La0.5R0.5Ba2Cu3O7,Pr0.5R0.5Ba2Cu3O7以及RBa2Cu3o7（R=稀土）的键共价性计

使用复杂晶体化学键理论计算了Ｌａ０．５Ｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｙ,Ｈｏ,Ｅｒ,Ｔｍ,Ｙｂ,Ｌｕ）（Ｌａ－Ｒ１２３）,Ｐｒ０．５Ｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｈｏ,Ｙ,Ｅｒ,Ｔｍ,Ｙｂ,Ｌｕ）（Ｐｒ－Ｒ１２３）以及ＲＢａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｈｏ,Ｙ,Ｅｒ,Ｔｍ）（Ｒ１２３）中Ｃｕ－Ｏ键的键共价性,结果表明Ｐｒ－Ｒ１２３,Ｌａ－Ｒ１２３,以及Ｒ１２３都应具有超导性,而实验结果是Ｌａ０．５Ｐｒ０．５Ｂａ２Ｃｕ０７,Ｒ０．５,Ｐｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ）无超导性,产生这种矛盾的原因尚不明确,需要做进一步的研究。     

交流电弧中共存稀土元素对光谱线强度影响的研究

本工作较系统地研究了在交流电弧中不同量的共存稀土元素镝、钬，饵，铥和镱对某些被测稀土元素光谱线强度的影响。用交流电弧激发溶液干渣样品，其样品是在固定量的被测元素溶液中各自分别加入不同量的共存元素镝、钬、铒、铥和镱，摄谱后测量各被测元素的光谱线强度对共存元素在溶液中各个不同浓度作关系曲线。     

Comparison of Sample Digestion Procedures for the Determination of Arsenic in Bottom Sediment Using Hydride Generation AAS

Certified reference materials (JMS-2 and JMS-1 – Marine sediment, LKSD-1 Lake Sediment, and STSD-1 Stream Sediment) and bottom sediment were analysed for arsenic by hydride generation atomic absorption spectrometry (HG-AAS) after digestion by different methods (microwave digestion, digestion in aluminium block, dry digestion) and different combinations of acids (HNO₃, HCl, HClO₄, H₂SO₄). The study revealed that both wet and dry digestion can be used to digest the reference materials and bottom sediment. Exceptionally satisfactory results were produced by the application of aqua regia, HNO₃ + HCl + HClO₄, and HNO₃ + HCl mixtures. Addition of Mg(NO₃)₂ during dry digestion caused an increase in arsenic recovery in the reference materials and improved the accuracy of arsenic determination in the bottom sediments.     

Mg(OH)_2共沉淀和直接稀释联用ICP-MS法准确测定海水中的多种常量-微量元素

对海水中多种常量/微量元素分别用Mg(OH)_2共沉淀和直接稀释ICP-MS法进行方法比较研究,分别确定了这些元素适宜的准确分析方法,为海水中常量/微量元素的ICP-MS测定提供了实用的检测手段。结果表明,Mg(OH)_2共沉淀法能够实现对V,Cr,Mn,Co,Cd及稀土元素(La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)等19种微量元素的分离富集和准确测定;10倍直接稀释法能够同时准确测定海水中B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn 13种微量元素,但不适合Zn,Ni,Co和Pb,以及稀土元素等在海水中浓度过低元素的测定;两种方法对适宜测定的元素均操作简便快速,具有较高的准确度和精密度。这两种方法联用,就可用约50 mL的海水实现大洋和近海海水中Co,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu(这15个元素采用Mg(OH)_2共沉淀法)及B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn(这13个元素采用10倍直接稀释法)等28种元素的准确测定。     

Syntheses, structure and rare earth metal photoluminescence of new and known isostructural A2Mo4Sb2O18 (A=Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) compounds

Nine new A₂Mo₄Sb₂O₁₈ (A=Ce, Pr, Eu, Tb, Ho, Er, Tm, Yb, Lu) compounds have been synthesized by solid-state reactions. They are isostructural with six reported analogues of yttrium and other lanthanides and the monoclinic unit cell parameters of all fifteen of them vary linearly with the size of A³⁺ ion. Single crystal X-ray structures of eight A₂Mo₄Sb₂O₁₈ (A=Ce, Pr, Eu, Gd, Tb, Ho, Er, Tm) compounds have been determined. Neat A₂Mo₄Sb₂O₁₈ (A=Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm) compounds exhibit characteristic rare earth metal photoluminescence.     

