铥对铂催化剂反应性能的影响

在铂催化剂中引入铥,它对环巳烷脱氢、甲基环戊烷芳构化和正庚烷的转化有不同的影响。这些催化剂中,以铥含量为0.2%的铂铥催化剂的催化性能最突出。电镜图象表明,铂铥催化剂中铂的分散情况比铂催化剂均匀。     

Solid-state Compounds of 4-chloro-benzylidenepyruvate With Lanthanides. Preparation and thermal studies

Solid-state compounds Ln-4Cl-BP, where Ln represents lighter trivalent lanthanides and 4Cl-BP is 4-chlorobenzylidenepyruvate, were prepared. Thermogravimetry, derivative thermogravimetry (TG and DTG), differential scanning calorimetry (DSC) and other methods of analysis were used to characterize and to study the thermal behaviour of these compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

Concentration dependence of the quantum yield of luminescence of Tm<Superscript>3+</Superscript> ions in gadolinium oxychloride

The concentration dependence of the quantum yield of luminescence of Tm³⁺ ions in an oxychloride matrix has been measured in individual bands of their luminescence excited at different wavelengths. The concentration dependences of the quantum yield of luminescence were calculated with allowance for the effect of the unintentional impurity of rare-earth ions. The cross-relaxation nature of the concentration dependence of the rare-earth ion luminescence is discussed.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 759–765, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Magneto-optical effect of TEB30A liquid crystal doped with thulium oxides

The influences of an external magnetic field on the optical properties of the TEB30A nematic liquid crystal doped with thulium oxides （Gd203, Dy203, Nd203, Y203, and Sm203） are studied. It is shown that a magnetic field applied parallelly to the sample cell surface leads to the rotational orientation of mesogenes. All samples except for the sample doped with Sm203 nanoparticles undergo structural deformations. The behavior of the TEB30A/Sm203 differs from those of the TEB30A liquid crystal doped with other four nanoparticles. The presence of Sm203 nanoparticles in the TEB30A liquid crystal does not cause the structural deformation of the liquid crystal matrix. At the same time, the anchoring type of the liquid crystal molecules on the nanoparticle surface is different. The director n is parallel to the magnetic moment/~ in the TEB30A/Sm203, and inclined to the magnetic moment/~ in the TEB30A/Nd203, and perpendicular to the magnetic moment/~ in each of TEB30A/Gd203, TEB30A/Dy203, and TEB30A/Y203. Besides, the dependence of the structural deformation on the critical magnetic field for the TEB30A is obtained.     

Investigations of the ionic self-diffusion coefficients of the trivalent lanthanide 152Eu(III) in diluted Eu(ClO4)3 solutions in 1,4-dioxane + water mixtures at 298.15 K

The measurement of ionic self-diffusion coefficient D of the trivalent lanthanide ion ¹⁵²Eu(III) in asymmetrical electrolytes of Eu(ClO₄)₃ in hydro-organic water–dioxane mixtures (at a low dielectric constant) at 298.15?K, by the open-end capillary method gives evidence of the progressive association of ion pairs. The study of the different physicochemical properties in all the domains of composition shows the existence of three distinct behaviours. The application of association theory to such an asymmetrical electrolyte (3?:?1) with a polyvalent cation enables us to delimit the validity of the Bjerrum and Fuoss's association theories. Since there is similarity of the coordination chemistry of trivalent lanthanide and actinide ions, this study comes within the framework of previous works of the investigation of structure properties of the f-elements in solution carried out in some previous papers.     

Study of the trivalent elements polyphosphates by thermal analysis

Mechanisms of formation of polyphosphates Me^III(PO₃)₃, where M ^III=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, Fe, Ga, Al and Cr has been simulated by thermal analysis technique. Me^III oxides and ammonium dibasic phosphate (NH₄)₂HPO₄ were used as starting materials. For M ^III=La-Lu, Y and Fe three main stages were observed: 1. elimination of water and ammonia leading to the formation of ammonium tripolyphosphate (NH₄)₅P₃O₁₀; 2. reaction of the latter with Me₂^IIIO₃ and formation of acidic polyphosphates Me^IIIH₂P₃O₁₀ or their isomers Me^III(PO₃)₃·H₂O; 3. final loss of water and formation of Me^III(PO₃)₃. For Me ^III=Sc and Ga the second stage is prolonged and the polyphosphates form at higher temperatures. Aluminum and chromium polyphosphates are unstable. It is suggested that thermal behavior of the compounds is determined by Me^III ionic radii.     

