Cation Transport at 25°C from Binary Cd2+–Mn+ Mixtures in a H2O-CHCl3–H2O Liquid Membrane System Containing a Series of Macrocyclic Carriers[1]

Macrocycle-mediated fluxes of Cd(NO₃)₂ and of several binary mixtures of Cd(NO₃)₂ with the nitrate salt of either Na⁺, K⁺, Rb⁺ Cs⁺, Ag⁺, Ca²⁺, Sr²⁺, Pb²⁺, Zn²⁺, or Cu²⁺ have been determined in a H₂O-CHCl₃–H₂O liquid membrane system. Of the macrocycles studied, 2.2 and 2.2DD most successfully transported Cd²⁺ In the Cd²⁺–Mⁿ⁺ mixtures, Cd²⁺ was transported selectively with 2.2 when Mⁿ⁺ was either an alkali or an alkaline earth cation. However, when Mⁿ⁺ was either Ag⁺, Pb²⁺, or Cu²⁺ the Cd²⁺ flux was reduced sharply. Generally, cation flux was greater for 2.2DD than for 2.2 with selectivity for Cd²⁺ being altered also in several cases. Relative fluxes from binary cation mixtures depend on metal cation radius, macrocycle cavity diameter, ligand ring substituent and log K for metal ion-macrocycle interaction.     

Selective Transport of Cu2+ Ions through Bulk Liquid Membrane System Mediated by Erythromycin Ethyl Succinate

The carrier mediated transport of Cu²⁺ ions from an aqueous medium has been examined. The ability of Erythromycin Ethyl Succinate (EES) as a carrier to form a complex with Cu²⁺ ions and transport them to the receiving phase is reported. The fundamental parameters influencing the transport of Cu²⁺ ions such as the pH in the source and receiving phases and concentration of the stripping agent in the receiving phase have been optimized and accordingly, the amount of Cu²⁺ transported across the liquid membrane after 5 h was 94.3 ± 1.8% in the presence of L-histidine as a suitable stripping agent. Moreover, the selectivity and efficiency of Cu²⁺ ions transport from aqueous solution over other cations in ternary and quaternary mixtures have been investigated. The results indicate that our fabricated membrane is very sensitive toward Cu⁺² ions in the presence of heavy metal ions.     

Extraction of Cs+ and Sr2+ from HNO3 Solution Using Macrocyclic Polyethers

Abstract

A series of crown compounds has been studied in connection with the development of a solvent extraction process for removing Cs⁺ and Srs²⁺ from acidic high activity nuclear waste. Crown compounds were investigated because of their ability to form organic soluble complexes with the alkali metals and the alkaline earth metals. The solvent (tributyl phosphate and kerosene) was chosen because of its compatibility with the Purex process currently used at the Savannah River Plant for plutonium and uranium purification. The crown compounds were found not to be sufficiently strong complexing agents to extract these metals from an aqueous phase with an inorganic anion such as nitrate or chloride. However, the use of large organic soluble anions which also functioned as liquid ion exchangers made it possible to extract Cs⁺ from 3 M HNO₃ while leaving Sr²⁺ and La³⁺ behind. The use of .02 M bis-(4,4′(5′)-[q-hydroxyheptyl]-benzo)-18-crown-6 in 0.076 M (5 vol-%) didodecylnaphthalene sulfonic acid (DNS)-27 vol-% TBP-68 vol-% kerosene gave the most favorable results for cesium extraction. The two phases separated cleanly and rapidly, yielding a distribution coefficient of 2.0 org/aq from 3 M HNQ₃. Strontium and lanthanum did not extract significantly at this acid concentration. The distribution data in the low acid region (10^?4 M) are best explained by steric hindrance effects. The lanthanum did not extract at any acid concentration while the strontium extracted very well by a liquid ion-exchange mechanism but the addition of the crown compound did not improve the distribution. The addition of the crown compound improved the Cs⁺ distribution markedly in the low acid region even though the Cs⁺ diameter is larger than the 18-crown-6-crown cavity while Sr²⁺ should fit very well.     

