectively in the polymerization reaction. The existence of Ce(III) ion bonded to polymer was investigated by UV-visible spectrometry and fluorescence measurements. The amount of Mn(II) that is incorporated to the polymer was determined using graphite furnace atomic absorption spectrometry. The mechanism of this phenomenon is discussed.     

The enhanced performance of Cr(VI) photoreduction and antibiotic removal on 2D/3D TiO2/ZnIn2S4 nanostructures

In this study, 2D/3D TiO₂/ZnIn₂S₄ nanostructures with TiO₂ sheet cluster embedded into ZnIn₂S₄ micro flowers were fabricated via hydrothermal method. The matched band structure, the enlarged surface area and the efficient photo-induced charge transfer offered by effective heterostructures formed between the two components endowed the TiO₂/ZnIn₂S₄ nanoarchitecture with excellent photocatalytic Cr(VI) reduction and tetracycline hydrochloride (TC) degradation performance. Especially, the Cr(VI) photoreduction efficiency of 50% TiO₂/ZnIn₂S₄ was 8.8 times higher compared to pure ZnIn₂S₄. The enhanced separation efficiency of photo-excited charge carriers was induced by the matched band structure, the enlarged surface area and the strong interaction between TiO₂ and ZnIn₂S₄. The key roles of ·O₂^? was confirmed via trapping experiments. Otherwise, the pathway of TC degradation was investigated. The proposed mechanism during photocatalysis process was also discussed according to the photocatalytic and characterization results.