Preparation and Characterization of ZrO_2 Nanoparticles Capped by Trioctylphosphine Oxide (TOPO)

Monodisperse ZrO2 nanoparticles capped by trioctylphosphine oxide （TOPO） were prepared in non-aqueous solvent using in-situ synthesis method. Transmission electron microscopy（TEM）, X-ray diffraction（XRD）, X-ray photoelectron spectrometer（XPS）, Fourier transformation infrared spectroscopy （FTIR）, and thermogravimetric analysis（TGA） were adopted to characterize and investigate the size, structure, composition, and the binding manners between organic capping agent TOPO and inorganic ZrO2 nanocores of the as-prepared nanoparticles. In addition, the nanoparticles were also studied to determine their solubility and relative stability. The experimental results show that the prepared nanoparticles contain about 25% organic capping shell TOPO, 75% inorganic ZrO2 nanocores, and can be easily dissolved and be stably disersed in non-polar organic solvents.

Solvent Extraction of Some Lanthanides with Trioctylphosphine Oxide in Molten Paraffin Wax

The extraction behavior of Ln(III) (Ln=Nd, Sm, Tb and Yb) with trioctylphosphine oxide (TOPO) in molten paraffin wax has been studied. The effect of pH, TOPO concentration, medium, stirring time and the amount of sails added on the distribution of lanthanides between two phases were investigated. Two different compositions Ln(H2O)(t-2) (TOPO)(2)(OH)(2)NO3 (Ln=Nd and Sm) and Ln(H2O)(s-1) (TOPO)(2)(OH)(NO3)(2) (Ln=Tb and Yb) were determined by slope analysis method. The equilibrium extraction constant K-ex and pH(1/2) value were calculated and the thermodynamic parameters were obtained from the dependence of K-ex on the temperature.

Syntheses and cofluorescence of complexes of Eu(Ⅲ)/Y(Ⅲ) with terephthalic acid, 2-thenoyltrifluoroacetone and trioctylphosphine oxide

A series of Eu( Ⅲ )/Y( Ⅲ ) complexes of terephthalic acid(TPA) with 2-thenoyltrifluoroacetone(HTTA) and trioctylphosphine oxide(TPPO) were synthesized. Compositions of these complexes are revealed to be Eu2(1-x)Y2x(TPA)(TTA)4- (TPPO)4 or Eu1-xYx(TPA)(TTA)(TPPO)2. Their IR spectra, fluorescent spectra and the thermal and optical stability were studied. The fluorescent excitation spectra of these complexes show more broad excitation bands than those of Eu2(TPA)3(TPPO)4 and Eu(TTA)3(TPPO)2 corresponding to their formations. In addition, both the binuclear complex EuY(TPA)(TTA)4(TPPO)4 and the chain complex Eu0.4Y0.6(TPA)(TTA)(TPPO)2 present higher thermal stability and better optical stability than the mononuclear complex Eu(TTA)3(TPPO)2 does. And their thermal and optical stabilities are preferably interpreted from the binuclear structure together with the chain polynuclear structure of the complexes. The fluorescence enhancement of cofluorescence Y3+ ions to the Eu(Ⅲ) complexes is clear. The optimum content of Y3+ is 0.6 (molar fraction) for the chain complexes Eu1-xYx(TPA)(TTA)- (TPPO)2 and 0.5 for the binuclear complexes Eu2(1-x)Y2x(TPA)(TTA)4(TPPO)4. The formation of polynuclear structure of the complex Eu1-xYx(TPA)(TTA)(TPPO)2 appears to be responsible for the good cofluorescence effect of Y3+ ions.

Synergistic Extraction of Lanthanides by 1-Nitroso-2-Naphthol and Trioctylphosphine Oxide in Paraffin Wax

The paraffin wax was used as a diluent for 1-nitroso-2-naphthol(HA) and trioctylphosphine oxide(TOPO) in the extraction of lanthanides at 70℃. The composition of the extracted species was given as LnA_3(TOPO)_2 by means of the slope analysis. The variation of the synergistic extraction equilibrium constant(K_ sex) was investigated at 60～80℃, and the thermodynamic data were calculated. The dependence of separation factors on temperature was also studied.

激光诱导荧光光谱分析法研究Ⅵ——Eu-DBM-TOPO-Tween-60体系的发光机理和分析应用

本文以Nd;YAG激光器的三倍频输出为激发光源,硅增强靶型光学多道分析仪为检测器,研究了铕-二苯甲酰甲烷-氧化三正辛基膦(Eu-DBM-TOPO)体系的激光诱导发光特性、发光机理和影响荧光发射强度的因素。提出了该体系荧光发射过程的两步能量传递机制,拟定出用DBM-TOPO-Tween-60体系测定痕量铕的激光诱导荧光光谱分析方法。采用标准加入法测定了高纯稀土氧化物和合成水样中的痕量铕,结果令人满意。

1,9-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)壬二酮-[1,9]与TOPO协同萃取钍(Ⅳ)机理的研究