Luminescence characteristics of SrZnSO:M (M = Bi3+, Mn2+ and Tb3+) phosphors

Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors were prepared to investigate their luminescence characteristics. The SrZnSO:Bi³⁺, SrZnSO:Mn²⁺ and SrZnSO:Tb³⁺ phosphors, excited by the NUV/blue light, show blue, orange and green emissions, respectively. The Bi³⁺ → Tb³⁺, Tb³⁺ → Mn²⁺ and Bi³⁺ → Mn²⁺ energy transfer processes take place in Bi³⁺/Tb³⁺-, Tb³⁺/Mn²⁺-, Bi³⁺/Mn²⁺- and Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors, which result in tunable luminescence of these phosphors. The CIE coordinates were calculated on the basis of the emission spectra, and they reflect the emission color changes of phosphors. For the Bi³⁺/Tb³⁺-, Tb³⁺/Mn²⁺- and Bi³⁺/Mn²⁺- activated SrZnSO phosphors, the emission points are located in the cyan, yellow and white light regions, respectively. For the Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors, the light is in warm white light region.     

Liquid-vapor distribution of acids in HNO3-H2O and HNO3-H2O-HA systems in evaporators

Equilibrium data on the liquid-vapor distribution for HNO₃-H₂O, HNO₃-HF-H₂O, HNO₃-CH₃COOH-H₂O, and HNO₃-HCl-H₂O are given. Equations for the calculation of the acid distribution coefficients in the first three systems have been obtained and a mathematic model for nitric acid rectification containing the impurities has been derived, excluding the case of azeotropic rectification. The model could not be applied to the process based on ox-red reactions such as in the HCl-HNO₃ system. The HNO₃ liquid-vapor distribution during uninterrupted evaporation in the apparatus with bottom circulation is in equilibrium, while that in direct-flow evaporators with ascending and descending flows is characterized by a significantly higher distribution coefficient because of the linear evaporation effect.     

以D2EHPA-TOPO为载体的乳化液膜体系萃取磷酸中La（Ⅲ）的工艺及传质机理研究

通过以二（2-乙基己基）磷酸酯／氧化三辛基膦（D2EHPA／TOPO）为流动载体,磺化聚丁二烯（LYF）为表面活性剂,液体石蜡为膜增溶剂,煤油为稀释剂,盐酸为内水相的W／O型乳液,与含La（Ⅲ）的磷酸的外水相进行萃取的过程,制备了W／O／W的双重乳化液膜体系,用单因素法考察了载体浓度,表面活性剂浓度,内相酸度,水乳比等对液膜提取率的影响,确定了最佳工艺条件,迁移率达94．21％以上。并以单浓度递变斜率法研究了载体浓度,表面活性剂浓度,磷酸浓度,H2PO4^-浓度,水相平衡H^＋浓度对分配比的影响,推导出了该乳化液膜的传质机理所经历的步骤。传质机理中包括萃取-反萃表达式,和协萃物组成La（H2PO4）L2（HL）2·（H3PO4）·2TOPO。     

Mn2+对掺Ce3+BiB3O6纳米材料发光强度的影响

采用溶胶-凝胶的方法合成了一系列掺杂Mn2+,Ce3+的BiB3O6纳米发光材料.通过激发光谱和发射光谱研究了其发光性质,并探讨了Mn2+对Ce3+发光性能的影响.BiB3O6:Ce3+的发射光谱有位于370nm和405nm处的2个发射峰,由于Mn2+对Ce3+的敏化作用,Ce3+在BiB3O6:Ce3+,Mn2+中的发光强度有了显著的增强.     

Transport of Eu3+ through a Bis(2-ethylhexyl)-phosphoric Acid,n-Dodecane Solid Supported Liquid Membrane

Abstract

The coupled transport of Eu³⁺ and H⁺ ions through a solid supported liquid membrane consisting of a porous polypropylene film immobilizing an HDEHP solution in n-dodecane has been studied as a function of the membrane area, stirring speed of the aqueous solutions, membrane composition, and acidity of the feed solution. The experimental results are in agreement with predictions derived from a theoretical permeability coefficient equation which assumes that membrane diffusion and aqueous film diffusion are the only rate-controlling factors.     

Broadband deep-red-to-near-infrared emission from Mn2+ in strong crystal-field of nitride MgAlSiN3

Broadband near-infrared (NIR) phosphors have received increasing attention for fabricating phosphor-converted light-emitting diodes (pc-LEDs) as NIR light source. Most of the reported broadband NIR phosphors originate from Cr³⁺ in weak crystal field environments. Herein, we report a luminescent material, MgAlSiN₃:Mn²⁺ with CaAlSiN₃-type structure, demonstrating that broadband deep-red-to-NIR emission can be achieved via doping Mn²⁺ into crystallographic sites with strong crystal field in inorganic solids. This phosphor is synthesized via easy-handle solid-state reaction, and the optimized sample, (Mg_0.93Mn_0.07) AlSiN₃ shows an emission band with peak at ~754 nm, FWHM of 150 nm, and internal quantum efficiency of 70.1%. The photoluminescence intensity can further be enhanced by co-doping Eu²⁺ as sensitizer. This work provides a new strategy for discovering new broadband NIR phosphors using Mn²⁺ in strong crystal field as luminescence center.     