用非等温DSC曲线确定Ln(NCS)3-·4C3H5CH2NH2的热分解反应机理函数及热分解反应动力学参数

本文利用非等温DSC曲线对十二种镧系元素异硫氰酸盐与苄胺形成的配合物Ln(NCS)3·4C6H5CH2NH2(Ln=La、Pr、Nd、Sm、Eu、Ge、Tb、Dy、Ho、Er、Tm、Yb)进行了非等温动力学研究, 并运用积分法和微分法进行了分析, 推断了它们的热分解反应机理函数。     

化学气相传输法分离二元混合重稀土氧化物

稀土气态配合物;化学气相传输法分离二元混合重稀土氧化物     

Digestion of titanium bearing geologic materials involving microwaves

An environmentally friendly and rapid digestion procedure involving 10 mL of acid mixture (HNO3 : HCl : HF = 2:2:1) for 0.1 g of sample in closed vessel microwave digester following heating program : 250W for 10 min., hold time 2 min., 600 W for 17 min, and Ventilation time 10 min was developed. The operating parameters were varied and optimized by factorial design approach using "Steepest Ascent" method. The validity of the recommended digestion procedure were examined by analyzing several well characterized standard reference materials such as diabase (W2), basalt (BIR-1, JB-3, BHVO-1), granite (G2), gabbro (JGb-1), Mn-nodule (Nod-A-1, Nod-P-1), sediment (STSD-4, LKSD-2), limestone (KH-2), soil (SAu-1), ilmenite (IGS-31), rutile (IGS-32), Zircon (IGS-35) and titanium dioxide (SRM-154b) employing both inductively coupled plasma-atomic emission spectrometry (ICP-AES) and well known spectrophotometric method. An excellent agreement between the methods and the certified values of standard reference materials suggest that the digestion procedure can be used for quality control and allied purposes.     

A simple solution to expanding available reference materials for Laser Ablation Inductively Coupled Plasma Mass Spectrometry analysis: Applications to sedimentary materials

Analytical data on sediments are of great importance in understanding and documenting environmental issues. For laboratories interested in in-situ chemical analysis of sediments by LA-ICP-MS, a major issue is the lack of appropriate matrix matched sediment reference materials. Those available were largely designed for partial extractions which generally do not reflect the total elemental compositions. In this work we provide a comprehensive study on chemical compositions of seven currently available sediment reference materials (Lake sediments: LKSD-1, LKSD-2, LKSD-3, Stream sediments: STSD-2, STSD-3, and Marine sediments: PACS-2, MESS-3) as determined by Solution Nebulization Inductively Coupled Plasma Mass Spectrometry (SN-ICP-MS) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after digestion in a mixture of concentrated HNO₃ and HF acids. We also report a simple method to prepare these sediment reference materials and more generally appropriate sediment cores for LA-ICP-MS analysis using epoxy resin. This sample preparation method maintains sediment integrity for high spatial resolution analysis which is required for tracing changes in environmental conditions over short time periods. This work also demonstrates the application of fs-LA-ICP-MS as a tool for direct, rapid and high spatial resolution analysis of sediments.     

Extraction of rare earth elements with 2-[2'-(methoxydiphenylphosphoryl)phenyldiazenyl]-4-<Emphasis Type="Italic">tert</Emphasis>-butylphenol in the presence of 1-butyl-3-methylimidazolium and trioctylmethylammonium picrates

Extraction of micro amounts of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y with solutions of 2-[2'-(methoxydiphenylphosphoryl)phenyldiazenyl]-4-tert-butylphenol in 1,2-dichloroethane in the presence of 1-butyl-3-methylimidazolium and trioctylmethylammonium picrates has been studied. The stoichiometry of extracted complexes has been determined, the effect of HNO₃ concentration in aqueous phase on the efficiency of rare earth elements recovery into organic phase has been considered.     