Lanthanide Recognition: Determination of Thulium(III) Ions in Presence of Other Rare Earth Elements by a Thulium(III) Sensor Based on 4-Methyl-1,2-Bis(2-Pyridinecarboxamido)benzene as a Sensing Material

Abstract

In this research, a novel thulium(III) potentiometric membrane sensor based on 4-methyl-1,2-bis(2-pyridinecarboxamido) benzene (MPB) is described. The sensor exhibits a Nernstian response over a concentration range of 1.0 × 10^?7 M to 1.0 × 10^?1 M, with a detection limit of 9.0 × 10^?8 M. The best performance was achieved with a membrane composition of 30% PVC, 60% nitrobenzene (NB), 6% MPB, and 4% sodium tetraphenylborate (NaTPB). It was found that at the pH range of 3.6 to 9.0, the potential response of the sensor was not affected by the pH. Furthermore, the electrode presents satisfactory reproducibility, very fast response time (15 s), and relatively good discriminating ability for Tm(III) ions with respect to many common cations and lanthanide ions. The validation of the proposed electrode was tested by using Coal and Fuel Ash (FFA 1 Fly Ash) as a Certified Reference Material (CRM).     

快速溶剂萃取-离子色谱法同时测定塑料中的三价铬和六价铬

建立了采用快速溶剂萃取-离子色谱同时测定塑料中三价铬和六价铬的方法。三价铬和六价铬分别以吡啶-2,6-二羧酸(PDCA)和1,5-二苯卡巴肼(DPC)作为络合剂在柱前和柱后进行衍生化,分别在紫外和可见波长下采用紫外检测器进行检测,灵敏度高,基体干扰小。本方法对三价铬和六价铬的检出限分别为5.0 μg/L和0.5 μg/L;分别在50～1000 μg/L和5.0～100 μg/L范围内呈现良好的线性关系,线性相关系数分别为0.9994和0.9998;三价铬和六价铬的回收率范围为90.7%～101.1%,相对标准偏差(RSD)为1.7%～4.4%。该方法分析速度快、灵敏度高、重现性好,可用于塑料中三价铬和六价铬的同时测定。     

Challenges to develop single-column MA(III) separation from HLLW using R-BTP type adsorbents

In order to directly separate trivalent minor actinides(MA:Am,Cm) from fission products(FP) containing rare earths(RE) in high level radioactive liquid waste(HLLW),the authors have challenged to develop a simplified MA separation process by extraction chromatography using a single column.Attention has been paid to a new type of nitrogen-donor ligands,R-BTP(2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl) pyridine,R:alkyl group) as an extractant because it shows high extraction selectivity for Am(Ⅲ) over RE(Ⅲ).It is known that the R-BTP ligands show different properties such as adsorbability and stability by having different alkyl groups.Therefore,some novel adsorbents were prepared by impregnating different types of R-BTP ligands(isohexyl-,isoheptyl-and cyheptyl-BTP) and a similar ligand to the R-BTP,ATP(2,6-bis(1-aryl-1H-tetrazol-5-yl)pyridines),into the porous silica/polymer support(SiO2-P particles).This work deals with comparison in adsorption and desorption properties of Am and some FP in HNO 3 solution onto such R-BTP type adsorbents,as well as chemical and radiolytic stability of the adsorbents.Then the possibility of a single-column separation of MA from main FP was pursued by evaluating the results of column experiments using the most promising adsorbent(isohexyl-BTP/SiO2-P) under temperature control.In addition,elution behaviors of U and Pd were also estimated.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.