由锌锰硫酸溶液三相萃取锌锰离子

以P204煤油溶液(油相,O)、PEG 10000水溶液(水相1,W1)及锌锰离子的硫酸铵盐溶液(水相2,W2)构建三相萃取体系(O-W1-W2),将其对锌锰离子的萃取效率与传统溶剂萃取[O-W'2(锌锰硫酸溶液)]和双水相萃取(W1-W2)作了比较. 结果表明,加入KSCN后,三相体系能有效地一步分离锌锰离子. 将SCN-/Zn2+摩尔比由10增大至60,W1相只富集Zn2+,且Zn2+总的萃取率(90%)高于O-W'2(52.8%)和W1-W2(86.2%),O相对Mn2+的萃取率(28%)高于O-W1(10.2%).     

Ga掺杂的La_(1/2)(Pr_(1/4+3y/4)Ca_(3/4-3y/4))_(1/2)Mn_(1-y)Ga_yO_3的磁性和电输运性质

实验详细研究了Ga掺杂对锰基氧化物La1/2(Pr1/4+3y/4Ca3/4-3y/4)1/2Mn1-yGayO3(Mn3+:Mn4+=5:3,y=0,0.02,0.05,0.08和0.10)的磁性和电输运性质的影响。实验发现,用Ga3+离子替代Mn3+离子会显著地抑制样品的铁磁性和金属导电特性。随着Ga掺杂量从0增加到0.10,样品的居里温度TC、金属-绝缘转变温度TM I和最大磁电阻所对应的温度均向低温方向偏移,然而样品的电阻率以及最大磁电阻却显著地增加。除了在金属-绝缘转变温度TM I附近出现的本征庞磁电阻外,我们在低温区域还发现了显著的磁电阻效应,这种低温磁电阻是由多晶样品中的晶界效应导致的。另外,通过对宏观磁性的分析,我们没有发现Pr3+离子对磁性的贡献。实验结果表明:磁稀释和无序效应在决定样品的磁性和电输运性质方面起到了重要的作用。     

Use of Masking Agents in Promoting Selective Transport of Zn2+ through Nafion Membrane

ABSTRACT

The effect of H⁺ ion concentration on the ion-exchange selectivity of Nafion 117 cation-exchange membrane toward Zn²⁺, Pb²⁺, Cu²⁺, Al³⁺, and Fe³⁺ have been studied. A selective transport of any particular metal ion was not possible by controlling the pH alone. However, selective permeation of Zn²⁺ across the membrane could be accomplished by selectively masking the metal ion as the cationic 1,10-phenanthroline complex while the permeation of other interfering ions could be suppressed by masking them as their anionic EDTA complex. About 20% of Zn²⁺ selectively permeated from the mixture in 6 hours and the quantity increased to 67% after 60 hours of permeation.     

Electrochemical behaviour of Mn3+/Mn2+, Co3+/Co2+ and Ce4+/Ce4+ redox mediators in methanesulfonic acid

The redox behaviour of Mn³⁺/Mn²⁺, Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ mediators commonly used in indirect oxidation of organic compounds were evaluated in methane sulfonic acid on a glassy carbon working electrode employing cyclic voltammetry. Manganic methanesulfonate exhibits higher instability in dilute methanesulfonic acid. The solid MnO₂ formed during disproportionation on the glassy carbon electrode further affects the reproducibility. Cobaltic methanesulfonate formation occurs only at oxygen evolution region rendering the overall oxidation process less efficient. Ceric methane sulfonate formation is highly efficient over a wide acid concentration range. Ceric methanesulfonate can also be employed over a wide temperature range to oxidize different aromatic compounds.     