Ultratrace Elements in Terrestrial Water as Determined by High-Resolution ICP-MS

The double-focusing inductively coupled plasma-mass spectrometry (ICP-MS) was proved to be an extraordinarily sensitive analytical technique. When this ICP-MS was combined with an ultrasonic nebulizer to increase the sample introduction efficiency, the detection power of the system was enhanced even further. The detection limits of most elements attained by this technique were less than 0.1 ppt and reached as low as 1 ppq (1/1000 ppt) for several elements. Analytical results of the standard reference materials, SRM 1643c (trace elements in water) provided by the National Institute of Standards and Technology, and SLRS-2 (riverine water) supplied by the National Research Council of Canada showed that the concentration values obtained by this method were in good agreement with the certified values for all the elements examined. Although the concentration levels of elements in freshwater were in most cases lower than 1 ppm with the exception of several major elements (Na, K, Ca, Mg, Si, S, and CI), it was possible to determine around 40 ultratrace elements (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Cd, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, TI, Pb, Bi, Th, and U) with acceptable speed (less than 30 s per element) and precision (around 5% RSD) by direct sample introduction. No sample pretreatment, such as chemical separation and/or preconcentration, was necessary. It was also possible to directly determine as many as about 40 ultratrace elements in rainwater on as routine basis, although a much longer integration time (about 5 min/element) was applied because the concentration levels of elements in rainwater are far lower than those observed in river and lake water,     

Determination of yttrium and rare-earth elements in rocks by graphite-furnace atomic-absorption spectrometry

With use of synthetic solutions and several international standard reference materials a method has been developed for determining traces of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in rocks by electrothermal atomization in a pyrolytically-coated graphite furnace. Depending on the element, the sensitivity is of the order of 10(-9)-10(-12) g at 2500 degrees . To avoid matrix interferences the lanthanides are separated from the common elements by co-precipitation with calcium and iron as carriers. The data for Canadian reference rock SY-2 (syenite), U.S.G.S. reference rocks W-2 (diabase), DNC-1 (diabase) and BIR-1 (basalt), and South African reference rock NIM-18/69 (carbonatite) obtained by graphite-furnace atomization are compared with the values obtained by flame atomic-absorption. The results are in good agreement with literature values.     

电感耦合等离子体质谱法测定人参中稀土元素含量

通过测定不同年份,同年不同月份采收的人参根、茎和叶中稀土元素(RE′s)的含量,研究稀土元素在人参中分配规律。样品经硝酸和过氧化氢微波消解后,以Re、Rh元素为内标,用电感耦合等离子体质谱法测定~(89)Y、~(139)La、~(140)Ce、~(141)Pr、~(146)Nd、~(147)Sm、~(151)Eu、~(157)Gd、~(159)Tb、~(163)Dy、~(165)Ho、~(166)Er、~(169)Tm、~(172)Yb和~(175)Lu共15种稀土元素在人参根茎叶中的含量。15种稀土元素的检出限在0.24～2.46μg·kg~(-1)之间。稀土元素在人参叶中含量最高,根部居中,茎中最少,在人参根中具有逐年累积的趋势。     

ICP-MS测定高纯氧化铒中稀土杂质的研究

从同位素的选择、基体效应,内标元素的选择及仪器工作等方面对实验参数进行了优化,重点研究了等离子体功率及仪器分辩率的改变对铒基体所形成的氢化物多原子离子干扰的影响。通过提高等离子体功率、改变仪器分辨率及数学方程校正等方法,减小和剔除了ErH对Ho和Tm测定的干扰。实验中选取Cs为内标元素,测定了不同含量的高纯氧化铒样品。分析结果与标准加入法结果进行了比较,之间无显著性差异。     

重水溶液中稀土-吡啶-2,6-二羧酸配合物的第二配位圈^1HNMR顺磁位移

对稀土-吡啶-2,6-二羧酸(DPA)配合物Ln(DPA)3进行了NMR研究并观察到了由溶剂分子形成的第二配位圈的顺磁位移效应.     