<正> 一、前言 1,9-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)壬二酮-[1,9] (简称H_2A)为新近合成的一种双-β二酮螯合剂,它较HPMBP类试剂多一倍螯合功能团,不但能与钍(Ⅳ)形成较稳定的可萃络合物,而且还能与某些中性萃取剂产生协萃作用。本文以氯仿为溶剂研究了它对钍(Ⅳ)的单独萃取及它与三辛基氧膦(TOPO)协同萃取钍的作用,测得了萃合物的组成为ThA_2·TOPO。求得单独萃取和协同萃取反应的平衡常数分别为β_(20)=1.03×10~8和β_(21)=1.18×10~9。

环己烷激发态超常能量传递速率常数的研究II—TOPO高效的能量接受剂

研究了三辛基氧化膦 (TOPO)—环己烷体系的主要γ辐解产物氢气、二环己烷和环己烯的产额 ,由此计算了环己烷激发态能量传递的速率常数k约为 1.4× 10 13L·mol·s- 1。

铕-速尿-TOPO荧光配合物的研究及速尿的测定

在pH7.8的缓冲溶液中,铕离子、速尿和三辛基氧膦(TOPO)反应生成稳定的三元配合物,该配合物溶解在Triton X-100胶束中。以280 nm光波激发,配合物发射出铕离子的特征荧光。分析了三元配合物的紫外及荧光光谱,对配合物的生成及TOPO和Triton X-100的荧光增敏机理进行了探讨。采用时间分辨荧光法测定配合物的荧光强度,其荧光强度和速尿的浓度在一定范围内呈线性关系,建立了工作曲线的线性回归方程。方法的检出限为6.6×10-8mol/L,测定精度RSD为1.3%(4.00×10-6mol/L,n=11)。用此方法测定尿液中痕量速尿,回收率为93.0%～103%。

Solvent extraction of U(VI) by trioctylphosphine oxide using a room-temperature ionic liquid

The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete(> 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.

三辛基氧化膦修饰电极测定Au(Ⅲ)的研究

用玻碳电极为基体制成了TOPO修饰电极,研究了Au(Ⅲ)在该电极上的阴极溶出伏安特性,并用于痕量Au(Ⅲ)的测定。在1～20 ng/mL的范围内Au(Ⅲ)的浓度与峰高呈线性关系。同时,对电极反应的机理进行了讨论。

稀土离子对钐-铕-噻酚甲酰三氟丙酮-三正辛基膦化氧己烷萃取体系纸上荧光的增敏作用及其应用

在Sm3 + 、Eu3 + 噻酚甲酰三氟丙酮 三正辛基膦化氧己烷萃取体系中Y3 + 、La3 + 、Gd3 + 、Tb3 + 、Dy3 + 、Lu3 + 等离子可增强Sm3 + 、Eu3 + 的纸上荧光 ,其中以Tb3 + 的增敏效应最强 ,灵敏度提高了 6倍。将滤纸适当处理后可使Sm3 + 、Eu3 + 的检出限分别达到 0 .15和 0 .0 0 7ng。本法用于混合稀土氧化物中 0 .xng级的Sm3 + 和0 0 0xng级Eu3 + 的同时测定 。

三正辛胺和三正辛基氧化膦协同萃取硫酸铀酰的动力学研究

应用恒界面池法研究了三正辛胺和三正辛基氧化膦的正庚烷溶液从硫酸介质中协同萃取硫酸铀酰的动力学。提出了协萃反应的机理 ,认为萃取过程是界面区域内的两步连续反应。考察了温度对速率的影响 。

1,9-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)壬二酮-[1,9]与三辛基氧膦对镧(Ⅲ)、镝(Ⅲ)的协同萃取

研究了１，９－双（１－苯基－３－甲基－５－氧代吡唑－４－基）壬二酮－［１，９］（ＢＰＭＰＮＤ，Ｈ２Ａ）与三辛基氧膦（ＴＯＰＯ，Ｂ）的氯仿溶液，从硝酸介质中对Ｌａ（Ⅲ）、Ｄｙ（Ⅲ）的协同萃取，计算了体系的酸性协萃系数ＲＡ和协萃系数Ｒ，用斜率法测得协萃合物的组成为ＬａＡ·ＨＡ·Ｂ和ＤｙＡ·ＨＡ·Ｂ，计算了协萃平衡常数，研究了温度对协萃反应的影响，用萃取法制得了固态协萃合物，并对其组成、ＩＲ及ＴＧ－ＤＴＡ进行了研究．

三辛基氧膦化学修饰钨电极电富集-石墨炉原子吸收法测定镓的研究

用三辛基氧膦(TOPO)化学修饰钨电极预富集-石墨炉原子吸收法测定镓。在5.0×10^(-2)mol/L HAc 底液中,Ga(Ⅲ)被络合富集于 TOPO-钨修饰电极表面,测定线性范围7.17×10^(-10)～1.43×10^(-7)mol/L,检测下限1.43×10^(-10)mol/L,相对标准偏差5.5%。用于人发和水样分析,结果满意。