Kinetics of Mn(II) Transport from Aqueous Sulfate Solution through a Supported Liquid Membrane Containing Di(2-ethylhexyl) Phosphoric Acid in Kerosene

Abstract

The permeation rate of Mn(II) from its aqueous sulfate solution through a solid supported liquid membrane containing di(2-ethylhexyl) phosphoric acid (D2EHPA) in kerosene as the mobile carrier has been studied as a function of hydrodynamic conditions, concentrations of Mn²⁺ (0.91–16.38 mol/m³) and H⁺ (pH 2.0–5.0) in the feed solution, carrier concentration (10–800 mol/m³) in the membrane, and temperature. It is observed that as the Mn(II) flux approaches a plateau region, the rate of permeation is predominantly controlled by diffusion through the membrane. On the other hand, at low Mn(II) and high H⁺ ion concentrations, the high diffusivity of the Mn–D2EHPA complex causes the overall permeation rate to be controlled by the interfacial reaction. It is also observed that the rate of Mn(II) permeation is first order with respect to dimer concentration up to 40 mol/m³ and half order above this concentration. Kinetic equations derived on the basis of the proposed mechanism are found to fit the experimental data satisfactorily.     

硫代杯[4]冠-4在硝酸体系中对Sr2+的萃取

乏燃料后处理的高放废液分离过程中,发展新型分离材料实现对锶的高效萃取至关重要。合成了1,2交替构象的硫代杯[4]冠-4(TCACE),利用FT-IR、¹H NMR和MS对目标产物进行了表征。研究不同稀释剂对萃取的影响,优化得出CH₂Cl₂为稀释剂,在硝酸浓度为3 mol·L^-1,有机相中硫代杯[4]冠-4浓度为1×10^-3 mol·L^-1,水相中Sr²⁺浓度为5×10^-4 mol·L^-1,萃取温度为25℃,萃取80 min条件下,平均传质系数为1.36×10^{-5 m}·s^-1,Sr²⁺的分配比为0.69。分析了不同条件对硫代杯[4]冠-4对Sr²⁺的萃取影响,研究了萃取计量方程式,实验结果表明萃合物为{Sr(NO₃)₂}·{TCACE}。研究了TCACE对其他金属离子Mo⁶⁺、Ni²⁺、Ag⁺、Sn⁴⁺等的萃取效果,表明对Sr²⁺具有较好的选择性。     

Hydrazine Radiolysis by Gamma-Ray in the N2H4–Cu+–HNO3 System

Radiolysis of chemical agents occurs during the decontamination of nuclear power plants. The γ-ray irradiation tests of the N₂H₄–Cu⁺–HNO₃ solution, a decontamination agent, were performed to investigate the effect of Cu⁺ ion and HNO₃ on N₂H₄ decomposition using a Co-60 high-dose irradiator. After the irradiation, the residues of N₂H₄ decomposition were analyzed by Ultraviolet-visible (UV) spectroscopy. NH₄⁺ ions generated from N₂H₄ radiolysis were analyzed by ion chromatography. Based on the results, the decomposition mechanism of N₂H₄ in the N₂H₄–Cu⁺–HNO₃ solution under γ-ray irradiation condition was derived. Cu⁺ ions form Cu⁺N₂H₄ complexes with N₂H₄, and then N₂H₄ is decomposed into intermediates. H⁺ ions and H^● radicals generated from the reaction between H⁺ ion and e_aq⁻ increased the N₂H₄ decomposition reaction. NO₃⁻ ions promoted the N₂H₄ decomposition by providing additional reaction paths: (1) the reaction between NO₃⁻ ions and N₂H₄^●+, and (2) the reaction between NO^● radical, which is the radiolysis product of NO₃⁻ ion, and N₂H₅⁺. Finally, the radiolytic decomposition mechanism of N₂H₄ obtained in the N₂H₄–Cu⁺–HNO₃ was schematically suggested.     

Preparation and properties of CdSiO3: Mn2+, Tb3+ phosphor

CdSiO₃: Mn²⁺, Tb³⁺ long-lasting phosphor was prepared by the conventional high temperature solid-state method. Effects of the content of Mn²⁺ and Tb³⁺ on the luminescent properties of phosphor CdSiO₃: Mn²⁺, Tb³⁺ were investigated by means of photoluminescence (PL) spectra, the afterglow intensity decay curves and the thermoluminescence (TL) spectra. It was found that when the Mn²⁺ and Tb³⁺ dopant-concentrations were 0.4 mol% and 0.8 mol% of Cd²⁺ ions in CdSiO₃, respectively, the luminescence of phosphor prepared had better luminescent property and longer afterglow time. Role of Tb³⁺ co-doped into CdSiO₃: Mn²⁺ matrix was discussed in this paper.     

Al2O3-SiO2-ZrO2-TiO2复合溶胶的制备与研究

以硝酸铝、正硅酸乙酯、氧氯化锆、钛酸丁酯为前驱体,水和无水乙醇为溶剂,用溶胶-凝胶法制备适合涂膜的复合溶胶.