Extraction of rare earth elements with functionalized ionic liquid, 1,11-bis(1-methylimidazol-3-yl)-3,6,9-trioxaundecane bis(hexafluorophosphate)

Interfacial distribution of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y between aqueous solutions of their salts and solutions of functionalized ionic liquid, 1,11-bis(1-methylimidazol-3-yl)-3,6,9-trioxaundecane bis(hexafluorophosphate) has been studied. The stoichiometry of extracted complexes has been determined, the effect of HNO₃ concentration in aqueous phase on the efficiency of rare earth elements(III) recovery into organic phase has been considered.     

1,5-双(1'-苯基-3'-甲基-5'-吡唑啉酮-4')-戊二酮-[1,5]和十六烷基吡啶盐的稀土配合物的合成及表征

合成了13种1,5-双(1′-苯基-3′-甲基-5′-吡唑啉酮-4′)-戊二酮-[1,5](BPMPPD)和溴化十六烷基吡啶盐(CPB)的稀土配合物.研究了配合物的红外光谱、紫外可见光谱、差热-热重谱、荧光光谱、核磁共振谱及摩尔电导等性质,发现配合物属离子型缔合物CP⁺[Ln(BPMPPD)₂]^-.Pr、Nd、Ho、Er、Tm配合物发生超灵敏跃迁.配合物的热分解温度具有"四分组"效应,Sm、Eu、Tb、Oy为线性荧光。     

Colloidal nanoparticles of Ln3+-doped LaVO4: energy transfer to visible- and near-infrared-emitting lanthanide ions

Colloidal, organic solvent-soluble Ln3+-doped LaVO4 nanoparticles have been synthesized by a precipitation reaction in the presence of (C18H37O)2PS2- as ligand, that coordinates to the surface of the nanoparticles. The materials are well soluble in chlorinated solvent such as chloroform. Energy transfer of excited vanadate groups has been observed for Ln3+ ions that emit in the visible and the near-infrared (Eu3+, Tm3+, Nd3+, Er3+, Ho3+, Dy3+, Sm3+, Pr3+), thus making it a very generic sensitization mechanism. The LaVO4 nanoparticles have a different crystal structure than bulk LaVO4 ones (xenotime instead of monazite), similar to YVO4 nanoparticles. This xenotime crystal structure results in a more asymmetric crystal field around the Ln3+ ions that is advantageous to their luminescence, for it increases the radiative rate constant, thus reducing quenching processes.     

Synthesis and single-crystal x-ray diffraction examination of a structurally homologous series of tetracoordinate heteroleptic anionic lanthanide complexes: Ln[N[Si(CH3)2CH2CH2Si(CH3)2]]3(mu-Cl)Li(L)3 (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; (L)3 =(THF)3, (Et2O)3, (THF)2(Et2O)

Anhydrous lanthanide(III) chlorides (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) react with 3 equiv of lithium 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentanide, Li[N[Si(CH3)2CH2Ch2Si(CH3)2]], in THF or Et(2)O to afford the monomeric four-coordinate heteroleptic ate complexes Ln[N[Si(CH3)2CH2CH2Si(CH3)2]]3(mu-Cl)Li(THF/Et2O)3 (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Tm (8), Yb (9)), whose solid-state structures were determined by the single-crystal X-ray diffraction technique. All complexes additionally were characterized by melting point determination, elemental analyses, and mass spectrometry.     

Determination of rare earth elements in Indian kimberlite using inductively coupled plasma mass spectrometer (ICP-MS)

A method has been developed for the analysis of rare earth elements (REEs) in kimberlite samples using inductively coupled plasma mass spectrometer (ICP-MS). The samples were dissolved using sodium peroxide fusion and after appropriate dilutions the solutions were analyzed using ICP-MS. The paper presents the concentration of rare-earth elements as determined by ICP-MS in eight kimberlite samples from Central India. The method was validated using certified reference materials STSD-1 and STSD-2 from Canadian Certified Reference Material Project. The method detection limit of various REEs varies from 0.12 to 1.54?mg?kg^?1. The total REE concentrations range from 418 to 726?mg?kg^?1 and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those for kimberlites. In order to compare ICP-MS results, the samples were analyzed using instrumental neutron activation analysis which is a reference method for determination of REEs in geological samples.