环己烷激发态超常能量传递速率常数的研究

用终产物分析的方法研究了环己烷 (CH) -三辛基氧化膦 (TOPO)体系在γ辐解过程中环己烷激发态能量传递的速率常数。结果表明 ,此过程中激发能传递的速率常数为 1.9× 10 10 L·mol·s- 1。

Tb^(3+)与苯二甲酸的荧光反应及其分析应用

研究了Tb(3+)离子与三种苯二甲酸发生的荧光反应。研究发现，引入三辛基氧化膦（TOPO）后，Tb(3+)～（间－）苯二甲酸体系和Tb(3+)～（对－）苯二甲酸体系中Tb(3+)离子的545nm特征荧光增强了数十倍，而Tb(3+)～（邻－）苯二甲酸体系的荧光没有明显增强。简单讨论了荧光增敏的机理，并利用Tb(3+)～（间－）苯二甲酸～TOPO和Tb(3+)～（对－）苯二甲酸～TOPO两个体系，采用标准加入法测定了稀土样品中的微量Tb(3+)，结果令人满意。

1-苯基-3-甲基-4-(α-呋喃甲酰基)-5-吡唑酮与氧化三正辛基膦对镧(Ⅲ)、铕(Ⅲ)的协同萃取

研究了１－苯基－３－甲基－４－（α－呋喃甲酰基）－５－吡唑酮（ＨＰＭＦＰ，简作ＨＡ）与氧化三正辛 基膦（ＴＯＰＯ）的氯仿溶液对Ｌａ（Ⅲ）、Ｅｕ（Ⅲ）的协同萃取行为，计算了体系的协萃系数Ｒ和酸性协萃系数ＲＡ．用 斜率法测得协萃合物的组成为：ＬａＡ３·ＴＯＰＯ和ＥｕＡ３·ＴＯＰＯ，计算了相应的协萃平衡常数，用萃取法制得了固 态协萃合物，并对其组成，ＩＲ进行了研究．

Solvent extraction and stripping of lithium ion from aqueous solution and its application to seawater

For the development of lithium ion recovery process from seawater, a series of experimental researches were performed. Solvent extraction of lithium ion from aqueous solution using kerosene as solvent was proposed. Lithium ion is effectively extracted by thenoyltrifluoroace- tone-trioctylphosphine oxide （TTA-TOPO） in kerosene within 80 min. Extraction efficiency is severely influenced by stoichiometric parameters. Among the stoichiometric parameters, volume ratio of aqueous （A） to extraction （E） solution is the most influential parameter. After extrac- tion, lithium ion could be easily stripped from the extraction solution by acidic solutions. Stripping efficiency decreases with pH of acidic solutions, and the kind of acid does not affect the stripping efficiency. Extraction efficiency main- tains at more than 93 % even when the extraction solution is recycled three times. 65 % of lithium ion can be extracted from seawater by this solvent extraction process when magnesium ion is precipitated by NHaOH prior to solvent extraction process. Other metallic ions in seawater decrease the extraction efficiency of lithium ion.

新型镝离子掺杂的三元荧光体系的构建及应用

在无水乙醇体系中构建了镝-磺基水杨酸-三正辛基氧化磷的三元配合物荧光体系,使用荧光分光光度计在激发波长305 nm,发射波长574 nm的条件下对体系进行荧光强度的检测,同时进行条件的优化,对试剂的配比和加入顺序以及反应时间进行筛选。得出了三元配合物体系中镝∶磺基水杨酸∶三正辛基氧化磷的最佳配比为2∶1∶7,最优检测时间为30 min,同时得出了最优的试剂加入顺序依次为Dy^(3+), SSA,TOPO。通过加入镧来构建新的荧光强度更为良好的发光体系。并进行了常见离子的干扰实验以及加入体系中的镧离子的条件进行了优化。在已构建的体系中加入盐酸四环素,发现体系荧光强度明显降低,并利用四环素这一荧光淬灭效应对药品中四环素含量进行检测。

三辛基氧化膦萃取硫氰酸与硫氰酸镍（Ⅱ）的平衡

研究了三辛基氧化膦（ＴＯＰＯ）的正辛烷溶液萃取硫氰酸的分配平衡和三辛基氧化膦从硫氰酸介质中对镍（Ⅱ）的萃取平衡．结果表明：ＴＯＰＯ与硫氰酸形成ＴＯＰＯ·ＨＳＣＮ萃合物，萃取常数ｌｇβ＝２．４２；萃取镍（Ⅱ）时形成Ｎｉ（ＳＣＮ）２：·２ＴＯＰＯ和Ｎｉ（ＳＣＮ）２·４ＴＯＰＯ两种萃合物，萃取平衡常数分别为ｌｇＫ２＝４．７３和ｌｇＫ２＝７．１２，ＴＯＰＯ在硫氰酸介质中对Ｎｉ（Ⅱ）有较强的萃取能力．